Cross-linked alpha-glucan derivatives

Abstract

This document discloses compositions comprising at least one cross-linked α-glucan derivative. Such a derivative can be generated by contacting ethylene glycol diglycidyl ether with the α-glucan derivative, thereby cross-linking the α-glucan derivative. Methods for producing the cross-linked α-glucan derivative are further disclosed, as well as its use in various applications and products.

Description

[0001] This application claims the benefit of U.S. Provisional Applications Nos. 63 / 587,005 (filed September 29, 2023) and 63 / 598,263 (filed November 13, 2023), each of which is incorporated herein by reference in its entirety. Technical Field

[0002] This disclosure pertains to the field of polysaccharide derivatives. For example, this disclosure relates to cross-linked derivatized α-glucan and the use of such materials in various applications. Background Technology

[0003] Multifunctional detergent compositions that provide cleaning, water softening, and rinsing benefits have been produced. For example, detergent formulations for automatic dishwashing machines and other appliances are designed to function under hard water conditions. Hard water cations such as Ca... 2+ and Mg 2+ Hard water cations can crystallize with carbonates and form insoluble salts, which deposit (also known as scale) on surfaces such as tableware or internal parts of appliances (e.g., pipes, sprayers). Hard water cations also play a role in soap scum formation. Bio-based ingredients such as sodium citrate, trisodium methylglycine diacetate (MGDA), and L-glutamic acid-N,N-diacetic acid (GLDA) can help prevent these unwanted deposits by chelating hard water cations and keeping them in solution. However, these ingredients are insufficient to prevent hard water surface deposits after repeated washing steps. The inhibition of hard water deposit formation has been more successfully addressed by incorporating fully synthetic polymers (typically 100% petroleum-based) into detergent compositions, such as polyacrylates (e.g., sulfonated polyacrylates) or bisphosphonates (e.g., 1-hydroxyethylidene-1,1-bisphosphonic acid [HEDP]). These ingredients are non-renewable and not readily biodegradable; due to such environmental concerns, these and related ingredients are increasingly subject to government regulation.

[0004] Several detergent products containing one or more environmentally friendly components have been developed, but these products typically fail to provide consumers with acceptable cleaning performance (e.g., the aforementioned bio-based agents). Therefore, there remains a need for cleaning composition ingredients that are renewable and / or biodegradable and provide cleaning performance equal to or better than that of products containing synthetic components. For example, this document discloses polysaccharide derivatives and detergent compositions containing one or more of these polysaccharide derivatives to address this need. Summary of the Invention

[0005] In one embodiment, this disclosure relates to a composition / product comprising a cross-linked α-glucan derivative, wherein the cross-linked α-glucan derivative is generated by contacting ethylene glycol diglycidyl ether (EGDE) with a first α-glucan derivative, thereby cross-linking the first α-glucan derivative, wherein the ratio of EGDE to the first α-glucan derivative is about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative.

[0006] In another embodiment, this disclosure relates to a method of washing or treating a hard surface, the method comprising: (a) contacting the hard surface with a washing / treatment composition comprising a crosslinked α-glucan derivative as disclosed herein, and (b) removing all or a portion of the washing / treatment composition from the hard surface; thereby washing or treating the hard surface, wherein the washed / treated hard surface has reduced film formation, spots, turbidity, or other deposits, optionally wherein the hard surface is a hard surface of glass, plastic, ceramic, porcelain, metal, or stone.

[0007] In another embodiment, this disclosure relates to a method for producing a cross-linked α-glucan derivative as disclosed herein, the method comprising: (a) contacting EGDE with a first α-glucan derivative (the first α-glucan derivative has typically been derivatized herein, such as by etherification, sulfonation, or oxidation) to cross-link the first α-glucan derivative, wherein the ratio of EGDE to the first α-glucan derivative is about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative; and (b) optionally separating the cross-linked α-glucan derivative produced in step (a). Attached Figure Description

[0008] Figure 1 The effect of cross-linked α-1,3-glucan anionic derivatives on scale deposition in a simulated automatic dishwashing study. See Example 1.

[0009] Figure 2 The effect of cross-linked α-1,3-glucan anionic derivatives on scale deposition was investigated in a simulated automatic dishwashing study. The effect of increasing the level of cross-linking on the same CMG materials (DoS 0.54–0.56) was examined. See Example 1.

[0010] Figure 3 The effect of carboxymethyl cellulose (CMC) (uncrosslinked) on scale deposition was investigated in a simulated automatic dishwashing study. The effect of increasing molecular weight was examined. See Example 1.

[0011] Figure 4The effect of using uncrosslinked α-1,3-glucan anionic derivatives on scale deposition in a simulated automatic dishwashing study. The effect of increasing the anionic charge level of the derivatives was examined. See Example 1.

[0012] Figure 5 The effect of α-1,3-glucan anionic derivatives crosslinked with alternative crosslinking agents (other than EGDE) on scale deposition in a simulated automatic dishwashing study. See Example 1.

[0013] Figure 6 The effect of uncrosslinked α-1,2-branched α-1,6-glucan derivatives on scale deposition in a simulated automatic dishwashing study. See Example 1.

[0014] Figure 7 The effect of carboxymethyl benzyl α-1,3-glucan ether derivatives (uncrosslinked) on scale deposition in a simulated automatic dishwashing study. See Example 1.

[0015] Figure 8 The effect of using sulfonated α-1,3-glucan derivatives (uncrosslinked) on scale deposition in a simulated automatic dishwashing study. See Example 1.

[0016] Figure 9 Results of transmittance testing on demineralized (demi) water. Y-axis (OD600), Z-axis (time, in seconds). See Example 1.

[0017] Figure 10 Results of transmittance tests on liquids containing ACUSOL 588 (long). Y-axis (OD600), x-axis (normalized polymer content), z-axis (time, in seconds). See Example 1.

[0018] Figure 11 Results of transmittance tests on liquids containing ACUSOL 588. Y-axis (OD600), x-axis (normalized polymer content), z-axis (time, in seconds). See Example 1.

[0019] Figure 12 Results of transmittance testing on liquids containing OPE 98 compound (EGDE-crosslinked carboxymethylated α-1,3-glucan product). Y-axis (OD600), x-axis (normalized polymer amount), z-axis (time, in seconds). See Example 1.

[0020] Figure 13Results of transmittance testing on liquids containing compound I (carboxymethylated α-1,2-branched α-1,6-glucan product). Y-axis (OD600), x-axis (normalized polymer amount), z-axis (time, in seconds). See Example 1.

[0021] Figure 14 Results of an automatic dishwashing test on a MEPAL tube. See Example 1.

[0022] Figure 15 Results of an automatic dishwashing test on melamine trays. See Example 1.

[0023] Figure 16 Results of an automatic dishwashing test on drinking glasses. See Example 1.

[0024] Figure 17 Effect of polymer concentration on the relative viscosity of crosslinked CMG (DoS 0.46) compared to synthetic carbomer (ULTREZ 30) and natural gum (xanthan gum). See Example 2.

[0025] Figure 18 The effect of crosslinked CMG (DoS 0.46) at a concentration of 1% w / v on relative viscosity stability compared to synthetic carbomer (Ultrez 30). See Example 2.

[0026] Figures 19A-19D : Rheological curves, which show the relationship with Carbomer ( Figure 19A ULTREZ 30; Figure 19B Compared to ULTREZ 10, the viscosity of crosslinked CMG at concentrations ranging from 0.25% to 2% w / v varies with shear rate. Figure 19C DoS 0.46; Figure 19D (DoS 0.48). See Example 2 for reference.

[0027] Figure 20 and 21 Rheological profiles of aqueous dispersions of cross-linked CMG (DoS 0.4-0.5) or carbomer (highlighted with an asterisk in each figure) Figure 20 ) and yield stress range ( Figure 21 See Example 2 for reference.

[0028] Figure 22 The yield stress of 0.5% w / v crosslinked CMG in an aqueous dispersion changes with increasing carboxymethyl DoS. Data were collected from oscillatory sweep rheological curves at a normalized pH of 6.5. See Example 2.

[0029] Figure 23 Optical microscopy imaging (20X magnification) of a polymer-stabilized O / W emulsion (0.5% polymer content) diluted tenfold in water, showing differences in droplet size and distribution. See Example 2.

[0030] Figures 24A-24B Compared to 0.5% w / v carbomer (ULTREZ 30) (highlighted with an asterisk in each figure), it contains different DoS and concentrations (0.5% w / v, Figure 24A 0.25% w / v Figure 24B The rheological behavior of crosslinked CMG polymer-stabilized O / W emulsions. See Example 2. Detailed Implementation

[0031] All cited patent and non-patent literature publications are incorporated into this paper in their full text by reference.

[0032] Unless otherwise disclosed, the term "a / an" as used herein is intended to cover one / an or more / multiple (i.e., at least one / an) of the features referenced.

[0033] If they exist, all ranges are inclusive and composable unless otherwise stated. For example, when listing the range “1 to 5” (i.e., 1-5), the listed range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1-2”, “1-2 and 4-5”, “1-3 and 5”, etc. Unless otherwise expressly indicated, the numerical values ​​of the various ranges in this disclosure are stated as approximate values, as the minimum and maximum values ​​within the stated ranges are preceded by the word “approximately”. In this way, typically, slightly higher and lower variables than the stated ranges can achieve substantially the same results as values ​​within these ranges. Moreover, these ranges are intended to be disclosed as continuous ranges including every value between the minimum and maximum values.

[0034] Each maximum numerical limit given throughout this specification is intended to include each lower numerical limit, as such lower numerical limit is explicitly stated herein. Each minimum numerical limit given throughout this specification will include each higher numerical limit, as such higher numerical limit is explicitly stated herein. Each numerical range given throughout this specification will include each narrower numerical range falling within such a wider numerical range, as such narrower numerical range is explicitly stated in its entirety herein.

[0035] It should be understood that, for clarity, certain features of this disclosure described above and below in the context of aspects / exercises may also be provided in combination in a single element. Conversely, for brevity, various features of this disclosure described in the context of a single aspect / exercise may also be provided individually or in any sub-combination.

[0036] The term "polysaccharide" (or "glycan") refers to a polymeric carbohydrate molecule composed of long chains of monosaccharide units linked together by glycosidic bonds, which, upon hydrolysis, yields a polysaccharide and / or oligosaccharide component. Polysaccharides as used herein can be linear or branched, and / or can be homopolysaccharides (composed of only one type of component monosaccharide) or heteropolysaccharides (composed of two or more different component monosaccharides). Examples of polysaccharides described herein include α-glucan (polydextrose).

[0037] As used herein, "dextran" refers to a class of polysaccharides, which are polymers of glucose (polydextrans). Dextran may comprise, for example, about 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, or 100% by weight of glucose monomer units. Examples of dextran in this document are α-glucan and β-glucan.

[0038] The terms “α-glucan”, “α-glucan polymer”, etc., are used interchangeably herein. α-glucan is a polymer comprising glucose monomer units linked together by α-glycosidic bonds. Typically, the glycosidic bonds of α-glucans herein are about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% α-glycosidic bonds. Examples of α-glucan polymers herein include α-1,3-glucan, α-1,4-glucan, and α-1,6-glucan.

[0039] Unless otherwise stated, the term "carbohydrate" and other similar terms herein refer to monosaccharides and / or disaccharides / oligosaccharides. "Disaccharide" herein refers to a carbohydrate having two monosaccharides linked by a glycosidic bond. "Oligosaccharide" herein can refer to a carbohydrate having, for example, 3 to 15 monosaccharides linked by a glycosidic bond. Oligosaccharides may also be referred to as "oligomers." Monosaccharides contained within a disaccharide / oligosaccharide (e.g., glucose and / or fructose) may be referred to as "monomer units," "monosaccharide units," or other similar terms.

[0040] The terms “α-1,3-glucan,” “poly-α-1,3-glucan,” and “α-1,3-glucan polymer” are used interchangeably herein. α-1,3-glucan is an α-glucan comprising glucose monomer units linked together by glycosidic bonds, wherein at least about 50% of the glycosidic bonds are α-1,3. In some aspects, α-1,3-glucan contains about, or at least about 90%, 95%, or 100% α-1,3 glycosidic bonds. Most or all of the other bonds (if present) in α-1,3-glucan herein are typically α-1,6, although some bonds may also be α-1,2 and / or α-1,4. α-1,3-glucan herein is typically water-insoluble.

[0041] The terms “α-1,6-glucan,” “poly-α-1,6-glucan,” “α-1,6-glucan polymer,” “dextran,” etc., used herein refer to water-soluble α-glucans comprising glucose monomer units linked together by glycosidic bonds, wherein at least about 40% of the glycosidic bonds are α-1,6. In some aspects, α-1,6-glucan comprises about, or at least about 90%, 95%, or 100% α-1,6 glycosidic bonds. Other bonds that may optionally be present in α-1,6-glucan include α-1,2, α-1,3, and / or α-1,4 bonds.

[0042] As used herein, the “α-1,2 branch” (and similar terms) typically comprises glucose α-1,2-linked to the dextran backbone; therefore, the α-1,2 branch in this paper may also be referred to as the α-1,2,6 bond. The α-1,2 branch in this paper typically has a glucose group (which may optionally be referred to as a side-chain glucose).

[0043] As used herein, the “α-1,3 branch” (and similar terms) typically comprises glucose α-1,3-linked to the dextran backbone; therefore, the α-1,3 branch in this document may also be referred to as the α-1,3,6 bond. The α-1,3 branch in this document typically has a glucose group (which may optionally be referred to as a side-chain glucose).

[0044] The branching percentage in α-glucan described herein refers to the percentage of all bonds in the α-glucan representing the branching point. For example, the percentage of α-1,2 branches in the α-glucan described herein refers to the percentage of all bonds in the glucan representing the α-1,2 branching point. Unless otherwise stated, the bond percentages disclosed herein are based on the total number of bonds in the α-glucan, or on the portion of the α-glucan specifically covered by the disclosure.

[0045] The terms “bond,” “glycosidic linkage,” and “glycosidic bond” refer to the covalent bonds that link sugar monomers within a sugar compound (oligosaccharide and / or polysaccharide). Examples of glycosidic bonds include 1,6-α-D-glycosidic bonds (also referred to herein as “α-1,6” bonds), 1,3-α-D-glycosidic bonds (also referred to herein as “α-1,3” bonds), 1,4-α-D-glycosidic bonds (also referred to herein as “α-1,4” bonds), and 1,2-α-D-glycosidic bonds (also referred to herein as “α-1,2” bonds).

[0046] The glycosidic bond profile of polysaccharides or their derivatives can be determined using any method known in the art. For example, nuclear magnetic resonance (NMR) spectroscopy can be used (e.g., 13 C NMR and / or 1 Bond spectra can be determined using methods such as 1H NMR. These and other methods that can be used are disclosed, for example, Food Carbohydrates: Chemistry, Physical Properties, and Applications [ Food carbohydrates: chemical and physical properties and applications [This is from SW Cui, ed., Chapter 3, Structural Analysis of Polysaccharides, Taylor & Francis Group LLC, Pocaraton, Florida, 2005, which is incorporated herein by reference.]

[0047] The “molecular weight” of polysaccharides or polysaccharide derivatives used herein may be expressed as weight-average molecular weight (Mw) or number-average molecular weight (Mn), in units of Daltons (Da) or grams per mole. Alternatively, molecular weight may be expressed as DPw (weight-average degree of polymerization) or DPn (number-average degree of polymerization). The molecular weight of smaller polysaccharide polymers (such as oligosaccharides) may optionally be provided as “DP” (degree of polymerization), which refers only to the number of monomers contained within the polysaccharide; “DP” may also characterize the molecular weight of the polymer based on a single molecule. Various methods for calculating these different molecular weight measurements are known in the art, such as high-performance liquid chromatography (HPLC), size exclusion chromatography (SEC), or gel permeation chromatography (GPC).

[0048] As used in this article, Mw = ΣNiMi 2Mw is calculated as / ΣNiMi; where Mi is the molecular weight of a single chain i and Ni is the number of chains having that molecular weight. Besides SEC, the Mw of a polymer can be determined by other techniques such as static light scattering, mass spectrometry, MALDI-TOF (matrix-assisted laser desorption / ionization time-of-flight), small-angle X-ray or neutron scattering, or ultracentrifugation. As used herein, Mn can be calculated as Mn = ΣNiMi / ΣNi, where Mi is the molecular weight of chain i and Ni is the number of chains having that molecular weight. Besides SEC, the Mn of a polymer can be determined by various colligative methods such as vapor pressure permeation, by spectroscopic methods such as proton NMR, proton FTIR, or UV-Vis end-group determination. As used herein, DPw and DPn can be calculated from Mw and Mn respectively by dividing them by the molar mass M1 of a monomer unit. In the case of unsubstituted dextran polymers, M1 = 162. In the case of substituted (derived) dextran polymers, M1 = 162 + M f x DoS, where M f It is the molar mass of the substituent group, and DoS is the degree of substitution (average number of substituent groups per glucose unit of the dextran polymer).

[0049] In this article, "ethylene glycol diglycidyl ether" (EGDE), "1,2-bis(2,3-epoxypropoxy)ethane" and similar terms refer to the compound with CAS number 2224-15-9, which has the following structure:

[0050] EGDE can be used in this paper to crosslink α-glucan derivatives.

[0051] The terms “crosslinked,” “crosslinked,” etc., used herein to refer to crosslinked α-glucan derivative compounds refer to one or more covalent bonds (chemical bonds) that link the polymer. Crosslinking with multiple bonds typically involves one or more atoms that are part of a crosslinking agent (e.g., EGDE) used to form the crosslink. The terms “crosslinking reaction” and similar terms (e.g., “crosslinked composition,” “crosslinking formulation”) herein typically refer to a reaction involving at least a solvent, a crosslinking agent (e.g., EGDE), and an α-glucan derivative. In some aspects, the crosslinking reaction involves an aqueous solvent, such as water.

[0052] As used herein, “crosslinked α-glucan derivative,” “EGDE-crosslinked α-glucan derivative,” and similar terms typically refer to α-glucan derivatives (e.g., α-glucans derivatized with ether-linked organic groups, sulfonate groups, and / or groups derived from oxidation) that have been contacted with the crosslinked compound EGDE, typically under suitable conditions for reacting EGDE with and crosslinking the α-glucan derivative. For ease of reference herein, the α-glucan derivative that acts as a substrate in the EGDE treatment / contact reaction may be referred to as the “first α-glucan derivative”; typically, any α-glucan derivative mentioned herein may refer to the first α-glucan derivative.

[0053] The organic groups used herein are typically uncharged (nonionic) or charged (e.g., anionic); generally, this charge can be as present in the organic group when it is in the aqueous composition herein, taking into account the pH of the aqueous composition (in some respects, the pH can be 4-10 or 5-9, or any pH as disclosed herein). If present in the first α-glucan derivative herein, the organic group containing a carboxylic acid or carboxylate group can itself be a carboxylic acid or carboxylate group (e.g., the C6 of glucose can be -COOH or -COO). - ), or it may be (i) an organic group connected to α-glucan ether-, ester-, carbamate-, sulfonyl-, or carbonate- and (ii) an organic group containing a carboxylic acid or carboxylate group (e.g., carboxylalkyl, such as carboxymethyl).

[0054] As used herein, the term "degree of substitution" (DoS, or DS) refers to the average number of hydroxyl groups in each monomer unit of an α-glucan derivative that are substituted by one or more organic groups (e.g., via ethers, esters, or other bonds, as described herein), sulfonate groups, and / or groups resulting from oxidation. The DoS of an α-glucan derivative herein may be stated with reference to the DoS of a specific substituent or the overall DoS, which is the sum of the DoS values ​​for different substituent types. Unless otherwise disclosed, when DoS is not stated with reference to a specific substituent type, it means the overall DoS.

[0055] The term "ether" (e.g., α-glucan ether derivative) as used herein may be disclosed, for example, in U.S. Patent Application Publication Nos. 2014 / 179913, 2016 / 0304629, 2015 / 0239995, 2018 / 0230241, 2018 / 0237816, 2020 / 0002646, 2023 / 0212325, 2023 / 0235097, or 2024 / 0301325 or International Patent Application Publication No. WO 2021 / 257786 (each of which is incorporated herein by reference). The terms "α-glucan ether derivative," "α-glucan ether compound," "α-glucan ether," etc., are used interchangeably herein. The α-glucan ether derivatives described herein are α-glucans that have been etherified by one or more organic groups (e.g., uncharged, anionic) to give the derivatives a DoS of up to about 3.0 contributed by one or more organic groups. The α-glucan ether derivatives described herein contain the substructure -C G -OC- is referred to as "ether", where "-C" is the ether. G "-" indicates the monomer unit (carbon atom of the α-glucan ether derivative, wherein such carbon atom is bonded to the hydroxyl group [-OH] in the α-glucan precursor of the ether), and wherein "-C-" is the carbon atom of the organic group.

[0056] The “sulfonate” group used herein may be disclosed, for example, in International Patent Application Publication No. WO 2019 / 246228 or U.S. Patent Application Publication No. 2021 / 0253977 (each incorporated herein by reference).

[0057] As used herein, “oxidized α-glucan derivative” (and similar terms) refers to compounds produced by the oxidation of α-glucan derivatives such as those disclosed herein. This oxidation can occur, for example, at one or more hydroxyl groups of the monomeric unit of the α-glucan derivative, and / or at one or more hydroxyl groups of the substituted organic groups of the α-glucan derivative. Oxidation can independently convert the hydroxyl groups to aldehydes, ketones, or carboxyl groups. For example, the α-glucan derivatives herein can be oxidized by contacting them with one or more oxidizing / oxidizing agents under aqueous conditions. In some aspects, oxidized α-glucan derivatives are α-glucan derivatives that have already been produced by oxidizing an α-glucan derivative (e.g., the α-glucan ether herein), essentially and therefore further derivatizing the α-glucan. In some aspects, the α-glucan derivative can be oxidized (typically) before or after it has been crosslinked herein and optionally further derivatized with organic groups. The oxidation reactions described herein may be carried out, for example, as disclosed in the following examples or as disclosed in International Patent Application Publication Nos. WO 2022 / 178073 or WO 2022 / 178075 or U.S. Patent Application Publication Nos. 2024 / 0199766 or 2024 / 0150497 (each of which is incorporated herein by reference).

[0058] As used herein, the terms “aqueous liquid,” “aqueous fluid,” “aqueous conditions,” “aqueous reaction conditions,” “aqueous environment,” and “aqueous system” can refer to water or an aqueous solution. An “aqueous solution” as used herein may contain one or more dissolved salts, wherein in some respects the maximum total salt concentration may be about 3.5 wt%. While aqueous liquids as used herein typically contain water as the sole solvent, aqueous liquids may optionally contain one or more other solvents miscible with water (e.g., polar organic solvents). Thus, an aqueous solution may contain a solvent having at least about 10 wt% water.

[0059] For example, the term "aqueous composition" as used herein refers to a liquid component comprising about, or at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 99, or 100 wt% water. Examples of aqueous compositions include, for example, mixtures, solutions, dispersions (e.g., suspensions, colloidal dispersions), and emulsions.

[0060] In some aspects, the compositions of this disclosure can provide stability to dispersions or emulsions. The term "stability" (or "stable" quality) of a dispersion or emulsion herein refers to, for example, the ability of dispersed particles of the dispersion or liquid droplets (emulsion) dispersed in another liquid to remain dispersed (e.g., about 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or 100 wt% of the particles of the dispersion or the liquid droplets of the emulsion being dispersed) for a period of about 2, 4, 6, 9, 12, 18, 24, 30, or 36 months after the initial preparation of the dispersion or emulsion. In some aspects, a stable dispersion or emulsion can resist complete deposition, flocculation, and / or aggregation of the dispersed / emulsifying material.

[0061] α-glucan derivatives described herein as “soluble,” “water-soluble,” or “water-insoluble” (and similar terms) are dissolved (or readily soluble) in water or other aqueous conditions, optionally characterized by a pH of 4-9 (e.g., pH 6-8) and / or a temperature of about 1°C to 130°C (e.g., 20°C-25°C). In some aspects, water-soluble α-glucan derivatives are soluble in water at pH 7 at 25°C at 1% by weight or higher. In contrast, α-glucan derivatives described herein as “insoluble,” “water-insoluble,” or “water-insoluble” (and similar terms) are insoluble under these conditions. In some aspects, less than 1.0 g (e.g., an undetectable amount) of water-insoluble α-glucan derivatives dissolves in 1000 mL of such aqueous conditions (e.g., water at 23°C).

[0062] The term "home care products" and similar terms typically refer to products, goods, and services relating to the handling, cleaning, care, and / or conditioning of the home and its interior. This includes, for example, chemicals, compositions, products, or combinations thereof intended for such care.

[0063] The terms “fabric,” “textile,” “cloth,” etc., are used interchangeably herein to refer to woven materials having a network of natural and / or man-made fibers. Such fibers may be in the form of, for example, silk threads or yarns.

[0064] "Fabric care composition" and similar terms refer to any composition suitable for treating fabrics in a certain way. Examples of such compositions include laundry detergents and fabric softeners, which are examples of fabric care compositions.

[0065] Typically, a “detergent composition” as used herein contains at least a surfactant (detergent compound) and / or a builder. A “surfactant” as used herein refers to a substance that tends to reduce the surface tension of a liquid in which a substance is dissolved. Surfactants can be used as, for example, detergents, wetting agents, emulsifiers, foaming agents, and / or dispersants.

[0066] The terms “heavy-duty detergent,” “general-purpose detergent,” etc., are used interchangeably herein to refer to detergents suitable for regular washing of white and / or colored textiles at any temperature. The terms “light-duty detergent,” “delicate fabric detergent,” etc., are used interchangeably herein to refer to detergents suitable for caring for delicate fabrics such as viscose, wool, silk, microfiber, or other fabrics requiring special care. “Special care” may include conditions such as using excess water, low agitation, and / or no bleaching.

[0067] The terms "builder," "builder agent," etc., used herein refer to compositions, for example, capable of complexing with hard water cations such as calcium and magnesium cations. It is believed that the formation of such complexes prevents one or more cations from forming water-insoluble salts and / or other complexes. In the context of detergent compositions used for cleaning or maintenance applications, builders added thereto typically enhance or maintain the cleaning efficiency of surfactants present in the detergent composition. The terms "builder capacity," "builder activity," etc., are used interchangeably herein and refer to the ability of an aqueous composition to exhibit characteristics conferred by one or more builders present in the aqueous composition. In some aspects herein, cross-linked α-glucan derivatives can be used as builders.

[0068] The terms “flocculator,” “flocculating agent,” “flocculating composition,” “agglomerator,” etc., used in this document refer to substances that can promote the agglomeration / clustering / agglomeration of insoluble particles suspended in water or other aqueous liquids, thereby making these particles easier to remove by sedimentation / deposition, filtration, granulation, and / or other suitable means. Particle flocculation typically occurs during the removal / separation of particles from aqueous suspensions. In some aspects of this document, cross-linked α-glucan derivatives can be used as flocculants.

[0069] The term "personal care products" and similar terms typically refer to products, goods, and services relating to the treatment, cleaning, washing, care, or conditioning of a person. This includes, for example, chemicals, compositions, products, or combinations thereof used in such care.

[0070] The terms “ingestible product”, “ingestible composition”, etc., refer to any substance that can be taken orally (i.e., through the mouth), alone or in combination with another substance. “Inedible product” (“inedible composition”) refers to any composition that can be ingested orally for purposes other than food or beverage consumption. Examples of inedible products in this article include supplements, health supplements, functional food products, pharmaceutical products, oral care products (e.g., dental floss, mouthwash), and cosmetics such as sweetened lip balms.

[0071] The term "medical product" and similar terms typically refer to products, goods and services related to the diagnosis, treatment and / or care of patients.

[0072] In this article, the terms “pharmaceutical product,” “medicine,” “medication,” “drug,” or similar terms refer to compositions used to treat a disease or injury and which may be administered orally or parenterally.

[0073] The term "industrial product" and similar terms typically refer to products, goods and services used in industrial and / or institutional settings, but not typically used by individual consumers.

[0074] As used herein, the term "viscosity" refers to a measure of the degree to which a fluid (aqueous or non-aqueous) resists forces that tend to cause it to flow. Various units of viscosity that may be used herein include, for example, centipoise (cP, cps) and pascal-second (Pa·s). One centipoise is one-hundredth of a poise; one poise is equal to 0.100 kg·m³. -1 ·s -1 In some respects, viscosity can be reported as “intrinsic viscosity” (IV, η, in dL / g); this term refers to a measure of the contribution of the dextran polymer to the viscosity of a liquid (e.g., a solution) containing the dextran polymer. IV measurements herein can be obtained, for example, using any suitable method, such as those described in U.S. Patent Application Publications 2017 / 0002335, 2017 / 0002336, or 2018 / 0340199, or Weaver et al. (…). J. Appl. Polym. Sci. [Journal of Applied Polymer Science] 35:1631-1637) or Chun and Park ( Macromol. Chem. Phys. [Polymer Chemistry and Physics] All of the information disclosed in (195:701-711) is incorporated herein by reference. For example, IV can be measured in part by dissolving (optionally at about 100°C for at least 2, 4, or 8 hours) the dextran polymer in DMSO having about 0.9 to 2.5 wt% (e.g., 1, 2, 1-2 wt%) of LiCl. IV as used herein can optionally be used as a relative measure of molecular weight.

[0075] As used herein, the terms “sequence identity,” “identity,” etc., relating to polypeptide amino acid sequences (e.g., polypeptide amino acid sequences of glucosyltransferases) are as defined and determined in U.S. Patent Application Publication No. 2017 / 0002336 (which is incorporated herein by reference).

[0076] The compositions described herein (which are “dry” or “dried”) typically contain less than 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% water.

[0077] The terms “percent by volume”, “volume percent”, “vol%”, and “v / v%” are used interchangeably in this document. The volume percentage of solute in a solution can be determined using the following formula: [(solute volume) / (solution volume)] x 100%.

[0078] The terms “percent by weight”, “weight percentage (wt%)”, and “weight-weight percentage (% w / w)” are used interchangeably herein. Weight percentage refers to the percentage of a material as a mass when it is contained in a composition, mixture, or solution.

[0079] The terms “weight / volume percentage”, “w / v%”, etc., are used interchangeably herein. Weight / volume percentage can be calculated as: ((mass of material [g]) / (total volume of material plus the liquid in which the material is placed [mL])) x 100%. The material may be insoluble in the liquid (i.e., a solid phase in the liquid phase, as in the case of a dispersion) or soluble in the liquid (i.e., a solute dissolved in the liquid).

[0080] The term "isolated" means a substance (or process) in a form not found in nature or in an environment not found in nature. Non-limiting examples of isolated substances include any α-glucan derivatives or cross-linked α-glucan derivatives disclosed herein. The embodiments disclosed herein are believed to be synthetic / artificial (impossible to manufacture or practice without human intervention / participation) and / or have properties not naturally occurring.

[0081] As used herein, the term "increased" can mean an increase in quantity or activity by at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 50%, 100%, or 200% compared to the increased quantity or activity. The terms "increased," "enhanced," "strengthened," "greater than," "improved," etc., are used interchangeably herein.

[0082] Some aspects of this disclosure relate to compositions (products) comprising α-glucan derivatives crosslinked with ethylene glycol diglycidyl ether (EGDE). Typically, such crosslinked α-glucan derivatives of this disclosure are produced by contacting EGDE with a first α-glucan derivative under suitable conditions (typically including aqueous conditions) for reacting and crosslinking EGDE with the first α-glucan derivative (i.e., the first α-glucan derivative has typically been derivatized, such as by etherification, sulfonation, or oxidation), thereby producing EGDE-crosslinked α-glucan derivatives. Regarding the relative amounts of EGDE and the first α-glucan derivative used in this crosslinking reaction, the ratio of EGDE to the first α-glucan derivative may be, for example, about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative. In some respects, the ratio of EGDE to the first α-glucan derivative can be about 0.04-0.06, 0.04-0.065, 0.04-0.07, 0.035-0.06, 0.035-0.065, 0.035-0.07, 0.03-0.06, or 0.03-0.065 moles of EGDE to about 1 mole of the first α-glucan derivative. However, in some respects, the ratio of EGDE to the first α-glucan derivative can be about 0.03-0.08, 0.03-0.09, 0.03-0.1, 0.04-0.08, 0.04-0.09, 0.04-0.1, 0.05-0.1, 0.05-0.09, 0.05-0.08, 0.06-0.1, 0.06-0.09, or 0.06-0.08 moles of EGDE to about 1 mole of the first α-glucan derivative. The cross-linked α-glucan derivatives disclosed herein have several advantageous features, such as the ability to prevent / reduce the formation of hard water cations (e.g., Ca2+) in various aqueous applications. 2+ Mg 2+ The interaction between ions and anionic compounds (e.g., carbonates, stearates) leads to the formation of unwanted deposits.

[0083] For example, the crosslinks formed using EGDE (“EGDE-based” or “EGDE-derived” crosslinks) described herein can be between two or more α-glucan derivative molecules (i.e., intermolecular crosslinks). In some respects, it is envisioned that EGDE-based crosslinks can also be intramolecular, i.e., crosslinks at different points within a single α-glucan derivative molecule.

[0084] The cross-linked α-glucan derivatives described herein may comprise homogeneous or heterogeneous α-glucan derivative components. Cross-linked α-glucan derivatives having homogeneous α-glucan derivative components can be prepared using one form / type, batch, or formulation of α-glucan derivatives (e.g., forms / types, batches, or formulations prepared using specific enzymatic reactions and / or derivatization). Cross-linked α-glucan derivatives having heterogeneous α-glucan derivative components can typically be prepared using, for example, two or more different forms / types, batches, or formulations of α-glucan derivatives. For example, heterogeneous cross-linked α-glucan derivatives may comprise two or more α-glucan derivatives that differ in substituent groups, DoS, molecular weight, and / or glycosidic bond characteristics.

[0085] In some aspects, compositions comprising the crosslinked α-glucan derivatives described herein may further comprise one or more uncrosslinked α-glucan derivatives. Examples of uncrosslinked α-glucan derivatives may be the same derivative used for crosslinking (i.e., such compositions comprise both crosslinked and uncrosslinked forms of the same α-glucan derivative) or α-glucan derivatives different from those used for crosslinking. The first α-glucan derivatives described herein are typically not chemically crosslinked prior to their use in the production of the EGDE-crosslinked α-glucan derivatives of this disclosure. However, in some alternative aspects herein, the α-glucan derivatives of this disclosure are not crosslinked.

[0086] In some aspects of this disclosure, the α-glucan derivative may be an α-1,3-glucan derivative. For example, the α-1,3-glucan derivative may serve as a first α-glucan derivative for the production of EGDE-crosslinked α-glucan derivatives. In some aspects, the α-1,3-glucan derivative may contain about or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% α-1,3 glycosidic bonds. Thus, in some aspects, the α-1,3-glucan derivative has about, or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% of non-α-1,3 glycosidic bonds. Typically, the non-α-1,3 glycosidic bonds are predominantly or entirely α-1,6. It should be understood that the higher the percentage of α-1,3 bonds present in an α-1,3-glucan derivative, the greater the likelihood that the dextran derivative is linear, because the occurrence of certain bonds that might be part of a branch point is lower. In some respects, as a percentage of glycosidic bonds in an α-1,3-glucan derivative, the α-1,3-glucan derivative has no branch points or has less than about 5%, 4%, 3%, 2%, or 1% of branch points.

[0087] In some respects, the DPw, DPn, or DP of the α-1,3-glucan moiety of the α-1,3-glucan derivative can be about, or at least about, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, or 4000. DPw, DPn, or DP can optionally be represented as a range between any two of these values. By way of example only, the DPw, DPn, or DP of the α-1,3-glucan moiety of an α-1,3-glucan derivative can be approximately 100-1600, 200-1600, 300-1600, 400-1600, 500-1600, 600-1600, 700-1600, 800-1600, 100-1250, 200-1250, 300-1250, 400-1250, 5 00-1250, 600-1250, 700-1250, 800-1250, 100-1000, 200-1000, 300-1000, 400-1000, 500-1000, 600-1000, 700-1000, 800-1000, 100-800, 200-800, 300-800, 400-800, 500-800, or 600-800. In some respects, the α-1,3-glucan moiety of the α-1,3-glucan derivative may have a high molecular weight as reflected by high intrinsic viscosity (IV); for example, IV may be about or at least about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 6-8, 6-7, 6-22, 6-20, 6-17, 6-15, 6-12, 10-22, 10-20, 10-17, 10-15, 10-12, 12-22, 12-20, 12-17, or 12-15 dL / g. For comparative purposes, it is noted that the IV of α-glucan having at least 90% (e.g., about 99% or 100%) α-1,3 bonds and about 800 DPw has an IV of about 2-2.5 dL / g. The IV in this document can be measured, for example, using α-glucan polymers dissolved in DMSO having about 0.9 to 2.5 wt% (e.g., 1, 2, 1-2 wt%) LiCl. If desired, the molecular weight of the crosslinked α-1,3-glucan derivatives in this document can be calculated or estimated based on the molecular weight of the first α-1,3-glucan derivative (e.g., based on its degree of polymerization and one or more substituents) and the average number of first α-1,3-glucan derivative molecules crosslinked together.

[0088] The α-1,3-glucan moiety of the α-1,3-glucan derivatives mentioned herein can be, for example, U.S. Patent Nos. 7,000,000, 8,871,474, 10301604, or 10260053, or U.S. Patent Application Publication Nos. 2019 / 0112456, 2019 / 0078062, 2019 / 0078063, 2018 / 0340199, 20 The molecular weight, bond characteristics, and production methods disclosed in 18 / 0021238, 2018 / 0273731, 2017 / 0002335, 2015 / 0232819, 2015 / 0064748, 2020 / 0165360, 2019 / 0276806, or 2019 / 0185893 (each of which is incorporated herein by reference) are also included.

[0089] In some aspects of this disclosure, the α-glucan derivative may be an α-1,6-glucan (dextran) derivative. For example, the α-1,6-glucan (dextran) derivative may serve as a first α-glucan derivative for the production of EGDE-crosslinked α-glucan derivatives. In some aspects, the α-1,6-glucan derivative may contain about 100% α-1,6-glycosidic bonds (i.e., completely linear), or about, or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 99.5% α-1,6-glycosidic bonds. In some aspects, the substantially linear α-1,6-glucan derivative may contain 5%, 4%, 3%, 2%, 1%, 0.5%, or less branches. If present, the branches from α-1,6-glucan are typically short, consisting of one, two, or three glucose monomers (side chains). In some respects, α-1,6-glucan derivatives may contain about, at least about, or less than 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% of α-1,4, α-1,3, and / or α-1,2 glycosidic bonds. Typically, such bonds are present entirely or almost entirely as branch points from α-1,6-glucan.

[0090] For example, the α-1,6-glucan moiety of the α-1,6-glucan derivatives described herein may have α-1,2, α-1,3, and / or α-1,4 branches. In some aspects, the percentages of all glycosidic bonds in the branched α-1,6-glucan are approximately, at least approximately, or less than approximately 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 30%, 35%, 40%, 45%, 50%, 2%-25%, 2%-20%, 2%-15%, 2%-10%, 3%-25%, 3%-20%, 3%-15%, 3%-10%, 5%-30%, 5%-25%, 5%-20%, 5%-15%, 5%-10%, 7%-13%. 8%-12%, 9%-11%, 10%-30%, 10%-25%, 10%-22%, 10%-20%, 10%-15%, 12%-20%, 12%-18%, 14%-20%, 14%-18%, 15%-30%, 15%-25%, 15%-20%, 15%-18%, 15%-17%, 20%-45%, 20%-40%, 20%-35%, 20%-30%, 20%-25%, 30%-45%, or 30%-40% are α-1,2, α-1,3, and / or α-1,4 glycosidic branched bonds (in some respects, α-1,2-branching or α-1,3-branching is the only type of branching present). The length of such branches is typically mostly (>90% or >95%) or entirely (100%) a single glucose monomer. In some respects, α-1,2-branched α-1,6-glucan can be produced enzymatically according to U.S. Patent Application Publication Nos. 2017 / 0218093 or 2018 / 0282385 (both incorporated herein by reference), wherein, for example, an α-1,2-branched enzyme, such as GTFJ18T1 or GTF9905, can be added during or after the production of dextran. In some respects, any other enzyme known to produce α-1,2-branching can be used. α-1,3-branched α-1,6-glucan can be produced, for example, as in Vuillemin et al. (2016, J. Biol Chem. [Journal of Biochemistry] Preparations disclosed in U.S. Patent Application Publication No. 291:7687-7702 or U.S. Patent Application Publication No. 2022 / 0267745 (which is incorporated herein by reference).

[0091] For example, the α-1,6-glucan moiety of the α-1,6-glucan derivative in this article may have about, at least about, or less than about 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 100-1600, 200-1600, 300-1600, 400-1600, 500-1600, 600-1600, 700-1600, 800-1600, 100-12 DPw, DPn, or DP of 50, 200-1250, 300-1250, 400-1250, 500-1250, 600-1250, 700-1250, 800-1250, 100-1000, 200-1000, 300-1000, 400-1000, 500-1000, 600-1000, 700-1000, 800-1000, 100-800, 200-800, 300-800, 400-800, 500-800, or 600-800. In some respects, the α-1,6-glucan moiety of the α-1,6-glucan derivatives described herein may have a Mw of about 5, 10, 15, 20, 25, 30, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 5-30, 5-25, 5-20, 10-30, 10-25, 10-20, 150-225, 150-200, 165-225, 165-200, 175-225, 175-200, 180-190, 5-250, 5-200, 10-250, or 10-200 kDa. For example, any of the aforementioned DPw, DPn, DP, or Mw values / ranges can characterize the α-1,6-glucan described herein, which has optionally been branched before or after (e.g., α-1,2 and / or α-1,3). In some aspects, any of the aforementioned DPw, DPn, DP, or Mw values / ranges can characterize the α-1,6-glucan derivative described herein. If desired, the molecular weight of the crosslinked α-1,6-glucan derivative described herein can be calculated or estimated based on the molecular weight of the first α-1,6-glucan derivative (e.g., based on its degree of polymerization and one or more substituents) and the average number of first α-1,6-glucan derivative molecules crosslinked together.

[0092] The α-1,6-glucan portion of the α-1,6-glucan derivatives described herein may be disclosed, for example, in U.S. Patent Application Publication Nos. 2016 / 0122445, 2017 / 0218093, 2018 / 0282385, 2020 / 0165360, or 2019 / 0185893 (e.g., molecular weight, bond / branching spectra, methods of production), each of which is incorporated herein by reference. In some respects, the α-1,6-glucan used for derivatization herein may be a glucan produced in a suitable reaction comprising glucosyltransferase (GTF) 0768 (SEQ ID NO: 1 or 2 of US 2016 / 0122445), GTF 8117, GTF 6831, or GTF 5604 (the latter three GTF enzymes being SEQ ID NO: 30, 32, and 33 of US 2018 / 0282385, respectively) or containing an amino acid sequence that is at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% identical to the amino acid sequence of GTF 0768, GTF 8117, GTF 6831, or GTF 5604.

[0093] In some respects, α-glucan derivatives, such as first α-glucan derivatives for the production of EGDE-crosslinked (or any type of crosslinked) α-glucan derivatives, may have a degree of substitution (DoS) of up to about 3.0 (e.g., 0.001 to 3.0) contributed by at least one group such as an organic group (e.g., via an ether, ester, sulfonyl, carbamate / carbamate, carbonate, or other bond), a sulfonate group, and / or an oxidized (oxidatively generated) group. DoS can be, for example, about, at least about, or up to about 0.001, 0.0025, 0.005, 0.01, 0.025, 0.05, 0.075, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0 (DoS can optionally be expressed as a range between any two of these values).Some examples of DoS ranges in this article include 0.005-2.0, 0.005-1.6, 0.005-1.5, 0.005-1.25, 0.005-1.0, 0.005-0.9, 0.005-0.8, 0.005-0.7, 0.005-0.6, 0.005-0.5, 0.005-0.25, 0.005-0.1, 0.04-0.1, 0.05-2.0, 0.05-1.6, 0.05-1.5, 0.05-1.25, 0. 0.5-1.0, 0.05-0.9, 0.05-0.8, 0.05-0.7, 0.05-0.6, 0.05-0.5, 0.1-2.0, 0.1-1.6, 0.1-1.5, 0.1-1.25, 0.1-1.0, 0.1-0.9, 0.1-0.8, 0.1-0.7, 0.1-0.6, 0.1-0.5, 0.15-2.0, 0.15-1.6, 0.15-1.5, 0.15-1.25, 0.15-1.0, 0.15-0. 9, 0.15-0.8, 0.15-0.7, 0.15-0.6, 0.15-0.5, 0.2-2.0, 0.2-1.6, 0.2-1.5, 0.2-1.25, 0.2-1.0, 0.2-0.9, 0.2-0.8, 0.2-0.7, 0.2-0.6, 0.2-0.5, 0.25-2.0, 0.25-1.6, 0.25-1.5, 0.25-1.25, 0.25-1.0, 0.25-0.9, 0.25-0.8, 0.2 5-0.7, 0.25-0.6, 0.25-0.5, 0.3-2.0, 0.3-1.6, 0.3-1.5, 0.3-1.25, 0.3-1.0, 0.3-0.9, 0.3-0.8, 0.3-0.7, 0.3-0.6, 0.3-0.5, 0.4-2.0, 0.4-1.6, 0.4-1.5, 0.4-1.25, 0.4-1.0, 0.4-0.9, 0.4-0.8, 0.4-0.7, 0.4-0.6, and 0.4-0.5. In some respects, mixed α-glucan derivatives, such as mixed α-glucan derivatives having two or more different organic groups (e.g., ether-, ester-, carbamate / carbamoyl-, sulfonyl-, or carbonate-linked organic groups) and / or other substituent groups (e.g., sulfonate or carboxylate groups), can be characterized as having any of the foregoing DoS values / ranges (wherein the DoS value / range refers to the total DoS of all substituents in aggregate, or the DoS of any particular substituent [i.e., on a separate basis]).

[0094] Because there are at most three hydroxyl groups in the glucose monomer unit of α-glucan, the overall DoS of α-glucan derivatives may not exceed 3.0. It should be understood that, since dextran derivatives as disclosed herein have a DoS contributed by at least one group other than hydrogen (such as an organic group) (e.g., between about 0.001 and about 3.0), all substituents of dextran derivatives cannot be hydroxyl groups only.

[0095] In some aspects, the first α-glucan derivative has a DoS of about 0.35 to 2.5, 0.4 to 2.5, 0.4 to 1.0, or 0.35 to 1.0 contributed by groups such as etherified organic groups, sulfonate groups, or groups generated by oxidation (e.g., carboxylate groups), and / or wherein such groups are anionic (negatively charged). For example, the etherified organic group may be carboxyl, such as carboxymethyl. Optionally, such a first α-glucan derivative may be further substituted with an organic group including an aryl group (e.g., via an ether bond); for example, such an organic group may be benzyl or a substituted benzyl (e.g., as above). Such a first α-glucan derivative may be an α-1,3-glucan derivative as described herein, such as an α-1,3-glucan derivative comprising about or at least about 90%, 95%, 99%, or 100% α-1,3 glycosidic bonds.

[0096] In some aspects, the first α-glucan derivative has a DoS of at least about 2.0, 2.25, or 2.5, or about 2.3 to 2.6, substituted by groups as described herein, such as etherified organic groups, sulfonate groups, or groups derived from oxidation (e.g., carboxylate groups), and / or wherein such groups are anionic (negatively charged). For example, the etherified organic group may be carboxyl, such as carboxymethyl. Optionally, such a first α-glucan derivative may be further substituted by an organic group comprising an aryl group (e.g., via an ether bond); for example, such an organic group may be benzyl or a substituted benzyl (e.g., as follows). Such a first α-glucan derivative may be an α-1,6-glucan derivative having at least about 50% α-1,6 glycosidic bonds and typically also having α-1,2 and / or α-1,3 branches (e.g., only α-1,2 branches are present).

[0097] The α-glucan derivatives (such as the first α-glucan derivative) described herein may be substituted with at least one group (e.g., an organic group). For example, the substituent group may be attached to the α-glucan derivative via an ether bond, ester bond, carbamate / carbamoyl bond, carbonate bond, or sulfonyl bond. Therefore, in some aspects, the α-glucan derivative may also be characterized as an α-glucan ether, ester, carbamate, carbonate, or sulfonyl derivative. The organic group described herein can typically be considered to contain at least one carbon atom and at least one hydrogen atom.

[0098] The organic group ether-bonded to the α-glucan derivative (e.g., the first α-glucan derivative) herein can be, for example, an alkyl group. In some aspects, the alkyl group can be straight-chain, branched, or cyclic (“cycloalkyl” or “alicyclic”). In some aspects, the alkyl group is C1 to C2. 18 Alkyl groups, such as C4 to C5 18 Alkyl, or C1 to C 10 Alkyl (in "C") # In this context, # indicates the number of carbon atoms in the alkyl group. Alkyl groups can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, or octadecyl; such alkyl groups are typically straight-chain. In some aspects, one or more carbons of the alkyl group can be substituted by another alkyl group, resulting in branching of the alkyl group. Suitable examples of branched isomers of straight-chain alkyl groups include isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, neopentyl, isohexyl, neohexyl, 2-ethylhexyl, 2-propylheptenyl, and isooctyl. In some aspects, the alkyl group is a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl.

[0099] In some respects, the organic group ether-bonded to the α-glucan derivatives herein may be a substituted alkyl group having a substituted carbon atom on one or more carbons of the alkyl group. This one or more substitutions may be one or more hydroxyl, aldehyde, ketone, and / or carboxyl groups. For example, the substituted alkyl group may be hydroxyalkyl, dihydroxyalkyl, or carboxylalkyl. Suitable examples of hydroxyalkyl groups are hydroxymethyl (-CH2OH), hydroxyethyl (e.g., -CH2CH2OH, -CH(OH)CH3), hydroxypropyl (e.g., -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3), hydroxybutyl, and hydroxypentyl. Other examples include dihydroxyalkyl (diols), such as dihydroxymethyl, dihydroxyethyl (e.g., -CH(OH)CH2OH), dihydroxypropyl (e.g., -CH2CH(OH)CH2OH, -CH(OH)CH(OH)CH3), dihydroxybutyl, and dihydroxypentyl. Suitable examples of carboxyl groups are carboxymethyl (-CH2COOH), carboxyethyl (e.g., -CH2CH2COOH, -CH(COOH)CH3), carboxypropyl (e.g., -CH2CH2CH2COOH, -CH2CH(COOH)CH3, -CH(COOH)CH2CH3), carboxybutyl and carboxypentyl.

[0100] In some respects, one or more carbons of the alkyl group ether-linked to the α-glucan derivative herein may have one or more substitutions with another alkyl group. Examples of such substituent alkyl groups are methyl, ethyl, and propyl. For example, the organic group may be, for instance, -CH(CH3)CH2CH3 or -CH2CH(CH3)CH3, both of which are propyl groups with methyl substitution.

[0101] As should be clear from the above examples of various substituted alkyl groups, in some respects, the substitution on the alkyl group (e.g., hydroxyl or carboxyl) can be at the terminal carbon atom of the alkyl group, wherein the terminal carbon group is opposite to the monomer unit of the α-glucan ether compound (e.g., glucose) on the ether-linked alkyl side. An example of such terminal substitution is hydroxypropyl-CH2CH2CH2OH. Alternatively, the substitution can be at the internal carbon atom of the alkyl group. An example of internal substitution is hydroxypropyl-CH2CH(OH)CH3. The alkyl group can have one or more substitutions, which can be the same (e.g., two hydroxyl groups [dihydroxyl]) or different (e.g., one hydroxyl group and one carboxyl group).

[0102] Optionally, the etherified alkyl group described herein may contain one or more heteroatoms, such as oxygen, sulfur, and / or nitrogen, within the hydrocarbon chain. Examples include alkyl groups containing an alkylglycerol alkoxylate moiety (-alkylene-OCH2CH(OH)CH2OH), a ring-opening moiety derived from 2-ethylhexyl glycidyl ether, and a tetrahydropyranyl group (e.g., as derived from dihydropyran). Further examples include alkyl groups substituted at their terminals with a cyano group (-C≡N); such substituted alkyl groups may optionally be referred to as cyanoalkyl or cyanoalkyl. Examples of cyanoalkyl groups described herein include cyanomethyl, cyanoethyl, cyanopropyl, and cyanobutyl.

[0103] In some respects, the etherified organic groups are C2 to C3. 18 (For example, C4 to C) 18 The alkenyl group is a hydrocarbon group containing at least one carbon-carbon double bond, and the alkenyl group can be straight-chain, branched, or cyclic. As used herein, the term "alkenyl" refers to a hydrocarbon group containing at least one carbon-carbon double bond. Examples of alkenyl groups include vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexyl, and allyl. In some aspects, one or more carbons of the alkenyl group may have one or more substitutions with alkyl, hydroxyalkyl, or dihydroxyalkyl groups, as disclosed herein. Examples of such substituent alkyl groups include methyl, ethyl, and propyl. Optionally, the alkenyl group herein may contain one or more heteroatoms, such as oxygen, sulfur, and / or nitrogen, within the hydrocarbon chain; for example, the alkenyl group may contain a ring-opening moiety derived from allyl glycidyl ether.

[0104] In some respects, the etherified organic groups are C2 to C3. 18 Alkynyl. As used herein, the term "alkynyl" refers to a straight-chain or branched hydrocarbon group containing at least one carbon-carbon triple bond. The alkynyl group in this document may be, for example, propynyl, butynyl, pentynyl, or hexynyl. The alkynyl group may optionally be substituted with alkyl, hydroxyalkyl, and / or dihydroxyalkyl groups. Optionally, the alkynyl group may contain one or more heteroatoms, such as oxygen, sulfur, and / or nitrogen, within the hydrocarbon chain.

[0105] In some aspects, the etherified organic group is a polyether comprising repeating units of (-CH2CH2O-), (-CH2CH(CH3)O-), or mixtures thereof, wherein the total number of repeating units is in the range of 2 to 100. In some aspects, the organic group comprises (-CH2CH2O-). 3-100 Or (-CH2CH2O-) 4-100 The polyether group. In some respects, the organic group contains (-CH2CH(CH3)O-). 3-100 Or (-CH2CH(CH3)O-) 4-100 The polyether group. As used herein for polyether groups, the subscript specifying the range indicates the potential number of repeating units; for example, (CH2CH2O). 2-100This refers to a polyether group containing 2 to 100 repeating units. In some respects, the polyether group in this document may be end-capped with, for example, methoxy, ethoxy, or propoxy.

[0106] In some respects, the etherified organic group comprises an aryl group. As used herein, the term "aryl" means an aromatic / carbocyclic group having a monocyclic (e.g., phenyl), polycyclic (e.g., biphenyl), or multiple fused rings, at least one of which is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthraceneyl, or phenanthrene) and optionally monosubstituted, disubstituted, or trisubstituted by an alkyl group (such as methyl, ethyl, or propyl). In some respects, the aryl group is C6 to C6. 20 Aryl. In some aspects, the aryl group is a methyl-substituted aryl group such as tolyl (-C6H4CH3) or xylyl [-C6H3(CH3)2] group. The tolyl group can be, for example, p-tolyl. In some aspects, the aryl group is benzyl (-CH2-phenyl). The benzyl group in this document may optionally be substituted (typically on its benzene ring) with one or more of a halogen, cyano, ester, amide, ether, alkyl (e.g., C1 to C6), aryl (e.g., phenyl), alkenyl (e.g., C2 to C6), or alkynyl (e.g., C2 to C6) group.

[0107] In some respects, α-glucan derivatives having an ether group may contain one type of etherified organic group. Examples of such compounds contain a carboxyl alkyl group (e.g., carboxymethyl) as the sole etherified organic group. Further examples include α-glucan ethers containing an alkyl group (e.g., methyl, ethyl, propyl) as the sole etherified organic group. Further examples include α-glucan ethers containing a dihydroxyalkyl group (e.g., dihydroxypropyl) as the sole etherified organic group.

[0108] In some respects, α-glucan derivatives having ether groups may contain two or more different types of etherified organic groups (i.e., mixed ethers of α-glucan). Examples of such α-glucan ethers contain (i) two different alkyl groups as etherified organic groups, (ii) alkyl and hydroxyalkyl groups as etherified organic groups (alkylhydroxyalkyl α-glucan), (iii) alkyl and carboxylalkyl groups as etherified organic groups (alkylcarboxylalkyl α-glucan), (iv) hydroxyalkyl and carboxylalkyl groups as etherified organic groups (hydroxyalkylcarboxylalkyl α-glucan), (v) two different hydroxyalkyl groups as etherified organic groups, (vi) two different carboxylalkyl groups as etherified organic groups, or (vii) carboxylalkyl (e.g., carboxymethyl) and aryl (e.g., benzyl). Non-limiting examples of some of these types of mixed ethers include ethylhydroxyethyl α-glucan, hydroxyalkylmethyl (e.g., hydroxypropylmethyl) α-glucan, carboxymethylhydroxyethyl α-glucan, carboxymethylhydroxypropyl α-glucan, and carboxymethylbenzyl α-glucan. In some cases, the ether group of the mixed α-glucan ether may be as disclosed in U.S. Patent Application Publication No. 2020 / 0002646 (which is incorporated herein by reference).

[0109] In some respects, the α-glucan derivatives described herein may include one or more ester groups. The ester groups of the α-glucan derivatives may, for example, contain at least one acyl group -CO-R', wherein R' comprises a chain of 1 to 26 carbon atoms. R' may be, for example, linear, branched, or cyclic. Examples of linear acyl groups described herein include acetyl, propionyl, butyryl, valeryl, hexanoyl, heptayl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, eicosanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, and hexadecanoyl. Some of the acyl groups listed above are commonly known as acetyl (or ethanoyl group), propionyl (or propanoyl group), butyryl (or butanoyl group), valeryl (or pentanoyl group), caproyl (or hexanoyl group); enanthyl (or heptanoyl group), caprylyl (or octanoyl group), pelargonyl (or nonanoyl group), capryl (or decanoyl group), lauroyl (dodecanoyl), myristyl (tetradecanoyl), palmityl (hexadecanoyl), stearyl (octadecanoyl), arachidyl (eicosyl), behenyl (dodecanoyl), creosyl (tetracosyl), and waxyl (hexacosyl).

[0110] In some aspects, the acyl group of the α-glucan derivative comprises an aryl group. For example, the aryl acyl group may include a benzoyl group (-CO-C6H5), which may also be referred to as a benzoate ester group. In some aspects, the aryl acyl group may comprise a benzoyl group substituted with at least one halogen (“X”; e.g., Cl, F), alkyl, haloalkyl, ether, cyano, or aldehyde group, or combinations thereof, such as those represented by the following structures III(a) to III(r):

[0111] Structure III(a) - III(r)

[0112] In some respects, the acyl group of the α-glucan derivative can be -CO-CH2-CH2-COOH, -CO-CH2-CH2-CH2-COOH, -CO-CH2-CH2-CH2-CH2-COOH, -CO-CH2-CH2-CH2-CH2-CH2-COOH, -CO-CH=CH-COOH, -CO-CH=CH-CH2-COOH, -CO-CH=CH-CH2-CH2-COOH, -CO-CH=CH-CH2-CH2-CH2-COOH, -CO-CH=CH-CH2-CH2-CH2-COOH, -CO-C H2-CH=CH-COOH, -CO-CH2-CH=CH-CH2-COOH, -CO-CH2-CH=CH-CH2-CH2-COOH, -CO-CH2-CH=CH-CH2-CH2-CH2-COOH, -CO-CH2-CH2-CH=CH-COOH, -CO-CH2-CH2-CH =CH-CH2-COOH, -CO-CH2-CH2-CH=CH-CH2-CH2-COOH, -CO-CH2-CH2-CH2-CH=CH-COOH, -CO-CH2-CH2-CH2-CH=CH-CH2-COOH, -CO-CH2-CH2-CH2-CH2-CH=CH-COOH, , Alternatively, cyclic organic acid anhydrides, for example, can be used as any other acyl group as an esterifying agent.

[0113] In some respects, α-glucan derivatives having ester groups may contain one type of esterified acyl group. Examples of such derivatives contain an acetyl group as the sole esterified acyl group. However, in some respects, α-glucan derivatives may contain two or more different types of esterified acyl groups (i.e., mixed esters of α-glucan). Examples of such mixed esters include those having at least (i) an acetyl and a propionyl group, (ii) an acetyl and a butyryl group, and (iii) a propionyl and a butyryl group.

[0114] The acyl groups of the α-glucan ester derivatives described herein may be disclosed, for example, in U.S. Patent Application Publication Nos. 2014 / 0187767, 2018 / 0155455, 2020 / 0308371, or 2023 / 0287148 or International Patent Application Publication No. WO 2021 / 252575 (each of which is incorporated herein by reference).

[0115] In some aspects, the α-glucan derivatives described herein may include one or more carbamate / carbamoyl groups. The carbamate groups of the α-glucan derivatives may be derived from aliphatic, alicyclic, or aromatic monoisocyanates. In some aspects, the substituents of the α-glucan derivatives may be carbamate-linked phenyl, benzyl, diphenylmethyl, or diphenylethyl groups; these groups may optionally be derived from aromatic monoisocyanates such as phenyl, benzyl, diphenylmethyl, or diphenylethyl isocyanates. In some aspects, the substituents of the α-glucan derivatives may be carbamate-linked ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or octadecyl groups; these groups may optionally be derived from aliphatic monoisocyanates such as ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or octadecyl isocyanates. In some respects, the substituents of the α-glucan derivative can be urethane-linked cyclohexyl, cycloheptyl, or cyclododecyl groups; these groups can optionally be derived from alicyclic monoisocyanates such as cyclohexyl, cycloheptyl, or cyclododecyl isocyanates.

[0116] The urethane groups of the α-glucan derivatives described herein may be disclosed, for example, in U.S. Patent Application Publication Nos. 2022 / 0033531 or 2023 / 0212325 or International Patent Application Publication No. WO 2021 / 252569 (each of which is incorporated herein by reference).

[0117] In some respects, the α-glucan derivatives herein may include one or more sulfonyl groups. The sulfonyl groups of the α-glucan derivatives herein may be disclosed, for example, in International Patent Application Publication No. WO 2021 / 252569 or U.S. Patent Application Publication No. 2023 / 0212325 (which are incorporated herein by reference).

[0118] This disclosure also relates to a method for producing cross-linked α-glucan derivatives. The method typically includes: (a) Contacting ethylene glycol diglycidyl ether (EGDE) with a first α-glucan derivative (under suitable conditions, typically including aqueous conditions, for reacting and crosslinking EGDE with the first α-glucan derivative), thereby crosslinking the first α-glucan derivative (thus producing an EGDE-crosslinked α-glucan derivative), wherein the ratio of EGDE to the first α-glucan derivative is about 0.03 to 0.07 moles (e.g., about 0.04 to 0.06 moles) of EGDE to about 1 mole of the first α-glucan derivative; and (b) Optionally, the cross-linked α-glucan derivative can be isolated.

[0119] Any characteristics of the cross-linked α-glucan derivative described herein can characterize the cross-linking method. Method parameters used to cross-link the α-glucan derivative EGDE (e.g., incubation time, temperature, reagents [e.g., solvents, pH adjusters / buffers], reagent [e.g., EGDE] concentration, α-glucan derivative substrate concentration, and / or step sequence) can be any of those disclosed in the examples below, or within 5%-10% of any of those parameters, as applicable.

[0120] The cross-linked α-glucan derivatives generated in the cross-linking reaction described herein can optionally be separated. In some respects, such products can be precipitated first from the aqueous conditions of the reaction. Precipitation and / or washing of the solid product (whether or not it initially precipitates) can be carried out by adding an excess (e.g., at least 2-3 times the reaction volume) of an alcohol (e.g., 100% or 95% concentration) such as methanol, ethanol, or isopropanol to the reaction. The products can then be separated using a filter funnel, centrifuge, filter press, or any other method or apparatus that allows the removal of liquid from the solid. The separated products can be dried, such as by vacuum drying, air drying, or freeze drying.

[0121] In some respects, cross-linked α-glucan derivative products can be separated by steps including filtering the completed reaction or its aqueous dilution form by ultrafiltration (e.g., using a 5 or 10 molecular weight cutoff filter). Alternatively, the completed reaction or its diluted form can be filtered periodically (i.e., without ultrafiltration) first, and then the filtrate can be subjected to ultrafiltration. The concentrated liquid obtained by ultrafiltration can then be dried to its component solids, such as by freeze-drying, or the solids can be precipitated from the liquid and then dried (e.g., freeze-drying).

[0122] The cross-linked α-glucan derivative products described herein can be used as starting materials for further modification to repeat the α-glucan cross-linking reaction. In some respects, the α-glucan derivatives used for cross-linking are water-insoluble, while in others they are water-soluble.

[0123] The cross-linked α-glucan derivatives of this disclosure can, for example, be in quantities of about, at least about, or less than about 0.01, 0.05, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 1.2, 1.25, 1.4, 1.5, 1.6, 1.75, 1.8, 2.0, 2.25, 2.5, 3.0. 3.5, 4.0, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 48, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 9 4, 95, 96, 97, 98, 99, 0.01-0.1, 0.01-0.08, 0.01-0.06, 0.01-0.05, 0.03-0.1, 0.03-0.08, 0.03-0.06, 0.03-0.05, 4-12, 4-10, 4-8, 5-12, 5-10, 5-8, 6-12, 6-10, or 6-8 wt% or w / v%, or a range between any two of these values, exist in the composition / system, such as an aqueous composition / system or a dry composition / system. The liquid component of the aqueous composition herein may be, for example, an aqueous fluid, such as water or an aqueous solution. The solvent of aqueous solutions is typically water, or may contain, for example, about or at least about 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, 98 wt%, or 99 wt% water. The aqueous or dry compositions mentioned herein may also refer to aqueous or dry systems, respectively. In some aspects, the compositions herein may comprise or be in the form of solutions, dispersions (e.g., emulsions), mixtures, wet cakes or wet powders, or dry powders.

[0124] In some aspects, the solvent of the compositions herein comprises water and, for example, at least about 40% (v / v or w / w) of one or more polar organic solvents. In some aspects, the solvent comprises about, or at least about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83 One or more polar organic solvents of the following amounts: 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 40-90, 40-80, 40-70, 40-60, 50-90, 50-80, 50-70, 50-60, 60-90, 60-80, 60-70, 70-90, 70-80, 40-70, 40-60, 75-85, or 85-95 v / v% or w / w%. The balance of the solvent is typically only water (e.g., a solvent having about 75 v / v% polar organic solvent has about 25 v / v% water), but may optionally contain (e.g., less than 2, 1, 0.5, or 0.25 v / v%) one or more other liquids besides the polar organic solvent. Given its presence of water, the solvents described herein may optionally be characterized as aqueous solvents. While the solvents described herein typically comprise one type of polar organic solvent, they may optionally comprise two, three, or more polar organic solvents; in such respects, the concentration of polar organic solvents is typically the concentration of a combination of polar organic solvents.

[0125] In some respects, polar organic solvents can be protons. Examples of proton-polar organic solvents in this document include alcohols (e.g., methanol, ethanol, isopropanol, 1-propanol, tert-butanol, n-butanol, isobutanol), methylformamide, and formamide. Other examples of proton-polar organic solvents in this document include n-butanol, ethylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, glycerol, 1,2-propanediol, and 1,3-propanetriol.

[0126] In some respects, polar organic solvents can be aprotic. Examples of aprotic polar organic solvents in this paper include acetonitrile, dimethyl sulfoxide, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, propylene carbonate, and sulfolane. Further examples of aprotic polar organic solvents in this paper include hexamethylphosphoramide, dimethylimidazolium ketone (1,3-dimethyl-2-imidazolium ketone), dioxane, nitromethane, and butanone. Generally, esters, ketones, and aldehydes that do not have acidic hydrogen atoms are other examples of aprotic polar organic solvents in this paper.

[0127] The aqueous compositions described herein may have, for example, about, at least about, or less than about 1, 5, 10, 100, 200, 300, 400, 500, 600, 700, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 1-300, 10-300, 2 Viscosities of 5-300, 50-300, 1-250, 10-250, 25-250, 50-250, 1-200, 10-200, 25-200, 50-200, 1-150, 10-150, 25-150, 50-150, 1-100, 10-100, 25-100, or 50-100 centipoise (cps). For example, viscosity can be measured with the aqueous compositions described herein at any temperature between about 3°C ​​and about 80°C (e.g., 4°C-30°C, 15°C-30°C, 15°C-25°C). Viscosities are typically measured at atmospheric pressure (about 760 Torr) or at ±10% of that pressure. Viscosity can be measured using, for example, a viscometer or rheometer, and can optionally be measured in, for example, at approximately 0.1, 0.5, 1.0, 5, 10, 50, 100, 500, 1000, 0.1-500, 0.1-100, 1.0-500, 1.0-1000, or 1.0-100 s. -1 Measured at a shear rate (rotational shear rate) of (1 / s) or at approximately 5, 10, 20, 25, 50, 100, 200, or 250 rpm (revolutions per minute).

[0128] For example, the compositions disclosed herein may have a concentration of about, or less than, about 1500, 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600, 500, 400, 300, 280, 260, 240, 220, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 45, 40, 35, 30, 25. Turbidity in NTUs (turbidimetric units) of 20, 18, 16, 14, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 1-250, 1-200, 1-150, 1-100, 1-50, 1-20, 1-15, 1-10, 1-5, 2-250, 2-200, 2-150, 2-100, 2-50, 2-20, 2-15, 2-10, 2-5, 10-250, 10-200, 10-150, 10-100, 10-50, or 10-20. Any of these NTU values ​​may optionally be relative to the cross-linked α-glucan derivative and solvent component portions of the compositions herein. In some respects, it is envisioned that any of these NTU levels will persist for approximately, at least approximately, or up to approximately 0.5, 1, 2, 4, 6, 8, 10, 20, 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, or 360 days, or for 1, 2, or 3 years (typically from the initial preparation). Turbidity can be measured using any suitable method, such as... Progress in Filtration and Separation The methods disclosed in (Version: 1, Chapter 16. Turbidity: Measurement of Filtrate and Supernatant Quality?, Publisher: Academic Press, Editor: ES Tarleton, July 2015) are incorporated herein by reference or as described in the following examples.

[0129] In some respects, for example, aqueous compositions containing cross-linked α-glucan derivatives may have one or more salt / buffer solutions (e.g., Na+). + Cl -NaCl, phosphates, tris, citrates (e.g., ≤ 0.1 wt%, 0.5 wt%, 1.0 wt%, 2.0 wt%, or 3.0 wt%) and / or about 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 4.0-10.0, 4.0-9.0, 4.0-8.0, 5.0-1 pH values ​​of 0.0, 5.0-9.0, 5.0-8.0, 6.0-10.0, 6.0-9.0, 6.0-8.0, 9.0-13.5, 10.0-13.5, 10.5-13.5, 11.0-13.5, 9.0-13.0, 10.0-13.0, 10.5-13.0, or 11.0-13.0. The cross-linked α-glucan derivatives described herein are typically anionic, typically due to having one or more anionic substituents (e.g., anionic organic groups, sulfonate groups, oxidizing groups). For example, the charge of the cross-linked α-glucan derivatives described herein can be the charge present when the derivative is in the aqueous composition described herein, further taking into account the pH of the aqueous composition (in some respects, the pH can be 4-10 or 5-9, or any pH as disclosed above).

[0130] In some aspects, for aqueous compositions of cross-linked α-glucan derivative particles (e.g., emulsions) as part of the present disclosure, these particles are dispersed in about or at least about 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 98%, 99%, or 100% of the dispersion volume. In some aspects, this level of dispersion (e.g., emulsion) is expected to persist for about, at least about, or up to about 0.5, 1, 2, 4, 6, 8, 10, 20, 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, or 360 days, or for 1, 2, or 3 years (typically from the initial preparation of the dispersion).

[0131] For example, the temperature of the compositions (e.g., aqueous compositions) containing cross-linked α-glucan derivatives described herein can be about, or at most about, or less than about 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 100°C. , 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 0°C- 160°C, 0°C-150°C, 0°C-140°C, 0°C-130°C, 0°C-120°C, 0°C-110°C, 0°C-100°C, 0°C-90°C, 0°C -80°C, 0°C-70°C, 0°C-60°C, 10°C-160°C, 10°C-150°C, 10°C-140°C, 10°C-130°C, 10°C-120° C, 10°C-110°C, 10°C-100°C, 10°C-90°C, 10°C-80°C, 10°C-70°C, 10°C-60°C, 50°C-80°C, 50°C -75°C, 50°C-70°C, 50°C-65°C, 55°C-80°C, 55°C-75°C, 55°C-70°C, 55°C-65°C, 60°C-80°C, 60 °C-75°C, 60°C-70°C, 60°C-65°C, 5°C-50°C, 15°C-25°C, 20°C-25°C, 20°C-30°C, or 20°C-40°C.

[0132] In some respects, the compositions comprising cross-linked α-glucan derivatives herein may be non-aqueous (e.g., dry compositions). Examples of such embodiments include powders, granules, microcapsules, flakes, or any other form of particulate matter. Other examples include larger compositions such as spheres, rods, cores, beads, tablets, strips, or other aggregates, or ointments or lotions (or any other form of non-aqueous or dry composition herein). Non-aqueous or dry compositions typically contain about 12, 10, 8, 6, 5, 4, 3, 2, 1.5, 1.0, 0.5, 0.25, 0.10, 0.05, or 0.01 wt% water. In some respects (e.g., for detergents used for washing clothes or dishes), the drying compositions described herein may be provided in the form of sachets, pouches, water-dispersible compositions / carriers (e.g., fibrous compositions, such as nonwoven or other fibrous structures, sponges or foams, aggregates), water-soluble compositions / carriers (e.g., sheets or films, fibrous compositions, such as nonwoven or other fibrous structures, sponges or foams, aggregates), or any other suitable unit dosage form.

[0133] In some respects, the compositions comprising cross-linked α-glucan derivatives described herein can be detergent compositions. Examples of such compositions as detergents for dishwashing and for fabric care are disclosed herein.

[0134] In some respects, the compositions comprising cross-linked α-glucan derivatives herein may contain one or more salts, such as sodium salts (e.g., NaCl, Na₂SO₄). Other examples of salts include those having (i) aluminum, ammonium, barium, calcium, chromium (II or III), copper (I or II), iron (II or III), hydrogen, lead (II), lithium, magnesium, manganese (II or III), mercury (I or II), potassium, silver, sodium, strontium, tin (II or IV), or zinc cations, and (ii) Salts containing anions of acetate, borates, bromates, bromides, carbonates, chlorates, chlorides, chlorites, chromates, ammonia nitrile, cyanides, dichromates, dihydrogen phosphates, ferrocyanides, ferrocyanides, fluorides, bicarbonates, hydrogen phosphates, bisulfates, hydrogen sulfide, bisulfites, hydrides, hydroxides, hypochlorites, iodates, iodides, nitrates, nitrites, oxalates, oxides, perchlorates, permanganates, peroxides, phosphates, phosphides, phosphites, silicates, stannates, stansites, sulfates, sulfides, sulfites, tartrates, or thiocyanates. Therefore, for example, any salt having a cation from (i) above and an anion from (ii) above can be in the composition. Salts may be present in the aqueous compositions herein at, for example, about or at least about .01, .025, .05, .075, .1, .25, .5, .75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.5, 3.0, 3.5, .01-3.5, .5-3.5, .5-2.5, or .5-1.5 wt% (such wt% values ​​typically refer to the total concentration of one or more salts).

[0135] The compositions comprising cross-linked α-glucan derivatives described herein may optionally contain one or more enzymes (active enzymes). Examples of suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g., metallolipases), xylanases, lipases, phospholipases, esterases (e.g., aryl esterases, polyesterases), peroxyhydrolases, keratins, pectins, pectinases, pectin lyases, mannanases, keratinases, reductases, oxidases (e.g., choline oxidases), phenol oxidases, lipoxygenases, ligninases, amylopectinases, tanninases, pentosanases, malicases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, metalloproteinases, amadoriases, glucosylamylases, arabinofuranases, inositol hexaphosphatases, isomerases, transferases, nucleases, and amylases. If one or more enzymes are included, they may be included in the compositions herein, for example, at an activity level of about 0.0001 wt% to 0.1 wt% (e.g., 0.01 wt% to 0.03 wt%) of the enzyme (e.g., calculated as pure enzyme protein). In fabric care or automatic dishwashing applications, the enzymes (e.g., any of the above, such as cellulase, protease, amylase, nuclease, and / or lipase) may be present, for example, at a concentration of at least about 0.01 to 0.1 ppm total enzyme protein, or about 0.1 to 10 ppb total enzyme protein (e.g., less than 1 ppm) to at most about 100, 200, 500, 1000, 2000, 3000, 4000, or 5000 ppm total enzyme protein in the aqueous composition (e.g., detergent, greywater) in which the fabrics or tableware are treated.

[0136] In some respects, the cross-linked α-glucan derivatives and / or compositions containing such derivatives are biodegradable. After testing at 15, 30, 45, 60, 75, or 90 days, for example, such biodegradation rates can be determined as, for instance, by the carbon dioxide emission test method (OECD Guideline 301B, incorporated herein by reference), to be about, at least about, or at most about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 5%–60%, 5%–80%, 5%. -90%, 40%-70%, 50%-70%, 60%-70%, 40%-75%, 50%-75%, 60%-75%, 70%-75%, 40%-80%, 50%-80%, 60%-80%, 70%-80%, 40%-85%, 50%-85%, 60%-85%, 70%-85%, 40%-90%, 50%-90%, 60%-90%, or 70%-90%, or any value between 5% and 90%. This biodegradability is expected to be about, at least about, or at most about 10%, 25%, 50%, 75%, 100%, 150%, 200%, 250%, 500%, 750%, or 1000% higher than that of existing materials.

[0137] The composition may comprise one, two, three, four or more different cross-linked α-glucan derivatives as described herein and optionally at least one uncross-linked α-glucan derivative (e.g., as disclosed herein). For example, the composition may comprise at least one type of cross-linked α-glucan derivative and at least one type of uncross-linked α-glucan derivative; in some aspects, the latter may be (or can be) a precursor compound of the former. In some aspects, uncross-linked α-glucan derivatives (e.g., precursor compounds) are not present.

[0138] In some respects, the aqueous compositions comprising cross-linked α-glucan derivatives described herein further comprise at least one cation, and the derivative is bound to the cation. This binding is typically via ionic bonding. Examples of cations include one or more hard water cations such as Ca2+. 2+ and / or Mg 2+ The cross-linked α-glucan derivatives described herein, when bound to cations in aqueous compositions / systems, can, for example, be used to soften water in aqueous compositions / systems (as a detergent builder).

[0139] The aqueous compositions / systems in which the crosslinked α-glucan derivatives of this document can bind to at least one cation can be, for example, detergents / grey water used for washing dishes (e.g., in automatic dishwashing machines) or containing textiles (e.g., clothing, such as in washing machines), or any other aqueous compositions / systems to which a detergent for washing and / or providing retention has been added; such aqueous compositions / systems typically benefit from the ability of the crosslinked α-glucan derivatives to prevent / reduce the negative effects (e.g., scale deposition and / or scale formation) caused by the presence of one or more cations. In some aspects, the aqueous compositions / systems in which the crosslinked α-glucan derivatives can bind to at least one cation can be any system disclosed herein in which water or aqueous solutions are circulated, transported, and / or stored (the presence of a detergent is not necessarily required); such systems typically also benefit for the same reasons disclosed above. Typically, the crosslinked α-glucan derivatives of this document can be used as builder / softener by isolating / chelating and / or precipitating cations. In some respects, the water-soluble crosslinked α-glucan derivatives described herein can bind cations and remain water-soluble. In some respects, the dispersed (e.g., stably dispersed) water-insoluble crosslinked α-glucan derivatives described herein can bind cations and remain dispersed. The binding (or other interactions, however possible) between the crosslinked α-glucan derivatives described herein and cations can prevent / reduce the formation of undesirable insoluble salts (e.g., carbonates such as CaCO3 or MgCO3, hydroxides such as Mg(OH)2 or Ca(OH)2, sulfates such as CaSO4) and / or other insoluble compounds (e.g., calcium and / or magnesium salts of fatty acids such as stearates), and / or deposits (e.g., scale, scum such as soap scum) that can form in aqueous systems with hard water cations (e.g., preventing / reducing the formation by about or at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% compared to the uncrosslinked α-glucan derivatives). In some respects, scale can contain CaCO3, MgCO3, CaSO4, Fe2O3, FeS, and / or FeS2.

[0140] In addition to those mentioned above, some examples of aqueous systems that can be treated with cross-linked α-glucan derivatives in this paper include those in industrial environments. Examples of industrial environments in this paper include those in the following industries: energy (e.g., fossil fuels such as oil or natural gas), water (e.g., water treatment and / or purification, industrial water, wastewater treatment), agriculture (e.g., grains, fruits / vegetables, fisheries, aquaculture, dairy, livestock, timber, plants), chemicals (e.g., pharmaceutical processing, chemical processing), food processing / manufacturing, mining, or transportation (e.g., freshwater and / or maritime, train or freight container) industries. Further examples of aqueous systems that can be treated with the cross-linked α-glucan derivatives described herein include those used in water treatment, water storage, and / or other water-containing systems (e.g., pipes / ducts, heat exchangers, condensers, filters / filtration systems, storage tanks, water cooling towers, water cooling systems / equipment, pasteurizers, boilers, sprayers, nozzles, ship hulls, ballast water). Further examples of aqueous systems that can be treated with the cross-linked α-glucan derivatives described herein include those in the following: medical / dental / healthcare environments (e.g., hospitals, clinics, examination rooms, nursing homes; e.g., instrument cleaning), food service environments (e.g., restaurants, staff kitchens, cafeterias), retail environments (e.g., grocery stores, soft drink machines / vending machines), hospitality / tourism environments (e.g., hotels / motels), sports / recreation environments (e.g., swimming pools / bathtubs, spas), or office / home environments (e.g., bathrooms, bathtubs / showers, kitchens, appliances [e.g., washing machines, automatic dishwashing machines, refrigerators, freezers], sprinkler systems, home / building water pipes, water tanks, water heaters). Further examples of aqueous systems treatable with the cross-linked α-glucan derivatives described herein include those disclosed in any of the following: U.S. Patent Application Publication Nos. 2013 / 0029884, 2005 / 0238729, 2010 / 0298275, 2016 / 0152495, 2013 / 0052250, 2015 / 009891, 2016 / 0152495, 2 The following patents are incorporated herein by reference: 017 / 0044468, 2012 / 0207699, 2020 / 0308592, 2024 / 0199766, or 2024 / 0150497; or U.S. Patent Nos. 4,552,591, 4,925,582, 6,478,972, 6,514,458, 6,395,189, 7,927,496, or 8,784,659; or International Patent Application Publication Nos. WO2022 / 178073 or WO 2022 / 178075.In some respects, the aqueous systems that can be addressed herein comprise (i) brine such as seawater, or (ii) an aqueous solution having about 2.0 wt%, 2.25 wt%, 2.5 wt%, 2.75 wt%, 3.0 wt%, 3.25 wt%, 3.5 wt%, 3.75 wt%, 4.0 wt%, 2.5 wt%-4.0 wt%, 2.75 wt%-4.0 wt%, 3.0 wt%-4.0 wt%, 2.5 wt%-3.5 wt%, 2.75 wt%-3.5 wt%, 3.0 wt%-3.5 wt%, 3.0 wt%-4.0 wt%, or 3.0 wt%-3.5 wt%.

[0141] In some aspects, cross-linked α-glucan derivatives can form complexes with hard water salts (e.g., carbonates such as CaCO3) as described herein. Such complexes may, for example, comprise hard water salts encapsulated / covered (e.g., 100%, or at least 80%, 85%, 90%, 95%, 98%, or 99% encapsulation / coverage) by the cross-linked α-glucan derivative. Such complexes are typically water-insoluble; due to this characteristic, such complexes can be readily removed from aqueous compositions. Therefore, a method is further disclosed herein comprising treating an aqueous composition having at least one hard water salt (e.g., carbonates such as CaCO3 or MgCO3, hydroxides such as Ca(OH)2 or Mg(OH)2, sulfates such as CaSO4) with at least one cross-linked α-glucan derivative as described herein, wherein the treatment results in the formation of a water-insoluble complex comprising the hard water salt and the cross-linked α-glucan derivative. In some aspects, such water-insoluble complexes may be stably dispersed or stably dispersible. This method may optionally further include removing all or most of the water-insoluble complexes (complexes formed during the treatment steps) from the aqueous composition. In terms of the extent to which this method removes water-insoluble hard water salts, it may optionally be considered a flocculation method. Water-insoluble complexes comprising at least one cross-linked α-glucan derivative and at least one hard water salt can be used as ingredients in various products, such as paper products. Therefore, this document discloses products comprising complexes containing cross-linked α-glucan derivatives and hard water salts, such as paper.

[0142] Compositions / products comprising at least one crosslinked α-glucan derivative as described herein, such as aqueous or non-aqueous compositions, may be in the form of, for example, household care products, personal care products, industrial products, ingestible products (e.g., food products), medical products, or pharmaceutical products, as described in any of the following: U.S. Patent Application Publication Nos. 2018 / 0022834, 2018 / 0237816, 2018 / 0230241, 20180079832, 2016 / 0311935, 2016 / 0304629, 2015 / 0232785, 2015 / 0368594, 2015 / 0368595, 2016 / 0122445, 2019 / 0202942, or 2019 / 0309096, or International Patent Application Publication No. WO 2016 / 133734, the entire contents of which are incorporated herein by reference. In some aspects, the composition may comprise at least one component / raw material of a home care product, personal care product, industrial product, medical product, pharmaceutical product, or ingestible product (e.g., food product) as disclosed in any of the foregoing disclosures and / or as disclosed in this invention.

[0143] It is believed that, in some respects, the composition can be used to provide one or more of the following physical properties for personal care products, pharmaceutical products, household products, industrial products, medical products, or ingestible products (e.g., food products): for example, thickening, freeze / thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, adhesion, suspension, dispersion, gelling, and reduced mineral hardness.

[0144] The personal care products described herein are not particularly limited and include, for example, skin care compositions, cosmetic compositions, antifungal compositions, and antibacterial compositions. Personal care products described herein may be in the form of, for example, lotions, creams, foams, pastes, balms, ointments, hair oils, gels, liquids, serums, combinations thereof. If desired, the personal care products disclosed herein may include at least one active ingredient. An active ingredient is generally considered to be a component that causes the desired pharmacological effect.

[0145] In some respects, personal care products can be skin care products. Skin care products can be used and / or designed for, for example, general body application or targeted application (e.g., hands or feet). In some respects, skin care products can be used on hair and / or nails (or only on nails). In some respects, skin care products can be applied to the skin to address skin damage associated with dehydration. Skin care products can also be used to address the visual appearance of the skin (e.g., reducing the appearance of flaky, cracked, and / or red skin) and / or the feel of the skin (e.g., reducing skin roughness and / or dryness while improving skin softness and micro-refinement). Typically, skin care products can include at least one active ingredient for treating or preventing skin conditions, providing cosmetic effects, or providing moisturizing benefits to the skin, such as zinc oxide, petrolatum, white petrolatum, mineral oil, cod liver oil, lanolin, dimethicone, stearin, vitamin A, allantoin, calamine, kaolin, glycerin, or colloidal oatmeal, and combinations thereof. Skin care products may include one or more natural moisturizing factors, such as ceramides, hyaluronic acid, glycerin, squalane, amino acids, cholesterol, fatty acids, triglycerides, phospholipids, sphingolipids, urea, linoleic acid, glucosamine, mucopolysaccharides, sodium lactate, or sodium pyrrolidone carboxylate. Other ingredients that may be included in skin care products include, but are not limited to, glycerides, almond oil, low-erucic acid rapeseed oil, squalane, squalene, coconut oil, corn oil, jojoba oil, jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter, soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter, palm oil, cholesterol, cholesterol esters, wax esters, fatty acids, and orange peel oil. In some respects, skin care products may be ointments, lotions, or disinfectants (e.g., hand sanitizers).Skin care products / formulations adapted to be used as aqueous compositions herein may be disclosed, for example, as follows: US20100189669, US 20200093799, US 20080014162, US 20050002889, US 20020039565, US20080213323, US 20040022822, US 20070166249, US 20080152606, US 20080008668, US20140256830, US 20030206932, US 20030114323, US 20110152335, US 20150202139, US20040180026, US 4595586, US 4268526, US 4272519, US 4285967, US 4368189, US4372944, US 4699780, US 4816271, US 4839164, US 4464362, US 5552135, US 5693255, US5976555, US 5607921, US 5618523, US 5798108, US 5356627, US 5811083, US 5939085, US6280714, US 8465973, US 9867774, US 11110049、US 10546658、US 11033480, EP 0321929, or WO 2013092872, all of which are incorporated herein by reference. Skin care products may contain one or more ingredients / additives, such as those disclosed in any of the foregoing references.

[0146] Personal care products mentioned in this article may also take the form of, for example, cosmetics, lipsticks, mascaras, blush, foundation, blush, eyeliner gel, lip liner, lip gloss, other cosmetics, sunscreen, sun lotion, nail polish, nail conditioner, bath gel, shower gel, body wash, facial cleanser, lip balm, skin cream, cream, foam, cold cream, moisturizer, body spray, soap, body scrub, exfoliant, astringent, scruffing lotion, hair removal agent, permanent waving solution, anti-dandruff formulation, antiperspirant composition, deodorant, shaving products, pre-shaving products, after-shaving products, cleansers, skin gels, serums (skin serums), rinse, dental floss compositions, toothpaste, or mouthwash. Examples of personal care products (e.g., cleansers, soaps, scrubs, cosmetics) include carriers or exfoliants (e.g., jojoba beads [jojoba ester beads]) (e.g., about 1-10, 3-7, 4-6, or 5 wt%); such agents may optionally be dispersed within the product.

[0147] In some respects, personal care products can be hair care products. Examples of hair care products described herein include shampoos, conditioners (leave-in or bleach), nourishing hair products, hair dyes, hair coloring products, hair shine products, hair serums, anti-frizz products, split end repair products, mousses, hair sprays, and styling gels. In some embodiments, hair care products may be in the form of liquids, pastes, gels, creams, foams, solids, or powders. The hair care products disclosed in this invention typically comprise one or more of the following ingredients commonly used in the formulation of hair care products: anionic surfactants, such as sodium polyoxyethylene lauryl ether sulfate; cationic surfactants, such as stearoyl trimethylammonium chloride and / or distearyl dimethylammonium chloride; nonionic surfactants, such as glyceryl monostearate, sorbitol monopalmitate and / or polyoxyethylene cetyl ether; humectants, such as propylene glycol, 1,3-butanediol, glycerin, sorbitol, pyroglutamate, amino acids and / or trimethylglycine; hydrocarbons, such as liquid paraffin, petrolatum, solid paraffin, squalane and / or olefin oligomers; higher alcohols, such as stearyl alcohol and / or cetyl alcohol; lipophilic agents; anti-dandruff agents; disinfectants; anti-inflammatory agents; medicinal herbs; water-soluble polymers, such as methylcellulose, hydroxycellulose and / or partially deacetylated chitin; preservatives, such as parabens; ultraviolet absorbers; pearlescent agents; pH adjusters; fragrances; and pigments.

[0148] In some respects, personal care products can be hair care compositions, such as hair styling or setting compositions (e.g., hair gel or shampoo, hair mousse / foam, hair serum) (e.g., foam, cream, paste, non-flow gel, mousse, hair oil, lacquer, hair wax). Hair styling / setting compositions / formulas that can be adapted to the aqueous compositions described herein include, for example, US 20090074697, WO1999048462, US 20130068849, JPH0454116A, US 5304368, AU 667246 B2, US 5413775, US5441728, US 5939058, JP 2001302458 A, US 6346234, US 20020085988, US 7169380, US20090060858, US 20090326151, US 20160008257, WO 2020164769, or US All of the information disclosed in 20110217256 are incorporated herein by reference.Hair care compositions, such as hair styling / setting compositions, may contain one or more ingredients / additives as disclosed in any of the foregoing references, and / or one or more of the following: fragrances / fragrances, aromatherapy essences, vanilla, infusions, antimicrobial agents, stimulants (e.g., caffeine), essential oils, hair dyes, colorants or pigments, anti-greying agents, defoamers, sunscreens / UV blockers (e.g., benzophenone-4), vitamins, antioxidants, surfactants or other wetting agents, mica, silica, metallic flakes or other shimmering materials, conditioning agents (e.g., volatile or non-volatile silicone fluids), antistatic agents, sunscreens, detackifying agents, penetrants, preservatives (e.g., phenoxyethanol, ethylhexylglycerin, benzoates, diazolidinyl urea). This includes urea, butylcarbamate iodopropynyl ester, emollients (e.g., panthenol, isopropyl myristate), rheology-modified or thickening polymers (e.g., acrylate / methacrylamide copolymers, polyacrylic acid [e.g., CARBOMER]), emulsified oil phases, petrolatum, fatty alcohols, glycols and polyols, emulsifiers (e.g., PEG-40 hydrogenated castor oil, oleyl alcohol polyether-20), humectants (e.g., glycerin, octyl glycol), silicone derivatives, proteins, amino acids (e.g., isoleucine), conditioning agents, chelating agents (e.g., EDTA), solvents (e.g., see below), monosaccharides (e.g., dextrose), disaccharides, oligosaccharides, pH-stabilizing compounds (e.g., aminomethylpropanol), film-forming agents (e.g., acrylate / hydroxy acrylate copolymers, polyvinylpyrrolidone / vinyl acetate copolymers, triethyl acetate), and / or any other suitable materials described herein. The hair fixation / styling agents that may be used in this article include PVP (polyvinylpyrrolidone), octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, vinylcaprolactam / PVP / dimethylaminoethyl methacrylate copolymer, AMPHOMER, or any film-forming agent as listed above.

[0149] For example, hair styling / styling compositions may contain a solvent comprising water and optionally a water-miscible (typically polar) organic compound (e.g., liquid or gas), such as alcohols (e.g., ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol), alkylene glycol alkyl ethers, and / or monoalkyl or dialkyl ethers (e.g., dimethyl ether). If an organic compound is contained, it may constitute, for example, about 10%, 20%, 30%, 40%, 50%, or 60% by weight or volume of the solvent (the balance being water). For example, the amount of solvent in the hair styling / styling compositions herein may be about 50 wt%-90 wt%, 60 wt%-90 wt%, 70 wt%-90 wt%, 80 wt%-90 wt%, 50 wt%-95 wt%, 60 wt%-95 wt%, 70 wt%-95 wt%, 80 wt%-95 wt%, or 90 wt%-95 wt%.

[0150] The pharmaceutical products described herein may be in the form of, for example, lotions, liquids, elixirs, gels, suspensions, solutions, creams, foams, serums, or ointments. Furthermore, the pharmaceutical products described herein may be in the form of any personal care product disclosed herein, such as antibacterial or antifungal compositions. The pharmaceutical products may further comprise one or more pharmaceutically acceptable carriers, diluents, and / or pharmaceutically acceptable salts. The compositions described herein may also be used in capsules, encapsulants, tablets, tablet coatings, and as excipients for pharmaceutical preparations and drugs.

[0151] The home care and / or industrial products described herein may take the form of, for example, the following: drywall tape bonding mixes; mortars; slurries; cement plaster; spray plaster; cement mortar; adhesives; pastes; wall / ceiling conditioners; adhesives and processing aids for tape casting, extrusion molding, injection molding, and ceramics; spray adhesives and suspending / dispersing aids for pesticides, herbicides, and fertilizers; fabric care products, such as fabric softeners and laundry detergents; hard surface cleaners; air fresheners; polymer emulsions; latexes; gels, such as water-based gels; surfactant solutions; coatings, such as water-based coatings; protective coatings; adhesives; sealants and caulking agents; inks, such as water-based inks; metalworking fluids; films or coatings; or emulsion-based metal cleaners for electroplating, phosphating, galvanizing, and / or general metal cleaning operations. In some aspects, the compositions described herein are included in fluids as viscosity modifiers and / or drag reducers; such uses include downhole operations / fluids (e.g., hydraulic fracturing and enhanced oil recovery).

[0152] Examples of ingestible products described herein include foods, beverages, animal feed, animal health and / or nutritional products, and / or pharmaceutical products. The intended use of the compositions disclosed herein in ingestible products may, for example, provide texture, increase volume, and / or thicken.

[0153] Some aspects of this document relate to (i) brine such as seawater, or (ii) an aqueous solution having about 2.0 wt%, 2.25 wt%, 2.5 wt%, 2.75 wt%, 3.0 wt%, 3.25 wt%, 3.5 wt%, 3.75 wt%, 4.0 wt%, 2.5 wt%-4.0 wt%, 2.75 wt%-4.0 wt%, 3.0 wt%-4.0 wt%, 2.5 wt%-3.5 wt%, 2.75 wt%-3.5 wt%, 3.0 wt%-3.5 wt%, 3.0 wt%-4.0 wt%, or 3.0 wt%-3.5 wt%, of a salt or combination of salts (e.g., including at least NaCl), and (i) or (ii) having at least one cross-linked α-glucan derivative as disclosed herein. The concentration of the cross-linked α-glucan derivative in such water (i) or (ii) may be, for example, about, at least about, or less than about 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 0.1 wt%-0.6 wt%, 0.1 wt%-0.5 wt%, 0.1 wt%-0.4 wt%, 0.1 wt%-0.3 wt%, or 0.1 wt%-0.2 wt%. Despite the relatively high salt concentration in such aqueous compositions, it is envisioned that the cross-linked α-glucan derivative can, in some respects, be completely or substantially retained in the solution or dispersion and provide viscosity. Such solutions or dispersions, as described herein, with viscosity adjusted by (i) or (ii) of cross-linked α-glucan derivatives, may be used in systems utilizing such solutions or dispersions (e.g., any system described herein, such as downhole operations).

[0154] Further examples of using the compositions disclosed herein in ingestible products include their use as: expansion, binding, and / or coating ingredients; carriers for coloring agents, flavoring / fragrance agents, and / or high-intensity sweeteners; spray drying aids; expansion, thickening, dispersing, and / or emulsifying agents; and ingredients for promoting hydration (humectants). Illustrative examples of products that can be prepared having the compositions described herein include food products, beverage products, pharmaceutical products, nutritional products, and sports products. Examples of beverage products described herein include concentrated beverage mixtures, carbonated beverages, non-carbonated beverages, fruit-flavored beverages, fruit juices, tea, coffee, milk syrup, powdered beverages, liquid concentrates, dairy beverages, ready-to-drink (RTD) products, smoothies, alcoholic beverages, flavored water, and combinations thereof. Examples of food products described herein include baked goods (e.g., bread), confectionery, frozen dairy products, meat, artificial / synthetic / cultured meat, cereal products (e.g., breakfast cereals), dairy products (e.g., yogurt), condiments (e.g., mustard, ketchup, mayonnaise), snack bars, soups, seasonings, mixtures, pre-made foods, baby food, dietary preparations, peanut butter, syrups, sweeteners, food coatings, pet food, animal feed, animal health and nutrition products, dried fruit, sauces, gravy, jams / jelly, dessert products, spreads, batters, breadcrumbs, seasoning mixtures, frosting, etc. In some respects, the compositions described herein may provide or enhance the effervescence of beverages such as dairy beverages, non-dairy alternative beverages (e.g., “vegan” milk such as soy milk, almond milk, or coconut milk), dairy creamers, and / or non-dairy creamers (e.g., for hot beverages such as coffee [e.g., cappuccino], tea [e.g., chai tea]).

[0155] In some aspects, compositions comprising at least one crosslinked α-glucan derivative described herein may be in the form of fabric care compositions. For example, fabric care compositions may be used for hand washing, machine washing, and / or other purposes, such as soaking and / or pretreatment of fabrics. Fabric care compositions may take the form of: for example, laundry detergents; fabric conditioners; any product added during washing, rinsing, or drying; unit doses or sprays. Fabric care compositions in liquid form may be in the form of aqueous compositions. In other embodiments, fabric care compositions may be in dry forms, such as granular detergents or fabric softener sheets added to a dryer. Other non-limiting examples of fabric care compositions may include: general-purpose or heavy-duty detergents in granular or powder form; general-purpose or heavy-duty detergents in liquid, gel, or paste form; liquid or dry detergents for delicate fabrics (e.g., fine clothing); cleaning aids such as bleaching additives, “stain remover sticks,” or pretreatments; products containing a substrate, such as dry and wet wipes, pads, or sponges; sprays and mists; water-soluble unit dose products; water-dispersible unit dose products (e.g., products containing dispersible fibers). As another example, the compositions described herein may be in the form of liquid, gel, powder, hydrocolloid, aqueous solution, granules, tablet, capsule, beads or lozenges, single-compartment pouch, multi-compartment pouch, single-compartment sachet or multi-compartment sachet.

[0156] The detergent compositions described herein can be in any useful form, such as powder, granules, paste, rod, unit dose, or liquid. Liquid detergents can be aqueous, typically containing up to about 70 wt% water and 0 wt% to about 30 wt% organic solvent. Liquid detergents can also be in a tight gel-type form containing only about 30 wt% water.

[0157] Detergent compositions (e.g., compositions of fabric care products or any other products described herein) typically comprise one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, semipolar nonionic surfactants, and mixtures thereof. In some embodiments, the surfactant is present at a level from about 0.1% to about 60%, while in alternative embodiments the level is from about 1% to about 50%, and in still further embodiments the level is from about 5% to about 40%, by weight of the detergent composition. Typically, detergents will contain from 0 wt% to about 50 wt% of anionic surfactants, such as linear alkylbenzene sulfonates (LAS), α-olefin sulfonates (AOS), alkyl sulfates (fatty alcohol sulfates) (AS), alcohol ethoxysulfates (AEOS or AES), secondary alkyl sulfonates (SAS), α-sulfonyl fatty acid methyl esters, alkyl- or alkenyl succinic acids, or soaps. Additionally, the detergent composition may optionally contain 0 wt% to about 40 wt% of a nonionic surfactant, such as an alcohol ethoxylate (AEO or AE), a carboxylated alcohol ethoxylate, a nonylphenol ethoxylate, an alkyl polyglycoside, an alkyl dimethylamine oxide, an ethoxylated fatty acid monoethanolamide, a fatty acid monoethanolamide, or a polyhydroxyalkyl fatty acid amide (as described, for example, in WO92 / 06154, which is incorporated herein by reference). However, in some aspects, the detergent composition does not contain a surfactant, or has less than 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.25 wt%, 0.1 wt%, 0.05 wt%, or 0.025 wt% of a surfactant (e.g., such a “detergent composition” may optionally be referred to as a “composition,” a “washing composition,” or a “treatment composition”; in some aspects, any disclosure herein of a detergent composition does not necessarily require the inclusion of a surfactant).

[0158] In addition to the cross-linked α-glucan derivatives disclosed herein that can act as builder agents, the detergent compositions herein may optionally comprise one or more detergent builder agents or builder agent systems. In some aspects, oxidized α-1,3-glucan may be included as a co-builder agent; oxidized α-1,3-glucan compounds used herein are disclosed in U.S. Patent Application Publication No. 2015 / 0259439. In some aspects incorporating at least one builder agent, the cleaning composition comprises at least about 1%, from about 3% to about 60%, or even from about 5% to about 40% of the builder agent by weight of the composition. Examples of building blocks include alkali metal, ammonium, and alkanol ammonium salts of polyphosphates; alkali metal silicates, alkaline earth metals, and alkali metal carbonates; aluminosilicates; polycarboxylic acid compounds; ether hydroxy polycarboxylic acid esters; copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid; various alkali metal, ammonium, and substituted ammonium salts of polyacetic acid, such as ethylenediaminetetraacetic acid and hypozoxytriacetic acid; together with polycarboxylic acids, such as hexacarboxylic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts. Other examples of detergent builders or complexing agents include zeolites, diphosphates, triphosphates, phosphonates, diphosphonates (e.g., 1-hydroxyethylidene-1,1-diphosphonic acid [HEDP]), citrates, nitrotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTMPA), alkyl or alkenyl succinic acid, soluble silicates or layered cinnamates (e.g., SKS-6 from Hoechst).

[0159] In some embodiments, the builder forms a water-soluble hard ionic complex (e.g., a chelating builder), such as citrate and polyphosphate (e.g., sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate, and mixtures of sodium tripolyphosphate and potassium tripolyphosphate, etc.). Any suitable builder is contemplated to be available in this disclosure, including those known in the art (see, for example, EP 2100949).

[0160] In some embodiments, suitable builders may include phosphate builders and nonphosphate builders. In some embodiments, the builder is a phosphate builder. In some embodiments, the builder is a nonphosphate builder. The builder may be used at levels ranging from 0.1% to 80%, or from 5% to 60%, or from 10% to 50% by weight of the composition. In some embodiments, the product comprises a mixture of phosphate and nonphosphate builders. Suitable phosphate builders include monophosphates, diphosphates, tripolyphosphates, or oligomeric polyphosphates, including alkali metal salts of these compounds, including sodium salts. In some embodiments, the builder may be sodium tripolyphosphate (STPP). Additionally, the composition may contain carbonates and / or citrates, preferably citrates, to help achieve a neutral pH composition. Other suitable nonphosphate builders include polycarboxylic acids and their partially or fully neutralized salts, homopolymers and copolymers of monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. In some embodiments, the salts of the above compounds comprise ammonium salts and / or alkali metal salts, i.e., lithium salts, sodium salts, and potassium salts, including sodium salts. Suitable polycarboxylic acids include acyclic, alicyclic, heterocyclic, and aromatic carboxylic acids, wherein in some embodiments they may contain at least two carboxyl groups, which in each case are separated from each other, and in some cases are separated by no more than two carbon atoms.

[0161] The detergent compositions described herein may contain at least one chelating agent. Suitable chelating agents include, but are not limited to, copper, iron, and / or manganese chelating agents and mixtures thereof. In embodiments using at least one chelating agent, the composition contains from about 0.1% to about 15% or even from about 3.0% to about 10% of the chelating agent by weight of the composition.

[0162] The detergent compositions described herein may contain at least one depositing aid. Suitable depositing aids include, but are not limited to, polyethylene glycol, polypropylene glycol, polycarboxylate, detergency polymers (such as polyterephthalic acid), clays such as kaolin, montmorillonite, palygorskite, illite, bentonite, hydrous kaolin, and mixtures thereof.

[0163] The detergent compositions described herein may contain one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidinone, and polyvinylimidazole or mixtures thereof. Additional dye transfer inhibitors include manganese phthalocyanine, peroxidase, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidinone and polyvinylimidazole, and / or mixtures thereof; chelating agents, examples of which include ethylenediaminetetraacetic acid (EDTA); diethylenetriaminepentamethylenephosphonic acid (DTPMP); hydroxyethanediphosphonic acid (HEDP); ethylenediamine N,N'-disuccinic acid (EDDS); methylglycinin diacetic acid (MGDA); diethylenetriaminepentaacetic acid (DTPA); and propylenediaminetetraacetic acid (PDT). A); 2-hydroxypyridine-N-oxide (HPNO); or methylglycine diacetic acid (MGDA); N,N-diacetic acid (N,N-dicarboxymethylglutamate tetrasodium salt (GLDA); N-dioxotriacetic acid (NTA); 4,5-dihydroxyisophthalic acid; citric acid and any salt thereof; N-hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (EDTP) and its derivatives, which may be used alone or in combination with any of the above. In embodiments using at least one dye transfer inhibitor, the compositions herein may contain from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3% of the at least one dye transfer inhibitor by weight of the composition.

[0164] The detergent compositions described herein may contain silicates. In some of these embodiments, sodium silicate (e.g., sodium disilicate, sodium metasilicate, and / or crystalline folin silicate) may be used. In some embodiments, the silicate is present at a level from about 1% to about 20% by weight of the composition. In some embodiments, the silicate is present at a level from about 5% to about 15% by weight of the composition.

[0165] The detergent compositions described herein may contain dispersants. Suitable water-soluble organic materials include, but are not limited to, homopolymerized or copolymerized acids or their salts, wherein the polycarboxylic acids comprise at least two carboxyl radicals separated from each other by no more than two carbon atoms.

[0166] The detergent compositions described herein may additionally contain, for example, one or more enzymes as disclosed above. In some aspects, the detergent composition may contain one or more enzymes, each at a level from about 0.00001% to about 10% by weight of the composition, and the balance being cleaning aids by weight of the composition. In some other aspects, the detergent composition may also contain each enzyme at a level from about 0.0001% to about 10%, from about 0.001% to about 5%, from about 0.001% to about 2%, or from about 0.005% to about 0.5% by weight of the composition. The enzymes contained in the detergent compositions herein may be stabilized using conventional stabilizers such as: polyols, such as propylene glycol or glycerol; sugars or sugar alcohols; lactic acid; boric acid or boric acid derivatives (e.g., aromatic borate esters).

[0167] In some respects, in addition to crosslinked α-glucan derivatives as disclosed herein, detergent compositions may also contain one or more other types of polymers. Examples of other types of polymers that may be used herein include carboxymethyl cellulose (CMC), dextran, poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly(vinyl alcohol) (PVA), polycarboxylic acid esters such as polyacrylates, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0168] The detergent compositions described herein may contain a bleaching system. For example, the bleaching system may contain an H₂O₂ source such as perboric acid or percarbonic acid, which may be combined with a bleaching activator that forms a peracid (such as tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS)). Alternatively, the bleaching system may contain a peroxyacid (e.g., an amide, imide, or sulfone-type peroxyacid). Alternatively, the bleaching system may be an enzymatic bleaching system containing a perhydrolase, such as the system described in WO 2005 / 056783.

[0169] The detergent compositions described herein may also contain conventional detergent ingredients such as fabric conditioners, clays, foam promoters, foam inhibitors, corrosion inhibitors, soil suspenders, anti-redeposition agents, dyes, bactericides, color-changing inhibitors, optical brighteners, or fragrances. The pH of the detergent compositions described herein (measured in an aqueous solution at the concentration used) is generally neutral or alkaline (e.g., pH from about 7.0 to about 11.0).

[0170] Examples of suitable anti-redeposition agents and / or clay stain removers for use in the fabric care products described herein include polyethoxylated zwitterionic surfactants, water-soluble copolymers of acrylic acid or methacrylic acid with acrylic acid or methacrylic acid-ethylene oxide condensates (e.g., U.S. Patent No. 3,719,647), cellulose derivatives such as carboxymethyl cellulose and hydroxypropyl cellulose (e.g., U.S. Patent Nos. 3,597,416 and 3,523,088), and mixtures comprising nonionic alkyl polyethoxylated surfactants, polyethoxylated quaternary cationic surfactants, and fatty amide surfactants (e.g., U.S. Patent No. 4,228,044). Other non-limiting examples of suitable anti-redeposition and clay stain removers are disclosed in U.S. Patent Nos. 4,597,898 and 4,891,160 and International Patent Application Publication No. WO 95 / 32272, all of which are incorporated herein by reference.

[0171] Specific forms of detergent compositions suitable for the purposes disclosed herein are disclosed, for example, in US20090209445 A1, US 20100081598 A1, US 7001878 B2, EP 1504994 B1, WO 2001085888A2, WO 2003089562 A1, WO 2009098659 A1, WO 2009098660 A1, WO 2009112992 A1, WO2009124160 A1, WO 2009152031 A1, WO 2010059483 A1, WO 2010088112 A1, WO2010090915 A1, WO 2010135238 A1, and WO 2011094687. All of the following are incorporated herein by reference: A1, WO 2011094690 A1, WO2011127102 A1, WO 2011163428 A1, WO 2008000567 A1, WO 2006045391 A1, WO2006007911 A1, WO 2012027404 A1, EP 1740690 B1, WO 2012059336 A1, US 6730646 B1, WO 2008087426 A1, WO 2010116139 A1, and WO 2012104613 A1.

[0172] The laundry detergent compositions described herein may optionally be heavy-duty (general purpose) laundry detergent compositions. Exemplary heavy-duty laundry detergent compositions comprise cleaning surfactants (10%-40% wt / wt), including anionic cleaning surfactants (selected from the group consisting of linear, branched, or random, substituted or unsubstituted alkyl sulfates, alkyl sulfonates, alkyl alkoxylated sulfates, alkyl phosphates, alkyl phosphonates, alkyl carboxylates, and / or mixtures thereof) and optionally nonionic surfactants (selected from the group consisting of linear, branched, or random, substituted or unsubstituted alkyl alkoxylated alcohols, such as C8-C18 alkyl ethoxylated alcohols and / or C6-C12 alkylphenol alkoxylates), wherein the weight ratio of the anionic cleaning surfactant (having a hydrophilicity index (HIc) from 6.0 to 9) to the nonionic cleaning surfactant is greater than 1:1. Suitable cleaning surfactants also include cationic cleaning surfactants (selected from the group consisting of alkylpyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and / or mixtures thereof); zwitterionic and / or amphoteric cleaning surfactants (selected from the group consisting of alkanolamine sulfobetaine); amphoteric surfactants; semi-polar nonionic surfactants and mixtures thereof.

[0173] The detergent compositions described herein, such as heavy-duty laundry detergent compositions, may optionally include surface-enhancing polymers consisting of: amphiphilic alkoxylated grease-cleaning polymers (selected from the group consisting of alkoxylated polymers having branched hydrophilic and hydrophobic properties, such as alkoxylated polyalkylimides (in the range of 0.05 wt% to 10 wt%)) and / or random graft polymers (typically comprising a hydrophilic backbone containing monomers selected from the group consisting of: unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydrides, saturated polyols (such as glycerol) and mixtures thereof; and one or more hydrophobic side chains selected from the group consisting of: C4-C25 alkyl, polypropylene, polybutene, saturated C1-C6 monocarboxylic acid vinyl esters, C1-C6 alkyl esters of acrylic acid or methacrylic acid and mixtures thereof).

[0174] The detergent compositions described herein, such as heavy-duty laundry detergent compositions, may optionally include additional polymers, such as detergency polymers (including anionic-terminated polyesters (e.g., SRP1); polymers in a random or block configuration comprising at least one monomer unit selected from sugars, dicarboxylic acids, polyols, and combinations thereof; polymers and copolymers of ethylene glycol terephthalate-based polymers in a random or block configuration, such as REPEL-O-TEX SF, SF-2, and SRP6, TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN300, and SRN325, MARLOQUEST SL); and one or more anti-redeposition agents described herein (0.1 wt% to 10 wt%). (wt%), including carboxylic acid ester polymers, such as polymers containing at least one monomer selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesoconic acid, citraconic acid, methylene malonic acid and any mixture thereof; vinylpyrrolidone homopolymers; and / or polyethylene glycol, with a molecular weight range from 500 to 100,000 Da; and polymeric carboxylic acid esters (such as maleate / acrylate random copolymers or polyacrylate homopolymers).

[0175] The detergent compositions described herein, such as heavy-duty laundry detergent compositions, may optionally further comprise saturated or unsaturated fatty acids, preferably saturated or unsaturated C12-C24 fatty acids (0 wt% to 10 wt%); depositing aids (examples of which include polysaccharides; cellulose polymers; polypropylene dimethyl ammonium halide (DADMAC); and copolymers of DADMAC with vinylpyrrolidone, acrylamide, imidazole, imidazoline halides and mixtures thereof (in random or block configurations); cationic guar gum; cationic starch; cationic polyacrylamide, and mixtures thereof).

[0176] The detergent compositions described herein, such as heavy-duty laundry detergent compositions, may optionally further include dye transfer inhibitors, examples of which include manganese phthalocyanine, peroxidase, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidinone and polyvinylimidazole and / or mixtures thereof; chelating agents, examples of which include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), hydroxyethanediphosphonic acid (HEDP), ethylenediamine N,N'-disuccinic acid (EDDS), methylglycine diacetic acid (MGDA), and diethylenetriaminepentamethylenephosphonic acid (DTPMP). Triaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO), or methylglycine diacetic acid (MGDA), N,N-diacetic acid of glutamate (N,N-dicarboxymethylglutamate tetrasodium salt (GLDA), hyponitrotriacetic acid (NTA), 4,5-dihydroxyisophenylsulfonic acid, citric acid and any salt thereof, N-hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (EDTP), and their derivatives.

[0177] The detergent compositions described herein, such as heavy-duty laundry detergent compositions, may optionally include silicone- or fatty acid-based foam inhibitors; tinting dyes, calcium and magnesium cations, visual signaling components, antifoaming agents (0.001 wt% to about 4.0 wt%), and / or structural agents / thickeners (0.01 wt% to 5 wt%) selected from the group consisting of: diglycerides and triglycerides, polyethylene distearate, microcrystalline cellulose, ultrafine cellulose, biopolymers, xanthan gum, gellan gum, and mixtures thereof. A structural agent may also be referred to as a structural agent.

[0178] For example, the detergents described herein may be in the form of heavy-duty dry / solid laundry detergent compositions. Such detergents may include: (i) cleaning surfactants, such as any anionic cleaning surfactant disclosed herein, any nonionic cleaning surfactant disclosed herein, any cationic cleaning surfactant disclosed herein, any zwitterionic and / or amphoteric cleaning surfactant disclosed herein, any amphoteric surfactant, any semi-polar nonionic surfactant, and mixtures thereof; (ii) builders, such as any phosphate-free builders (e.g., zeolite builders in the range of 0 wt% to less than 10 wt%), any phosphate builders (e.g., sodium tripolyphosphate in the range of 0 wt% to less than 10 wt%), citric acid, citrates, and hypozinotriacetic acid, any silicates (e.g., sodium silicate, potassium silicate, or sodium metasilicate in the range of 0 wt% to less than 10 wt%); any carbonates (e.g., sodium carbonate and / or sodium bicarbonate in the range of 0 wt% to less than 80 wt%), and mixtures thereof; (iii) Bleaching agents, such as any photobleaching agent (e.g., zinc phthalocyanine sulfonate, aluminum phthalocyanine sulfonate, succinate dyes and mixtures thereof); any hydrophobic or hydrophilic bleaching activators (e.g., dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine-TAED, nonanoyloxybenzenesulfonate-NOBS, nitrile quaternary ammonium salts and mixtures thereof); any hydrogen peroxide source (e.g., inorganic peroxide hydrate salts, examples of which include mono- or tetrahydrated sodium salts of perborates, percarbonates, persulfates, superphosphates or persilicates); any pre-formed hydrophilic and / or hydrophobic peracids (e.g., percarboxylic acids and salts, percarbonates and salts, periodic acids and salts, peroxymonosulfate and salts, and mixtures thereof); and / or (iv) Any other components such as bleaching catalysts (e.g., imine bleaching promoters, examples of which include imine cations and polyanions, imine zwitterions, modified amines, modified amine oxides, N-sulfonylimides, N-phosphonylimides, N-acylimides, thiadiazole dioxide, perfluoroimides, cyclic glycosyl groups and mixtures thereof) and metal-containing bleaching catalysts (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations and auxiliary metal cations (such as zinc or aluminum)) and chelates (such as EDTA, ethylenediaminetetra(methylenephosphonic acid)).

[0179] Detergents used in this document, such as those for fabric care (e.g., clothing), may be contained in, for example, unit doses (e.g., pouches or sachets). The unit dose may be in the form of a water-soluble outer membrane that completely encapsulates the liquid or solid detergent composition. The unit dose may contain a single compartment, or at least two, three, or more compartments. Multiple compartments may be arranged in a stacked or side-by-side orientation. The unit dose described herein is typically a closed structure of any form / shape suitable for containing and protecting its contents without allowing the contents to dissipate before contact with water. In some aspects, the unit dose may contain water-dispersible or water-soluble fibers.

[0180] In some aspects, compositions comprising at least one crosslinked α-glucan derivative described herein may be in the form of a fabric softener or may contain a fabric softener (liquid fabric softener). An example of such a composition is typically a rinsing agent (e.g., a laundry detergent, such as that used in a laundry rinse cycle in a washing machine) used after cleaning a fabric-containing material described herein with a laundry detergent composition. The concentration of the crosslinked α-glucan derivative in the fabric softener-containing composition (e.g., rinsing agent) may be, for example, about, or at least about 20, 30, 40, 50, 60, 70, 80, 20-80, 20-70, 20-60, 30-80, 30-70, 30-60, 40-80, 40-70, or 40-60 ppm. The concentration of fabric softener in the composition (e.g., rinsing agent) may be, for example, about or at least about 50, 75, 100, 150, 200, 300, 400, 500, 600, 50-600, 50-500, 50-400, 50-300, 50-200, 100-600, 100-500, 100-400, 100-300, 100-200, 10-600, 50-500, 50-400, 50-300, 50-200, 200-600, 200-500, 200-400, or 200-300 ppm. The fabric softener concentration may be based on the total fabric softener composition added (not necessarily on individual fabric softener components) or on one or more fabric softeners in the fabric softener formulation. The fabric softener described herein may further comprise one or more of the following: fabric softener (e.g., diethyl ester dimethyl ammonium chloride), antistatic agent, fragrance, wetting agent, viscosity modifier (e.g., calcium chloride), pH buffer / buffer agent (e.g., formic acid), antimicrobial agent, antioxidant, free radical scavenger (e.g., ammonium chloride), chelating agent / builder (e.g., diethylenetriaminepentaacetate), defoamer / lubricant (e.g., polydimethylsiloxane), preservative (e.g., benzisothiazolinone), and colorant. In some aspects, the fabric softener may further comprise one or more of the following: fabric softener, viscosity modifier, pH buffer / buffer agent, free radical scavenger, chelating agent / builder, and defoamer / lubricant. The fabric softener may be fragrance-free and / or dye-free, or in some aspects may contain less than about 0.1 wt% fragrance and / or dye.In some respects, fabric softeners applicable herein may be disclosed in any of the following: U.S. Patent Application Publication Nos. 2014 / 0366282, 2001 / 0018410, 2006 / 0058214, 2021 / 0317384, or 2006 / 0014655; or International Patent Application Publication Nos. WO 2007 / 078782, WO 1998 / 016538, WO 1998 / 012293, WO 1998007920, WO 2000 / 070004, WO 2009 / 146981, WO 2000 / 70005, or WO 2013087366, which are incorporated herein by reference. If desired, some brands of fabric softeners suitable for use herein include DOWNY, DOWNY ULTRA, DOWNY INFUSIONS, ALL, SNUGGLE, LENOR, and GAIN. In some respects, liquid fabric softener products (e.g., as they are present prior to use in a laundry rinse cycle) can be formulated to include one or more cross-linked α-glucan derivatives. In some respects, fabric softeners can be supplied in unit doses, as disclosed herein with respect to detergents.

[0181] The compositions disclosed herein comprising at least one cross-linked α-glucan derivative may, for example, be in the form of a dishwashing detergent composition. Examples of dishwashing detergents include automatic dishwashing detergents (typically used in dishwashing machines) and hand-washing dishwashing detergents. Dishwashing detergent compositions may, for example, be in any dry or liquid / aqueous form as disclosed herein. Components that may be included in some aspects of a dishwashing detergent composition include, for example, one or more of the following: phosphates; oxygen- or chlorine-based bleach; nonionic surfactants; alkaline salts (e.g., metasilicates, alkali metal hydroxides, sodium carbonate); any active enzymes disclosed herein; corrosion inhibitors (e.g., sodium silicate); defoamers; additives that slow the removal of glaze and patterns from ceramics; fragrances; anti-caking agents (in granular detergents); starch (in tablet-based detergents); gelling agents (in liquid / gel-based detergents); and / or sand (in powdered detergents).

[0182] Dishwashing detergents, such as those for automatic dishwashers or liquid dishwashing detergents, may contain (i) nonionic surfactants, including any ethoxylated nonionic surfactants, alcohol alkoxylated surfactants, epoxy-terminated poly(oxyalkylated) alcohols, or amine oxide surfactants present in amounts from 0 to 10 wt%; (ii) approximately 5-60 The range of detergent builders in the wt% range includes any phosphate builders (e.g., monophosphate, diphosphate, tripolyphosphate, other oligomeric polyphosphates, sodium tripolyphosphate-STPP), any phosphate-free builders (e.g., amino acid-based compounds including methyl-glycine-diacetic acid [MGDA] and its salts or derivatives, glutamic acid-N,N-diacetic acid [GLDA] and its salts or derivatives, iminodisuccinic acid (IDS) and its salts or derivatives, carboxymethyl inulin and its salts or derivatives, hypozinotriacetic acid [NTA], diethylenetriaminepentaacetic acid [DTPA], β-alanine diacetic acid [B-ADA] and its salts), homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts in the range of 0.5 wt% to 50 wt%, or sulfonated / carboxylated polymers in the range of about 0.1 wt% to about 50 wt%; (iii) in the range of about 0.1 wt% to about 10 wt%. (iv) Drying aids in the range of about 1 wt% to about 20 wt% (e.g., polyesters, especially anionic polyesters (optionally with additional monomers having 3 to 6 functional groups that favor polycondensation - typically acid, alcohol or ester functional groups), polycarbonate-, polyurethane- and / or polyurea-polyorganosiloxane compounds or their precursors, especially reactive cyclic carbonates and urea types); (v) Silicates (e.g., sodium silicate or potassium silicate, such as disodium silicate, sodium metasilicate and crystalline succinate) in the range of about 1 wt% to about 20 wt%; (v) Inorganic bleaching agents (e.g., peroxyhydrate salts such as perborates, percarbonates, superphosphates, persulfates and persilicates) and / or organic bleaching agents (e.g., organic peroxy acids such as diacid- and tetraacyl peroxides, especially disperoxydodecanoic acid, disperoxytetradecanoic acid and disperoxyhexadecanoic acid); (vi) Bleaching activators (e.g., in the range of about 0.1 wt% to about 10 wt%). (vii) Organic peracid precursors in the range of about 0.1 wt% and / or bleaching catalysts (e.g., manganese triazacyclononane and related complexes; Co, Cu, Mn and Fe bispyridineamines and related complexes; and cobalt(III) pentamineacetate and related complexes); (vii) Metal care agents in the range of about 0.1 wt% to 5 wt% (e.g., benzotriazole, metal salts and complexes, and / or silicates); (viii) Glass corrosion inhibitors in the range of about 0.1 wt% to 5 wt% (e.g., salts and / or complexes of magnesium, zinc, or bismuth); and / or (ix) Any active enzymes disclosed herein (ranging from about 0.01 to 5 wt%).The dishwashing detergent composition contains 0 mg active enzyme per gram of automatic dishwashing detergent and enzyme stabilizer components (e.g., oligosaccharides, polysaccharides, and inorganic divalent metal salts). In some aspects, the dishwashing detergent components or the entire composition (but correspondingly adapted to include the cross-linked α-glucan derivatives described herein) may be as disclosed in U.S. Patent Nos. 8,575,083 or 9,796,951, U.S. Patent Application Publication No. 2017 / 0044468, or International Patent Application Publication Nos. WO 2023 / 111170, WO 2023 / 156427, WO 2023 / 105006, WO 2022 / 214385, or WO 2022189536 (each of which is incorporated herein by reference). For example, the cross-linked α-glucan derivatives described herein may replace or partially replace one or more builder ingredients (e.g., one or more acrylate compounds, and / or any other non-renewable or non-biodegradable builder ingredients) in automatic dishwashing detergents, such as those disclosed in any of the foregoing references or embodied in product brands disclosed herein. In some aspects, in addition to the cross-linked α-glucan derivatives described herein, dishwashing detergents may also contain at least one other builder (e.g., any disclosed in laundry detergents or dishwashing detergents herein, such as HEDP).

[0183] Detergents described herein, such as detergents for dishwashing, may be contained in, for example, unit doses (e.g., pouches or sachets) (e.g., water-soluble unit dose products, water-dispersible unit doses containing fibers), and may be as described above for fabric care detergents, but may contain suitable dishwashing detergent compositions.

[0184] It is believed that many commercially available detergent formulations are suitable for including at least one cross-linked α-glucan derivative as disclosed herein. Examples of commercially available detergent formulations include PUREX. ® ULTRAPACKS (Henkel), FINISH ® QUANTUM (Reckitt Benckiser), CLOROX™ 2 PACKS (Clorox), OXICLEAN MAX FORCE POWER PAKS (Church & Dwight), TIDE ® STAIN RELEASE, CASCADE ® ACTIONPACS and TIDE ® PODS™ (Procter & Gamble).

[0185] The compositions disclosed herein comprising at least one cross-linked α-glucan derivative may, for example, be in the form of oral care compositions. Examples of oral care compositions include dental cleaning agents, toothpastes, mouthwashes, oral rinses, chewing gums, and edible strips that provide some form of oral care (e.g., for the treatment or prevention of cavities [dental caries], gingivitis, plaque, tartar, and / or periodontal disease). Oral care compositions may also be used to treat “oral surfaces,” which encompass any soft or hard surface within the oral cavity, including the surfaces of the tongue, hard and soft palate, buccal mucosa, gingiva, and teeth. “Dental surfaces” herein refers to the surfaces of natural teeth or the hard surfaces of artificial dentition (including, for example, crowns, caps, fillings, bridges, dentures, or dental implants).

[0186] The oral care compositions described herein may contain, for example, about 0.01 wt% to 15.0 wt% (e.g., about 0.1 wt% to 10 wt% or about 0.1 wt% to 5.0 wt%, about 0.1 wt% to 2.0 wt%) of cross-linked α-glucan derivatives as disclosed herein. The cross-linked α-glucan derivatives contained in the oral care compositions may sometimes be provided therein as thickeners and / or dispersants that can be used to impart a desired consistency and / or mouthfeel to the composition. One or more other thickeners or dispersants may also be provided in the oral care compositions described herein, such as carboxyethylene polymers, carrageenan (e.g., L-carrageenan), natural gums (e.g., karaya gum, xanthan gum, gum arabic, astragalus gum), colloidal magnesium aluminum silicate, or colloidal silica.

[0187] The oral care compositions described herein may be, for example, toothpaste or other dental cleaning agents. Such compositions, and any other oral care compositions described herein, may additionally contain, but are not limited to, one or more anti-caries agents, antimicrobial or antibacterial agents, anti-tartar or plaque control agents, surfactants, abrasives, pH adjusters, foaming agents, humectants, flavorings, sweeteners, pigments / colorings, whitening agents, and / or other suitable components. Examples of oral care compositions to which cross-linked α-glucan derivatives described herein may be added are disclosed in U.S. Patent Application Publications 2006 / 0134025, 2002 / 0022006, and 2008 / 0057007, which are incorporated herein by reference.

[0188] The caries prevention agents described herein can be orally acceptable sources of fluoride ions. Suitable sources of fluoride ions include, for example, fluorides, monofluorophosphates and fluorosilicates, and amine fluorides, including olafluridine (N'-octadecyltrimethylenediamine-N,N,N'-tris(2-ethanol)-dihydrofluoride). For example, the caries prevention agent can be present in an amount providing a total of about 100-20000 ppm, about 200-5000 ppm, or about 500-2500 ppm of fluoride ions to the composition. In oral care compositions where sodium fluoride is the sole source of fluoride ions, for example, an amount of about 0.01-5.0 wt%, about 0.05-1.0 wt%, or about 0.1-0.5 wt% sodium fluoride can be present in the composition.

[0189] Antimicrobial or antibacterial agents in the oral care compositions applicable to this document include, for example, phenolic compounds (e.g., 4-allyl catechol; parabens such as benzyl paraben, butyl paraben, ethyl paraben, methyl paraben, and propyl paraben; 2-benzylphenol; butylated hydroxyanisole; butylated hydroxytoluene; capsaicin; carvacrol; lignochlorophenol; eugenol; guaiacol; halogenated bisphenols, such as hexachlorophenol). hexachlorophene and bromochlorophene; 4-hexylresorcinol; 8-hydroxyquinoline and its salts; salicylates, such as menthyl salicylate, methyl salicylate and phenyl salicylate; phenol; pyrocatechol; N-salicylic acid aniline; thymol; halodiphenyl ether compounds; copper(II) compounds (e.g., copper(II) chlorides, fluorides, sulfates and hydroxides); zinc ion sources (e.g., zinc acetates). Citrates, gluconates, glycine salts, oxides and sulfates); phthalic acid and its salts (e.g., magnesium monopotassium phthalate); dioctylhydrochloride; oterin; sanguisorbide; benzalkonium chloride; duloxetine bromide; alkylpyridine chlorides (e.g., hexadecylpyridine chloride, tetradecylpyridine chloride, N-tetradecyl-4-ethylpyridine chloride); iodine; sulfonamides; biguanides (e.g., aricetin, chlorhexidine, chlorhexidine digluconate); azacyclohexane derivatives ( For example, dimoptisol, octopiol; magnolia extract, grape seed extract, rosemary extract, menthol, geraniol, citral, eucalyptol; antibiotics (e.g., vogmundin, amoxicillin, tetracycline, doxycycline, minocycline, metronidazole, neomycin, kanamycin, clindamycin), and / or any antibacterial agent disclosed in U.S. Patent 5,776,435 (which is incorporated herein by reference). One or more antimicrobial agents may optionally be present in about 0.01-10 wt% (e.g., 0.1-3 wt%), for example, in the disclosed oral care compositions.

[0190] Anti-tartar or plaque control agents suitable for use in the oral care compositions described herein include, for example, phosphates and polyphosphates (e.g., pyrophosphates), polyaminopropanesulfonic acid (AMPS), zinc citrate trihydrate, peptides (e.g., polyaspartic acid and polyglutamic acid), polyolefin sulfonates, polyolefin phosphates, bisphosphonates (e.g., aziridine-2,2-bisphosphonates, such as aziridine-2,2-bisphosphonic acid), N-methylaziridine-2,3-bisphosphonic acid, 1-hydroxyethylidene-1,1-bisphosphonic acid (HEDP), ethane-1-amino-1,1-bisphosphonate, and / or phosphonoalkyl carboxylic acids and their salts (e.g., their alkali metal salts and ammonium salts). Useful inorganic phosphates and polyphosphates include, for example, monobasic, dibasic, and ternary sodium phosphates; sodium tripolyphosphate; tetrabasic phosphates; monosodium, disodium, trisodium, and tetrasodium pyrophosphate; disodium dihydrogen pyrophosphate; sodium trimetaphosphate; sodium hexametaphosphate; or any of these in which sodium is replaced by potassium or ammonium. In some embodiments, other useful anti-tartar agents include anionic polycarboxylic acid polymers (e.g., polymers or copolymers of acrylic acid, methacrylic acid, and maleic anhydride, such as polyvinyl methyl ether / maleic anhydride copolymer). Other useful anti-tartar agents include chelating agents such as hydroxycarboxylic acids (e.g., citric acid, fumaric acid, malic acid, glutaric acid, and oxalic acid and their salts) and aminopolycarboxylic acids (e.g., EDTA). One or more anti-tartar or plaque control agents may optionally be present in about 0.01-50 wt% (e.g., about 0.05-25 wt% or about 0.1-15 wt%), for example, in the disclosed oral care compositions.

[0191] Surfactants suitable for use in the oral care compositions described herein can be, for example, anionic, nonionic, or amphoteric. Suitable anionic surfactants include, but are not limited to, C64. 8-20 Water-soluble salts of alkyl sulfates, C 8-20 Fatty acid sulfonated monoglycerides, sarcosinates, and taurine salts are suitable surfactants. Examples of anionic surfactants include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl hydroxyethyl sulfonate, sodium polyethylene glycol monododecyl ether carboxylate, and sodium dodecylbenzene sulfonate. Suitable nonionic surfactants include, but are not limited to, poloxamer, polyoxyethylene dehydrated sorbitol esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfoxides. Suitable amphoteric surfactants include, but are not limited to, C-type surfactants having anionic groups such as carboxyl, sulfate, sulfonate, phosphate, or phosphonate groups. 8-20 Derivatives of aliphatic secondary and tertiary amines. An example of a suitable amphoteric surfactant is cocamidopropyl betaine. One or more surfactants may optionally be present in a total amount of about 0.01-10 wt% (e.g., about 0.05-5.0 wt% or about 0.1-2.0 wt%) in, for example, the disclosed oral care compositions.

[0192] Abrasives suitable for use in the oral care compositions herein may include, for example, silica (e.g., silica gel, hydrated silica, precipitated silica), alumina, insoluble phosphates, calcium carbonate, and resin abrasives (e.g., urea-formaldehyde condensate products). Examples of insoluble phosphates that may be used as abrasives herein are orthophosphates, polymetaphosphates, and pyrophosphates, and include dicalcium orthophosphate dihydrate, calcium pyrophosphate, β-calcium pyrophosphate, tricalcium phosphate, polymetaphosphate, and insoluble sodium polymetaphosphate. One or more abrasives may optionally be present in a total amount of about 5-70 wt% (e.g., about 10-56 wt% or about 15-30 wt%) in, for example, the disclosed oral care compositions. In some embodiments, the average particle size of the abrasive is about 0.1-30 micrometers (e.g., about 1-20 micrometers or about 5-15 micrometers).

[0193] In some embodiments, the oral care composition may contain at least one pH adjuster. Such agents may be selected to acidify the composition, make it more alkaline, or buffer a pH range of about 2-10 (e.g., pH ranges from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9). Examples of pH adjusters that may be used herein include, but are not limited to, carboxylic acids, phosphoric acids, and sulfonic acids; acidic salts (e.g., monosodium citrate, disodium citrate, monosodium malate); alkali metal hydroxides (e.g., sodium hydroxide, carbonates such as sodium carbonate, bicarbonate, sesquicarbonate); borates; silicates; phosphates (e.g., monosodium phosphate, trisodium phosphate, pyrophosphate); and imidazoles.

[0194] Foam modifiers suitable for use in the oral care compositions herein may be, for example, polyethylene glycol (PEG). High molecular weight PEGs are suitable, including those having, for example, an average molecular weight of about 200,000 to 7,000,000 (e.g., about 500,000 to 5,000,000 or about 1,000,000 to 2,500,000). One or more PEGs may optionally be present in a total amount of about 0.1 to 10 wt% (e.g., about 0.2 to 5.0 wt% or about 0.25 to 2.0 wt%) in, for example, the oral care compositions disclosed herein.

[0195] In some embodiments, the oral care composition may contain at least one humectant. In some embodiments, the humectant may be a polyol, such as glycerin, sorbitol, xylitol, or low molecular weight PEG. The most suitable humectant may also be used as a sweetener herein. One or more humectants may optionally be present in a total amount of about 1.0-70 wt% (e.g., about 1.0-50 wt%, about 2-25 wt%, or about 5-15 wt%) in, for example, the disclosed oral care composition.

[0196] Natural or artificial sweeteners may optionally be included in the oral care compositions described herein. Examples of suitable sweeteners include dextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose, ribose, fructose, levulose, galactose, corn syrup (e.g., high fructose corn syrup or corn syrup solids), partially hydrolyzed starch, hydrogenated starch hydrolysates, sorbitol, mannitol, xylitol, maltitol, isomaltitol, aspartame, neotame, saccharin and its salts, dipeptide-based strong sweeteners, and cyclosulfonates. One or more sweeteners may optionally be present in a total amount of about 0.005-5.0 wt% in, for example, the oral care compositions disclosed herein.

[0197] Natural or artificial edible flavorings may optionally be included in the oral care compositions described herein. Examples of suitable edible flavorings include vanillin; sage; marjoram; celery oil; spearmint oil; cinnamon oil; wintergreen oil (methyl salicylate); peppermint oil; clove oil; laurel oil; anise oil; eucalyptus oil; citrus oil; fruit oil; flavorings such as those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, or pineapple; flavorings derived from legumes and nuts, such as coffee, cocoa beans, cola, peanuts, or almonds; and adsorbent and encapsulated edible flavorings. Also included in the edible flavorings described herein are ingredients that provide flavor and / or other sensory effects in the mouth, including cooling or warming effects. Such ingredients include, but are not limited to, menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cinnamon, oxanone, and irrisone. ® Hydroxymethyl anethole, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthane-3-carboxamide, N,2,3-trimethyl-2-isopropylbutyramide, 3-(1-menthoxy)-propane-1,2-diol, cinnamaldehyde glycerol acetal (CGA), and menthone glycerol acetal (MGA). One or more edible flavorings are optionally present in a total amount of about 0.01-5.0 wt% (e.g., about 0.1-2.5 wt%) in, for example, the disclosed oral care compositions.

[0198] In some embodiments, the oral care composition may contain at least one bicarbonate. Any orally acceptable bicarbonate may be used, including, for example, alkali metal bicarbonates such as sodium or potassium bicarbonate, and ammonium bicarbonate. For example, one or more bicarbonates may optionally be present in the disclosed oral care composition in a total amount of about 0.1-50 wt% (e.g., about 1-20 wt%).

[0199] In some embodiments, the oral care composition may comprise at least one whitening agent and / or coloring agent. Suitable whitening agents are peroxide compounds, such as any of those disclosed in U.S. Patent No. 8,540,971, which is incorporated herein by reference. Suitable coloring agents herein include, for example, pigments, dyes, lakes, and agents such as pearlescent agents that impart a particular gloss or reflectivity. Specific examples of coloring agents that may be used herein include talc; mica; magnesium carbonate; calcium carbonate; magnesium silicate; magnesium aluminum silicate; silica; titanium dioxide; zinc oxide; red, yellow, brown, and black iron oxides; ferric ammonium ferrocyanide; manganese violet; deep blue; titanic mica; and bismuth oxychloride. For example, one or more coloring agents may optionally be present in the disclosed oral care composition in a total amount of about 0.001-20 wt% (e.g., about 0.01-10 wt% or about 0.1-5.0 wt%).

[0200] Additional components that may optionally be included in the oral compositions herein include, for example, one or more enzymes (above), vitamins, and anti-adhesion agents. Examples of vitamins that may be used herein include vitamin C, vitamin E, vitamin B5, and folic acid. Examples of suitable anti-adhesion agents include methylparaben (solbrol), figokinase, and quorum sensing inhibitors.

[0201] Further examples of personal care, home care, and other products and ingredients described herein may be any of those disclosed in U.S. Patent No. 8,796,196, which is incorporated herein by reference. Examples of personal care, home care, and other products and ingredients herein include fragrances, air fresheners, deodorizers, insect repellents and pesticides, foaming agents such as surfactants, pet deodorizers, pet insecticides, pet shampoos, disinfectants, hard surface treatments (e.g., floors, bathtubs / showers, sinks, toilets, door handles / panels, glass / windows, exterior or interior of cars / automobiles) (e.g., cleaning, disinfecting, and / or coating agents), wipes and other nonwoven materials, colorants, preservatives, antioxidants, emulsifiers, emollients, oils, pharmaceuticals, flavorings, and suspending agents.

[0202] This disclosure also relates to methods for processing materials. These methods typically involve contacting the material with an aqueous composition comprising at least one cross-linked α-glucan derivative as disclosed herein.

[0203] In some respects, the material in contact with the aqueous composition in the contact methods described herein may comprise a fabric. The fabric described herein may comprise natural fibers, synthetic fibers, semi-synthetic fibers, or any combination thereof. The semi-synthetic fibers described herein are produced using naturally occurring materials that have been chemically derived, examples of which are rayon. Non-limiting examples of fabric types described herein include fabrics made from: (i) cellulosic fibers such as cotton (e.g., velvet, canvas, striped or checkered fabrics, chenille, printed cotton, corduroy, brocade, denim, flannel, striped cotton, jacquard fabrics, knitted fabrics, matelassé, oxford cloth, high-denier cotton, poplin, plissé, cotton satin, seersucker, sheer fabrics, terry cloth, twill, velvet), rayon (e.g., viscose, modal, lyocell), linen, and Tencel. ® (ii) Protein fibers, such as silk, wool, and related mammalian fibers; (iii) Synthetic fibers, such as polyester, acrylic, nylon, etc.; (iv) Long plant fibers derived from jute, flax, ramie, coconut fiber, kapok, sisal, hemp, Manila hemp, hemp, and tamarisk; and (v) Any combination of fabrics from (i)-(iv). Fabrics containing a combination of fiber types (e.g., natural and synthetic) include, for example, those containing both cotton and polyester. Materials / articles containing one or more of the fabrics described herein include, for example, clothing, curtains, drapes, upholstery, carpets, bedding, bathroom towels, tablecloths, sleeping bags, tents, automotive interiors, etc. Other materials include natural and / or synthetic fibers, including, for example, nonwoven fabrics, padding, paper, and foam.

[0204] The aqueous composition that comes into contact with the fabric can be, for example, a fabric care composition (e.g., a laundry detergent, a fabric softener). Therefore, if a fabric care composition is used in a treatment method, the treatment method described in some embodiments can be considered a fabric care method or a laundry method. The fabric care compositions described herein are intended to achieve one or more of the following fabric care benefits (i.e., surface-substantial effects): wrinkle removal, wrinkle reduction, wrinkle resistance, reduced fabric abrasion, anti-abrasion, reduced pilling, extended fabric life, color retention, reduced color fading, reduced dye transfer, color restoration, reduced fabric staining, release of fabric dirt, maintenance of fabric shape, enhanced fabric smoothness, prevention of dirt redeposition on fabric, prevention of graying, improved fabric hand / handle, and / or reduced fabric shrinkage.

[0205] Examples of conditions (e.g., time, temperature, washing / rinsing volume) used in fabric care or laundry methods herein are disclosed in WO 1997 / 003161 and U.S. Patent Nos. 4,794,661, 4,580,421, and 5,945,394, which are incorporated herein by reference. In other instances, materials comprising fabrics may come into contact with the aqueous compositions described herein for at least: (i) for at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120 minutes; (ii) at temperatures of at least about 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C (e.g., for washing or rinsing clothes: “cold” temperatures of about 15°C–30°C, “warm” temperatures of about 30°C–50°C, and “hot” temperatures of about 50°C–95°C); (iii) At a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 (e.g., a pH range of about 2–12 or about 3–11); (iv) at a salt concentration (e.g., NaCl) of at least about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 wt%; or any combination of (i)–(iv).

[0206] For example, the contact step in a fabric care or laundry method may include any one of washing, soaking, and / or rinsing steps. In further embodiments, contact with a material or fabric may be performed by any means known in the art, such as dissolving, mixing, shaking, spraying, treating, impregnating, rinsing, pouring or casting, bonding, coloring, coating, applying, pasting, and / or communicating an effective amount of the crosslinked α-glucan derivative described herein with the fabric or material. In further embodiments, contact may be used to treat the fabric to provide a substantial surface effect. As used herein, the terms “fabric hand” or “handle” refer to an individual’s tactile sensory response to a fabric, which may be physical, physiological, psychological, social, or any combination thereof. In one embodiment, fabric hand may be measured using a PhabrOmeter for measuring relative hand feel values. ®The system is used to measure (available from NuCybertek, Inc. Davis, CA) (American Association of Textile Chemists and Colorists [AATCC Test Method "202-2012, Relative Hand Value of Textiles: Instrumental Method"]).

[0207] In some aspects of treating materials containing fabrics, the cross-linked α-glucan derivative component of an aqueous composition can be adsorbed onto the fabric. This characteristic is believed to enable the cross-linked α-glucan derivative described herein to be used as an anti-redeposition agent and / or anti-ashing agent (in addition to its viscosity-changing and / or detergent-building effects) in the disclosed fabric care compositions. The anti-redeposition agent or anti-ashing agent described herein helps prevent the stain from redepositing on the garment in the wash water after the stain has been removed. In some aspects, it is further envisioned that adsorbing the cross-linked α-glucan derivative described herein onto the fabric enhances the fabric's mechanical properties.

[0208] The adsorption of cross-linked α-glucan derivatives to the fabrics described herein can be demonstrated, for example, using colorimetric techniques (e.g., Dubois et al., 1956). Analytical Chemistry 28:350-356; Zemlji et al., 2006 Lenzinger Berichte [Linz Chemical Fiber Company Report] 85:68-76; both are measured by reference to and incorporated herein, or by any other method known in the art.

[0209] Other materials that may be accessed in the above-described processing methods include surfaces that can be treated with dishwashing detergents (e.g., automatic or hand-washing detergents). Examples of such materials include surfaces of tableware, glassware, bowls, plates, baking trays, cookware, and flat cutlery (collectively referred to herein as “tableware”) made of ceramic, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, polystyrene, melamine, etc.), and wood. Therefore, in some embodiments, the processing method may be considered, for example, a tableware washing method or a tableware washing method. Other surfaces that may be accessed in a tableware washing method include surfaces of internal tableware washing machine components, such as washing chambers / compartments, pipes / blades, one or more pumps, shelves / stands, and sensor surfaces. Examples of conditions (e.g., time, temperature, washing volume) used to perform the tableware washing or tableware washing methods described herein are disclosed herein as well as in U.S. Patent No. 8,575,083 and U.S. Patent Application Publication No. 2017 / 0044468, which are incorporated herein by reference. In some respects, tableware articles may be brought into contact with the aqueous compositions described herein under a set of suitable conditions, such as any of the sets of conditions disclosed above concerning contact with fabric-containing materials.

[0210] Other materials that may be contacted in the above-described processing methods include oral surfaces, such as any soft or hard surfaces within the oral cavity, including surfaces of the tongue, hard and soft palate, buccal mucosa, gingiva, and teeth (e.g., the hard surfaces of natural teeth or artificial dentitions such as crowns, caps, fillings, bridges, dentures, or dental implants). Therefore, in some embodiments, the processing methods can be considered, for example, oral care methods or dental care methods. The conditions (e.g., time, temperature) used to contact the oral surfaces with the aqueous composition described herein should be suitable for the intended purpose of such contact. Other surfaces that may be contacted in the processing methods include surfaces of the skin system such as skin, hair, or nails.

[0211] Therefore, some aspects of this disclosure relate to materials comprising the crosslinked α-glucan derivatives described herein (e.g., fabrics or fiber-containing products as disclosed herein). Such materials can be prepared according to, for example, material processing methods disclosed herein. In some aspects, the material may comprise the crosslinked α-glucan derivatives if the crosslinked α-glucan derivatives are adsorbed onto the surface of the material or otherwise contact the surface of the material.

[0212] Some aspects of the methods for treating materials described herein further include a drying step, wherein the material is dried after contact with the aqueous composition. The drying step may be performed directly after the contact step, or after one or more additional steps that may immediately follow the contact step (e.g., drying fabrics or tableware after washing in the aqueous composition described herein, such as rinsing in water). Drying can be carried out by any of several methods known in the art, such as air drying (e.g., about 20°C–25°C), or, for example, at temperatures of at least about 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 120°C, 140°C, 160°C, 170°C, 175°C, 180°C, or 200°C. Materials dried herein typically contain less than 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% water. Fabrics are preferred materials for carrying out the optional drying step.

[0213] The aqueous composition used in the treatment methods described herein can be any aqueous composition disclosed herein. Examples of aqueous compositions include detergents (e.g., laundry detergents or dishwashing liquids), fabric softeners, and water-based dental cleaning agents such as toothpaste.

[0214] Hard surfaces washed or treated in a washing / treatment composition comprising the anti-deposition detergent composition described herein may have reduced film formation, staining, turbidity, or other deposits. In some aspects, the washing / treatment composition may be a washing liquid (grey water) to which the anti-deposition detergent composition has been added (e.g., the detergent may be provided in concentrated form and diluted into a washing / treatment composition during washing). The washing / treatment composition described herein may be, for example, a composition used in an automatic dishwashing machine or washing machine; such a washing / treatment composition may be characterized as disclosed herein regarding dishwashing and fabric care compositions. In some aspects, the washing / treatment composition comprises at least one cation, and a cross-linked α-glucan derivative is bound to the cation; this aspect may have any of the characteristics disclosed herein regarding cation binding.

[0215] Anti-deposition detergent compositions may be formulated, for example, according to any automatic dishwashing or fabric care composition disclosed herein or in the incorporated references, and / or contain any of the disclosed ingredients (e.g., surfactants, enzymes, etc.), and / or in any form disclosed herein (e.g., powder, flakes, liquid, unit dose, etc.). The amount of the crosslinked α-glucan derivative herein may be, for example, about, or at least about 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 4 wt%-12 wt%, 4 wt%-10 wt%, 4 wt%-8 wt%, 5 wt%-12 wt%, 5 wt%-10 wt%, 5 wt%-8 wt%, 6 wt%-12 wt%, 6 wt%-10 wt%, or 6 wt%-8 wt%. In some respects, the anti-deposition detergent composition has each of the ingredients listed in Table A below; the amount (wt%) of each ingredient in such a composition may be within 5%, 10%, 15%, 5%-10%, or 5%-15% of the corresponding values ​​in Table A (plus / minus).

[0216] Table A

[0217] Some aspects of this disclosure relate to a method for washing / cleaning or treating hard surfaces. This washing / cleaning or treating method may include: (a) Contacting a hard surface with a washing / treatment composition comprising the anti-deposition detergent composition described herein, and (b) Removing all or part of the washing / treatment composition from a hard surface (e.g., by rinsing with water with or without rinsing aids [water / liquid removal aids] and / or added salt); thereby washing / cleaning or treating the hard surface, wherein the washed / cleaned / treated hard surface has reduced film formation, staining, turbidity, or other deposits. This method may include any conditions suitable for washing, treating materials / surfaces and / or cation binding, such as those disclosed herein (e.g., temperature, pH, time, salt / buffer, etc.) (e.g., conditions for an automated dishwashing machine).

[0218] The hard surface treated by the washing / cleaning method can be any hard surface, such as the hard surface of the aqueous composition or system disclosed herein, or a hard surface associated with / interacting with it. Examples of hard surfaces include glass, plastics (e.g., styrene-acrylonitrile, polystyrene, polypropylene, polyethylene, melamine), ceramics, porcelain, metals (e.g., steel, stainless steel, aluminum), or stone (e.g., marble, granite), or composed of them; any of these surfaces can be, for example, the surface of a piece of tableware disclosed herein. In some aspects, the hard surface can be a surface found in an automatic dishwashing machine, washing machine, or similar equipment (e.g., body / housing), and / or its internal components (e.g., pipes, sprayers, nozzles, frames, agitators).

[0219] In some aspects of the washing / cleaning method performed in an automatic dishwashing machine, the washing cycle may include the following continuous cycles: (i) optionally at least one pre-wash period during which water (e.g., at about 40°C-70°C, 45°C-70°C, 50°C-70°C, or 60°C-70°C) is circulated (e.g., for about 3-15, 3-10, or 3-6 minutes) to loosen food material on the dishes; (ii) a main wash period during which the anti-deposition detergent composition described herein (e.g., about 10-30, 10-25, 10-20, 15-30, 15-25, or 15-20) is used. (iii) at least one rinsing period during which water (e.g., dry weight) is added to water (e.g., at about 40°C-70°C, 45°C-70°C, or 50°C-70°C) for circulation (e.g., about 1-2.5, 1-2, 1.5-2.5, or 1.5-2 gallons) for circulation (thus providing the washing composition) for a suitable amount of time (e.g., about 3-20, 3-15, 3-10, 5-20, 5-15, or 5-10 minutes); (iv) at least one rinsing period during which water (e.g., at about 40°C-70°C, 45°C-70°C, 50°C-70°C, or 60°C-70°C) is circulated (e.g., for about 3-15, 3-10, or 3-6 minutes); and (iv) optionally, a drying period. After each of periods (ii) and (iii) of the washing cycle (and optionally after period [i]), the circulating liquid is typically removed, such as by pumping and / or draining.

[0220] The washing / cleaning methods described herein can be used to wash tableware (e.g., using an automatic dishwashing machine, or manual / handwashing). For example, tableware may be as disclosed herein or in U.S. Patent No. 8,575,083 or U.S. Patent Application Publication No. 2017 / 0044468, which are incorporated herein by reference. For example, tableware may include plates, cups, glassware, bowls, basins, cutlery, spoons, knives, forks, serving utensils, ceramics, plastics, cutting boards, porcelain, ceramics, glassware, tableware, utensilware, and kitchen utensils.

[0221] Hard surfaces washed using the washing / cleaning methods described herein exhibit reduced film formation, staining, turbidity, and / or other deposits. In some respects, this reduction is about or at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% compared to that observed when using a detergent composition that does not contain the cross-linked α-glucan derivatives described herein with the washing / cleaning methods; all other characteristics of the washing / cleaning methods may be identical. Film formation, staining, turbidity, and related deposits typically contain one or more insoluble salts (e.g., carbonates such as CaCO3 or MgCO3, hydroxides such as Mg(OH)2 or Ca(OH)2, sulfates such as CaSO4) and / or other insoluble compounds (e.g., calcium and / or magnesium salts of fatty acids such as stearic acid). Film formation and / or staining may also optionally be referred to as deposits of scale and / or scum (e.g., soap scum).

[0222] Rinse aids may be used optionally during or after the removal of the washing / treatment composition from hard surfaces, such as in the automatic dishwashing process described herein. Rinse aids are generally designed to remove residual water / liquid from hard surfaces and may therefore be optionally referred to as water / liquid removal aids. In this case, rinsing aids can improve the removal from hard surfaces of water / liquid containing any dissolved and / or dispersed compounds, such as complexes containing minerals and / or cross-linked α-glucan derivatives. In some aspects, rinsing aids / water / liquid removal aids may be disclosed as in any of U.S. Patent Nos. 6,630,440, 5,739,099, 5,516,452, 8,685,911, 9,567,551, or 1,111,8140 (each of which is incorporated herein by reference). In some respects, rinsing aids may contain carbonyl synthetic alcohols (oxoalcohols) (alkyl alcohols); an example of such a rinsing aid is GENAPOL EP 2564 (CAS No. 120313-48-6).

[0223] This disclosure also relates to a method for preparing an aqueous composition having increased detergent-building capacity. The method includes, for example, contacting an aqueous composition with at least one crosslinked α-glucan derivative as disclosed herein, wherein the derivative increases the detergent-building capacity of the aqueous composition compared to the detergent-building capacity present prior to the contact step. This method may optionally be characterized as a water (or any other aqueous composition) softening method.

[0224] The aqueous composition in this method can be any aqueous composition disclosed herein, such as household care products, personal care products, industrial products, pharmaceutical products, or food products. Examples of suitable household care products include household or industrial care products, such as laundry detergents or fabric softeners, and automatic dishwashing liquids. Examples of suitable personal care products include hair care products (e.g., shampoos, conditioners), dental hygiene compositions (e.g., toothpaste, mouthwash), and skin care products (e.g., hand soaps or bath soaps, lotions, cosmetics).

[0225] In some aspects, the aqueous composition in this method is a detergent and / or surfactant composition. Such compositions as described herein may contain, for example, at about 0.01 wt% to 10 wt% (e.g., about 0.05 wt% to 5.0 wt% or about 0.1 wt% to 2.0 wt%), at any of the disclosures herein. Those skilled in the art will recognize all the different products constituting examples of detergent / surfactant-containing compositions disclosed herein, such as certain household care products (e.g., laundry detergents, dishwashing liquids) and personal care products (e.g., hand soaps / bath soaps, dental floss), particularly those for cleaning applications.

[0226] In some respects, contacting an aqueous composition with one or more cross-linked α-glucan derivatives can increase the builder capacity of the aqueous composition. This increase, compared to the builder capacity of the aqueous composition prior to the contact step, can be, for example, about or at least about 1%, 5%, 10%, 25%, 50%, 100%, 500%, or 1000% (or any integer between 1% and 1000%). The extent of the increased builder capacity achieved can be measured in a variety of ways. For example, the increased builder capacity achieved by the cross-linked α-glucan derivatives described herein can be estimated by determining the extent to which the derivative supplies alkalinity to the aqueous composition or buffers the aqueous composition to maintain alkalinity. As another example, the increased builder capacity achieved by the cross-linked α-glucan derivatives described herein can be estimated by determining the extent to which the derivative reduces hardness in the aqueous composition (by sequestering / chelating hard water cations) and / or helps remove dirt from suspensions (a characteristic typically applicable to fabric care compositions). As other examples, the increased detergent-building capacity can be determined according to the methods disclosed in the following examples and / or U.S. Patent Application Publication Nos. 2018 / 0022834, 2024 / 0199766, or 2024 / 0150497 or International Patent Application Publication Nos. WO 2022 / 178073 or WO 2022 / 178075 (which are incorporated herein by reference) (e.g., calcium dispersibility, NTU determination, membrane reduction determination). For example, contacting the crosslinked α-glucan derivative described herein with an aqueous composition can be accomplished by dissolving or dispersing the derivative in the aqueous composition.

[0227] Non-limiting examples of the compositions and methods disclosed herein include: 1. A composition (product) comprising a crosslinked α-glucan derivative, wherein the crosslinked α-glucan derivative is generated by contacting ethylene glycol diglycidyl ether (EGDE) with a first α-glucan derivative (i.e., the first α-glucan derivative has typically been derivatized herein, such as by etherification, sulfonation, or oxidation) (under suitable conditions [typically including aqueous conditions] for reacting the ethylene glycol diglycidyl ether with and crosslinking the first α-glucan derivative), thereby crosslinking the first α-glucan derivative (thus generating the EGDE-crosslinked α-glucan derivative), wherein the ratio of EGDE to the first α-glucan derivative (for the contact) is about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative.

[0228] 1b. A composition (product) comprising an EGDE (ethylene glycol diglycidyl ether)-crosslinked α-glucan derivative, optionally wherein the ratio of EGDE to the α-glucan derivative in the EGDE-crosslinked α-glucan derivative is about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative.

[0229] 2. The composition as described in Example 1 or 1b, wherein at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,3 bonds (i.e., at least about 50% of the glycosidic bonds of the first α-glucan derivative are α-1,3 bonds).

[0230] 3. The composition as described in Example 2, wherein at least about 90% (or about 100%) of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,3 bonds (i.e., at least about 90% [or about 100%] of the glycosidic bonds of the first α-glucan derivative are α-1,3 bonds).

[0231] 4. The composition as described in Example 1 or 1b, wherein at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,6 bonds (i.e., at least about 50% of the glycosidic bonds of the first α-glucan derivative are α-1,6 bonds).

[0232] 5. The composition as described in Examples 1, 1b, or 4, wherein the crosslinked α-glucan derivative comprises at least 1% of α-1,2 and / or α-1,3 branches (i.e., the first α-glucan derivative comprises at least 1% of α-1,2 and / or α-1,3 branches).

[0233] 6. The composition as described in Examples 1, 1b, 2, 3, 4, or 5, wherein the dextran from which the first α-glucan derivative is derived has a weight-average degree of polymerization (DPw) of at least about 200 (e.g., about or at least about 700 or 800).

[0234] 7. The composition as described in Examples 1, 1b, 2, 3, 4, 5, or 6, wherein the first α-glucan derivative has a degree of substitution (DoS) of up to about 3.0 contributed by at least one organic group (typically wherein the DoS is at least about 0.005).

[0235] 8. The composition as described in Example 7, wherein the organic group is ether-linked to the first α-glucan derivative.

[0236] 9. The composition as described in Example 7 or 8, wherein the organic group comprises carboxyl, alkyl, hydroxyalkyl, or aryl.

[0237] 10. The composition as described in Examples 7, 8, or 9, wherein the organic group comprises carboxymethyl.

[0238] 11. The composition as described in Examples 7, 8, 9, or 10, wherein the organic group comprises benzyl.

[0239] 12. The composition as described in Examples 9, 10, or 11, wherein the first α-glucan derivative comprises the carboxyl group (e.g., carboxymethyl) and the aryl group (e.g., benzyl) (i.e., the first α-glucan derivative is a mixed ether).

[0240] 13. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein the first α-glucan derivative has a DoS of up to about 3.0 contributed by at least one sulfonate group.

[0241] 14. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, wherein the first α-glucan derivative has been oxidized (before being crosslinked).

[0242] 15. The composition as described in Examples 1, 1b, 2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, wherein the first α-glucan derivative has a DoS of about 0.35 to 2.5 (e.g., about 0.4 to 2.5, about 0.4 to 1.0, or about 0.35 to 1.0) (e.g., DoS contributed by etherified organic groups, sulfonate groups, and / or groups generated by oxidation), and wherein at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,3 bonds (e.g., at least about 90%, or about 100% of the glycosidic bonds are α-1,3 bonds).

[0243] 16. The composition as described in Examples 1, 1b, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, wherein the first α-glucan derivative has at least about 2.0 (e.g., at least about 2.25 or 2.5, or about 2.3 to 2.6) DoS (e.g., DoS contributed by etherified organic groups, sulfonate groups, and / or groups generated by oxidation), and wherein at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,6 bonds, optionally wherein the first α-glucan derivative comprises at least 1% α-1,2 and / or α-1,3 branches.

[0244] 17. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, wherein the ratio of EGDE to the first α-glucan derivative is about 0.04 to 0.06 moles of EGDE to about 1 mole of the first α-glucan derivative.

[0245] 17b. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, wherein the crosslinked α-glucan derivative has at least 10% biodegradability after 15, 60, or 90 days as determined by a carbon dioxide release test method.

[0246] 17c. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17b, except that the α-glucan derivative is not crosslinked (is uncrosslinked) (except or instead of using the EGDE-crosslinked α-glucan derivative) (i.e., where appropriate, “crosslinked α-glucan derivative” [and similar expressions] in this document may be replaced by “α-glucan derivative” [and similar expressions], wherein the derivative is uncrosslinked]).

[0247] 17d. Compositions as described in Examples 1, 1b, 2, 3, 6, 17, 17b, 18, 19, 20, 21, 22, 23, 24, 25, or 26, wherein at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,3 bonds (i.e., at least about 50% of the glycosidic bonds of the first α-glucan derivative are α-1,3 bonds), wherein the first α-glucan derivative has a DoS of about 0.3 to about 0.6 contributed by an ether-linked carboxyl group (e.g., carboxymethyl) (e.g., DoS 0.4-0.6 or 0.4-0.5), and optionally wherein the α-glucan from which the first α-glucan derivative is derived has a DPw of at least about 1400 (e.g., 1500-1900, 1600-1800); however, wherein (i) The cross-linked α-glucan derivative is produced by contacting a cross-linking agent (e.g., EGDE) with the first α-glucan derivative (i.e., the cross-linking agent is not necessarily EGDE, but may be EGDE in some respects), and (ii) optionally, the ratio of the cross-linking agent to the first α-glucan derivative is about 0.01 to 0.1 (e.g., 0.06-0.1, 0.07-0.9) molar cross-linking agent to about 1 molar first α-glucan derivative (wherein any of the foregoing features may be derived from this disclosure where appropriate); optionally, the composition is a personal care product (e.g., lotion, gel, serum, or ointment).

[0248] 18. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, or 17c, wherein the composition is an aqueous composition.

[0249] 19. The composition as described in Example 18, wherein the aqueous composition further comprises at least one cation, and the cross-linked polysaccharide derivative is bound to the cation.

[0250] 20. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 18, or 19, wherein the composition is a home care product, a personal care product, an industrial product, a medical product, or a pharmaceutical product.

[0251] 21. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 18, 19, or 20, wherein the composition is in or contained therein as a liquid, gel, powder, hydrocolloid, granule, tablet, capsule, bead or lozenge, single-compartment pouch, multi-compartment pouch, single-compartment sachet, multi-compartment sachet, water-dispersible unit dose (e.g., fibrous compositions such as nonwoven or other fibrous structures, sponges or foams, aggregates) or water-soluble unit dose (e.g., sheet or film, fibrous compositions such as nonwoven or other fibrous structures, sponges or foams, aggregates).

[0252] 22. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 18, 19, 20, or 21, further comprising at least one surfactant (i.e., the composition may optionally be considered a detergent composition).

[0253] 23. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 18, 19, 20, 21, or 22, further comprising at least one enzyme.

[0254] 24. The composition as described in Example 23, wherein the enzyme is a cellulase, protease, amylase, lipase, or nuclease.

[0255] 25. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 18, 19, 20, 21, 22, 23, or 24, further comprising at least one of the following: a complexing agent, a detergency polymer, a surfactant-enhancing polymer, a bleaching agent, a bleaching activator, a bleaching catalyst, a fabric conditioner, clay, a foaming agent, a foaming inhibitor, a corrosion inhibitor, a dirt suspending agent, an anti-dirt redeposition agent, a dye, a bactericide, a dulling inhibitor, an optical brightener, a fragrance, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a tinting dye, a visual signal transduction component, a defoamer, a structuring agent, a thickener, an anti-caking agent, starch, sand, or a gelling agent.

[0256] 26. The composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 18, 19, 20, 21, 22, 23, 24, or 25, wherein the composition is in the form of, or contained therein, a dishwashing detergent composition or a fabric care composition.

[0257] 27. A method of washing or treating a hard surface, the method comprising: (a) contacting the hard surface with a washing / treatment composition comprising a composition as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 17b, 17c, 17d, 18, 19, 20, 21, 22, 23, 24, 25, or 26; and (b) removing all or a portion of the washing / treatment composition from the hard surface; thereby washing or treating the hard surface, wherein the washed / treated hard surface has reduced film formation, spots, turbidity, or other deposits, optionally wherein the hard surface is a hard surface of glass, plastic, ceramic, porcelain, metal, or stone.

[0258] 28. The method as described in Example 27, wherein step (b) includes rinsing the hard surface.

[0259] 29. The method as described in Example 27 or 28, wherein the hard surface is the hard surface of the tableware.

[0260] 30. The method as described in Examples 27, 28, or 29, wherein it is performed in an automatic dishwashing machine or washing machine.

[0261] 31. A method for producing cross-linked α-glucan derivatives (e.g., as described in Examples 1, 1b, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 17b), said method comprising: (a) Ethylene glycol diglycidyl ether (EGDE) is contacted with a first α-glucan derivative (i.e., the first α-glucan derivative has typically been derivatized herein, such as by etherification, sulfonation, or oxidation) (under suitable conditions [typically including aqueous conditions] for reacting the EGDE with and crosslinking the first α-glucan derivative), thereby crosslinking the first α-glucan derivative (thus producing an EGDE-crosslinked α-glucan derivative), wherein the ratio of EGDE to the first α-glucan derivative (for the contact) is about 0.03 to 0.07 moles (e.g., about 0.04 to 0.06 moles) of EGDE to about 1 mole of the first α-glucan derivative, and (b) optionally, the crosslinked α-glucan derivative produced in step (a) is separated.

[0262] Example

[0263] This disclosure is further illustrated in the following examples. It should be understood that while these examples indicate certain aspects of this document, they are given by way of illustration only. From the foregoing discussion and these examples, those skilled in the art can determine the essential features of the disclosed embodiments, and various changes and modifications can be made to adapt the disclosed embodiments to a variety of uses and conditions without departing from the spirit and scope of the disclosed embodiments.

[0264] Materials / Methods

[0265] Representative preparation of α-1,3-glucan: α-1,3-glucan having approximately 100% α-1,3 glycosidic bonds can be synthesized, for example, by following the procedure disclosed in U.S. Application Publication No. 2014 / 0179913 (see, for example, Example 12 therein), which is incorporated herein by reference.

[0266] As another example, a slurry of α-1,3-glucan with approximately 100% α-1,3-glycosidic bonds was prepared by: an aqueous solution (0.5 L) adjusted to pH 5.5 containing *Streptococcus salivarius* gtfJ enzyme (100 units / L) (as described in U.S. Patent Application Publication No. 2013 / 0244288, which is incorporated herein by reference), sucrose (100 g / L), potassium phosphate buffer (10 mM), and FermaSure® antimicrobial agent (100 ppm). The resulting enzyme reaction mixture was maintained at 20°C–25°C for 24 hours. Since the α-1,3-glucan synthesized in the reaction is water-insoluble, a slurry was formed. The α-1,3-glucan solids were then collected on 40-micron filter paper using a Buchner funnel equipped with a 325-mesh sieve.

[0267] Representative preparation of α-1,6-glucan with α-1,2 branches

[0268] Each α-1,2-branched α-1,6-glucan listed below contains a 100% α-1,6-linked backbone, with individual side-chain glucosides already attached to the backbone via α-1,2 bonds; thus, each side-chain gluco is attached to the backbone via an α-1,2 bond / branching point. The example of an α-1,2-branched α-1,6-glucan in this paper has 40% α-1,2-branching and 60% α-1,6 bonds. In this example, 60% of all bonds in the α-glucan are α-1,6 bonds in the backbone, while the remaining 40% are α-1,2 bonds along the backbone to the side-chain glucosides.

[0269] A method for preparing α-1,6-glucan containing varying amounts of α-1,2-branched α-glucan is disclosed in U.S. Patent Application Publication No. 2018 / 0282385, which is incorporated herein by reference. Reaction parameters such as sucrose concentration, temperature, and pH can be adjusted to provide α-1,6-glucan with various levels of α-1,2-branching and molecular weight. A representative procedure for preparing α-1,2-branched α-1,6-glucan (containing 19% α-1,2-branching [i.e., 19% α-1,2 bonds] and 81% α-1,6 bonds) is provided below. Using 1D 1 ¹H-NMR spectra were used to quantify the distribution of glycosidic bonds. Similarly, other samples of α-1,6-glucan with α-1,2-branching were prepared. For example, one sample contained 32% α-1,2-branching and 68% α-1,6 bonds, and another contained 10% α-1,2-branching and 90% α-1,6 bonds.

[0270] Soluble α-1,6-glucan with approximately 19% α-1,2-branching was prepared using a stepwise combination of glucosyltransferase (dextran sucrase) GTF8117 and α-1,2-branching enzyme GTFJ18T1. A reaction mixture (2 L) consisting of sucrose (450 g / L), GTF8117 (9.4 U / mL), and 50 mM sodium acetate was adjusted to pH 5.5 and stirred at 47°C. Aliquots (0.2–1 mL) were removed at a predetermined time and quenched by heating at 90°C for 15 min. The resulting heat-treated aliquots were passed through a 0.45–µm filter. The concentrations of sucrose, glucose, fructose, Leuconostoc disaccharide, oligosaccharides, and polysaccharides were determined by HPLC analysis. After 23.5 h, the reaction mixture was heated to 90°C for 30 min. The heat-treated reaction mixture of aliquots was passed through a 0.45 µm filter, and the soluble monosaccharides / disaccharides, oligosaccharides, and polysaccharides in the flow were analyzed. The major product was a linear dextran with a DPw of 93 (i.e., 100% α-1,6 bonds).

[0271] A second reaction mixture was prepared by adding 238.2 g of sucrose and 210 mL of α-1,2-branching enzyme GTFJ18T1 (5.0 U / mL) to the remaining heat-treated reaction mixture obtained from the GTF8117 reaction described above. The mixture was stirred at 30°C to a volume of approximately 2.2 L. Aliquots (0.2–1 mL) were removed at a predetermined time and quenched by heating at 90°C for 15 minutes. The resulting heat-treated aliquots were passed through a 0.45–µm filter. The flow-through was analyzed by HPLC to determine the concentrations of sucrose, glucose, fructose, Leuconostoc disaccharide, oligosaccharides, and polysaccharides. After 95 hours, the reaction mixture was heated to 90°C for 30 minutes. The heat-treated reaction mixture of aliquots was passed through a 0.45–µm filter, and the soluble monosaccharides / disaccharides, oligosaccharides, and polysaccharides in the flow-through were analyzed. The remaining heat-treated mixture was centrifuged using a 1–L centrifuge flask. Collect the supernatant and clean it more than 200 times using an ultrafiltration system with a 1- or 5-kDa MWCO cartridge and deionized water. Dry the cleaned oligosaccharide / polysaccharide product solution. Then pass through... 1 H-NMR spectroscopy was used to analyze dried samples to determine the end-group isomer bonds of oligosaccharides and polysaccharides.

[0272] For example, various water-soluble α-1,2-branched α-1,6-glucans can be prepared by following the above (or similar) enzymatic reaction strategies. This type of α-glucan material can also be produced according to the methods disclosed, for example, in U.S. Patent Application Publication No. 2018 / 0282385 (which is incorporated herein by reference). Examples of different α-1,2-branched α-1,6-glucans that have been produced are listed in Table 1. In each of these α-glucans, the α-1,6-glucan backbone (in which α-1,2-branchs are present) has 100% α-1,6-glycosidic bonds; the molecular weights listed are the molecular weights of the α-1,6-glucan backbone. Each α-1,2-branch consists of a single (side-chain) glucose unit.

[0273] Table 1

[0274] α-1,2-branched α-1,6-glucan

[0275] For example, any α-1,2-branched α-1,6-glucan as disclosed herein (e.g., Table 1) can be used as a substrate for derivatization procedures as described below.

[0276] Representative preparation of carboxymethyl α-1,6-glucan

[0277] 267 g of a 37.5 wt% α-1,6-glucan solution (53 kDa, 6.4% α-1,2-branched) was added to a three-necked 2-L round-bottom flask equipped with a top stirrer. With stirring, 199 g of 50 wt% sodium hydroxide solution was added to the solution via a feeding funnel over 15 minutes. Chloroacetic acid solution (116 g dissolved in 77 g water) was added to the stirred solution via a feeding funnel over 30 minutes. The solution was heated to 55°C under nitrogen for 5 hours. The resulting amber solution was cooled and neutralized to pH 7 with 18 wt% HCl. The resulting pale yellow solution was diluted to 3 L and purified by percolation (using a 3X MWCO 5-kDa PES membrane, allowing approximately 9 L of water to pass through). The solution was concentrated using a rotary evaporator and freeze-dried to obtain a white powder. 1 1H-NMR analysis determined that the degree of substitution of the carboxymethyl α-1,6-glucan product prepared in this manner was 0.51.

[0278] Representative preparation of carboxymethyl α-1,3-glucan

[0279] α-1,3-glucan (DPw approx. 650, 110 g) and water (110 g) were added to a 4-necked, 2 L round-bottom flask equipped with a metal / mechanical stir bar, thermocouple, feeding funnel, and a condenser with an N2 inlet on top. The mixture was left to stand overnight at room temperature. Ethanol (220 g, 92 wt%) was added at room temperature. The mixture was stirred at 200 rpm and sodium hydroxide (191.1 g, 50 wt% solution) was added over a 20-minute period (25°C to 37°C). The white slurry was stirred for another 10 minutes. A solution containing 112.2 g of chloroacetic acid in 50 g of 92 wt% ethanol was added over a 20-minute period (35°C to 55°C). The white slurry was heated for 3 hours at 58°C–60°C using a heating mantle. The reaction mixture was cooled to 45°C and sodium hydroxide (108.6 g, 50 wt% solution) was added over 10 minutes, followed by the addition of a solution containing 64.13 g of chloroacetic acid in 35 g of 92 wt% ethanol. The resulting mixture was heated at 58°C–65°C for 2 hours. Large clumps formed. The liquid from the reaction mixture (approximately 500 mL) was decanted. Methanol (400 mL) was added and the pH of the mixture was adjusted to approximately 7 by adding HCl (18.5 wt%, 13.5 g). The liquid was decanted. The resulting solid was washed twice with methanol (90 wt%, 700 mL) (80 wt%, 700 mL each time) and filtered to obtain a solid, which was dried overnight under full vacuum to give 148.5 g of the desired product. 1 1H-NMR analysis determined that the degree of substitution of the carboxymethyl α-1,3-glucan product prepared in this manner was 0.91.

[0280] Representative preparation of oxidized carboxymethyl starch

[0281] Starch (20 g, Sigma-Aldrich product number S9765, soluble starch) was loaded into a 4-necked, 500-mL round-bottom flask equipped with a stir bar, thermocouple, feeding funnel, and air inlet. Sodium hydroxide solution (34 g in 50 wt% NaOH solution) was added. The solution was stirred overnight. The solution was heated in a 50°C oil bath, and monochloroacetic acid (MCA) solution (16 g MCA in 8 g DI-water) was added via the feeding funnel. The solution was then heated in a 65°C oil bath for 2 hours. The solution was cooled to room temperature and neutralized with 18 wt% HCl (13 mL). A 10-mL sample of the reaction was harvested, and the carboxymethyl starch product was purified in methanol. 13 C-NMR analysis determined the carboxymethyl DoS of the product to be 0.62.

[0282] TEMPO (0.1 g) and NaBr (1.0 g) were added to the above reaction. Then, NaClO (10 wt%–15 wt%, 100 mL) was added dropwise over 0.5 hours. The pH was adjusted using NaOH (2 N, 17 mL). The final pH was 9.9. The oxidation product thus prepared was stirred at room temperature for 1.5 hours. The crude material was diluted in 1 gallon of DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI, with a 5 kDa MWCO box), and lyophilized to provide 21.2 g of the oxidation product. The total carboxyl group DoS of the oxidized carboxymethyl starch product, contributed by the individual carboxylmethyl group and the individual carboxyl group, was determined by... 13 C-NMR analysis determined its value to be 0.67. Its Mw was determined by SEC to be 53 kDa.

[0283] Representative Synthesis of Oxidized Carboxymethyl Dextran

[0284] A 4-necked, 500-mL round-bottom flask equipped with a stir bar, thermocouple, addition funnel, and air inlet was filled with dextran (20 g) prepared using glucosyltransferase (GTF) 0768 as described in U.S. Patent Application Publication No. 2016 / 0122445 (incorporated herein by reference). Sodium hydroxide solution (34 g in 50 wt% NaOH solution) was added. The solution was stirred overnight. The solution was heated in a 50°C oil bath, and a monochloroacetic acid (MCA) solution (16 g MCA in 8 g DI-water) was added via a addition funnel. The solution was then heated in a 65°C oil bath for 2 hours. The solution was cooled to room temperature and neutralized with 18 wt% HCl (17 mL). A 10-mL sample of the reaction was harvested, and its carboxymethyl dextran product (referred to herein as "ADW36-comparison") was purified in methanol. 13 C-NMR analysis determined the carboxymethyl DoS of the product to be 0.46.

[0285] TEMPO (0.1 g) and NaBr (1.0 g) were added to the above reaction. NaClO (10 wt%–15 wt%, 90 mL) was added dropwise over 0.5 hours. The pH was adjusted using NaOH (2 N, 15 mL). The final pH was 9.6. The oxidation product thus prepared was stirred at room temperature for 1.5 hours. The crude material was diluted in 1 gallon of DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI, with a 5 kDa MWCO box), and lyophilized to provide 17.8 g of oxidation product. The total carboxyl group DoS of the oxidized carboxymethyl dextran product (referred to herein as “ADW36”) was determined by the contribution of a single carboxymethyl group and a single carboxyl group.13 C-NMR analysis determined the value to be 0.51. Its Mw was determined by SEC to be 49 kDa. Therefore, it was found that the ADW36 product was at least further substituted with a carboxyl group, compared with its parent compound (ADW36- in contrast).

[0286] Representative Synthesis of Oxidized Carboxymethyl Dextran

[0287] Dextran (30 g, Sigma-Aldrich product number D5376, Leuconostoc mesenteriae, Mw 1.5-2.8 million Da) and DI-water (120 mL) were added to a 4-necked, 500-mL round-bottom flask equipped with a stir bar, thermocouple, feeding funnel, and air inlet. Sodium hydroxide solution (51 g in 50 wt% NaOH solution) was added. The solution was stirred overnight. The solution was heated in a 50°C oil bath, and monochloroacetic acid (MCA) solution (24 g MCA in 12 g DI-water) was added via the feeding funnel. The solution was then heated in a 65°C oil bath for 2 hours. The solution was cooled to room temperature and neutralized with 18 wt% HCl (23 mL). A 10-mL sample of the reaction was harvested, and its carboxymethyl dextran product (referred to herein as "ADW39-comparison") was purified in methanol. 13 C10 NMR analysis determined the carboxymethyl DoS value of the product to be 0.58.

[0288] TEMPO (0.15 g) and NaBr (1.5 g) were added to the above reaction. NaClO (10 wt%–15 wt%, 135 mL) was added dropwise over 0.5 hours. The pH was adjusted using NaOH (2 N, 20 mL). The final pH was 9.6. The oxidation reaction thus prepared was stirred at room temperature for 1.5 hours. The crude material was diluted in 1 gallon of DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI, with a 5 kDa MWCO box), and lyophilized to provide 32.5 g of the oxidation product. The total carboxyl group DoS of the oxidized carboxymethyl dextran product (referred to herein as “ADW39”) was determined by the contribution of a single carboxymethyl group and a single carboxyl group. 13 C-NMR analysis determined the value to be 0.67. Its Mw was determined by SEC to be 27 kDa. Therefore, it was found that the ADW39 product was at least further substituted with a carboxyl group, compared with its parent compound (ADW39- in contrast).

[0289] Representative Synthesis of Cyanoethylcarboxyethylα-1,3-glucan

[0290] 260 g of α-1,3-glucan (DPw 800) wet cake (38.5 wt% dextran) and 550 g of DI-water were added to a 4-necked, 1-L round-bottom flask equipped with a mechanical stir bar, thermocouple, and feeding funnel. The mixture was stirred at room temperature while 64 g of 50 wt% sodium hydroxide solution was added over 15 minutes. Acrylonitrile (64 g) was then slowly added over 10 minutes at 25°C. The cyanoethylation reaction thus prepared was stirred at room temperature for 3.5 hours. HCl (18.5 wt%, 135 g) was then added to adjust the pH of the reaction to approximately 7. The crude product was precipitated and washed in methanol to provide 124 g of cyanoethylcarboxyethyl α-1,3-glucan (referred to herein as “ADW7-contrast”). 13 C10 NMR analysis determined the product's DoS values ​​to be 0.90 and 0.12 for cyanoethyl and carboxyethyl groups, respectively. The carboxyethyl group was formed in the above reaction under alkaline aqueous conditions via the hydrolysis of some cyano groups.

[0291] An aqueous solution of the cyanoethylcarboxyethyl α-1,3-glucan product (5 g, ADW7- control) prepared above in 50 mL of DI-water was added to a 4-necked, 250 mL round-bottom flask equipped with a stir bar, thermocouple, feeding funnel, and air inlet. Then, TEMPO (0.1 g) and NaBr (1 g) were added to the solution. NaClO (10 wt%–15 wt%, 25 mL) was added dropwise to the stirred solution over 0.5 hours. The pH of the solution was then adjusted to 10.5 using NaOH (2 N, 13 mL). The oxidation product thus prepared was stirred at room temperature for three hours. The crude material was then diluted in 1 gallon of DI-water, stirred at room temperature for 6 hours, filtered, purified by ultrafiltration (PELLICON MINI, with a 5 kDa MWCO cartridge), and lyophilized to provide 3.7 g of the oxidation product. 13 C-NMR analysis determined the DoS of the oxidation product (referred to as "ADW7" in this paper) to be 0.61 / 0.61 (cyanoethyl / carboxyl) (the DoS of the carboxyl group is reported as contributed by a single carboxyl ethyl group and a single carboxyl group). Its Mw was determined by SEC to be 37 kDa.

[0292] Example 1

[0293] Summary of Example 1

[0294] This example describes how a biopolymer, cross-linked in a specific manner, produces unexpected and significant benefits in automated dishwashing (ADW) applications, particularly in terms of shine (i.e., providing a form of detergent-aiding activity). For instance, no calcium carbonate (CaCO3) and magnesium carbonate (MgCO3) are deposited on cookware in the dishwashing machine, resulting in an advanced level of clean cookware and a glossy visual appearance. Calcium and magnesium ions are transported via a process that utilizes relatively high hardness (°D, which typically indicates CaCO3). 2+ and Mg 2+ The tap water (at the level of) is introduced.

[0295] In this work, α-1,3-glucan and α-1,2-branched α-1,6-glucan were used, both with weight-average polymerization degrees (DPw) of approximately 800 and 1600, respectively. These dextran polymers were functionalized with negatively charged groups (e.g., organic groups containing carboxyl or sulfonate groups) to produce anionic polymers; alternatively or additionally, the polymers could be oxidized to add a negative charge. The crosslinking agent used to further enhance the properties of the dextran derivatives was ethylene glycol diglycidyl ether. A specific molar ratio range (0.04:1 to 0.06:1) of this crosslinking agent to the level of dextran dry solids in the reactor was observed to be effective in providing the aforementioned detergent / builder benefits during the manufacturing process. Lower and higher crosslinking amounts had an impact on performance, while other types of crosslinking agents showed a negative impact on performance. Finally, the addition of hydrophobic groups to the charged dextran polymers also improved the gloss benefits.

[0296] Screening test methods for evaluating polymer effectiveness

[0297] To evaluate polymer properties from the perspective of gloss benefits, two separate screening methods were developed. One method is to evaluate the delay in turbidity formation in the dishwashing liquid. Turbidity formation is typically an indicator of inorganic scale formation. The so-called transmittance of a liquid indicates how well light passes through it unimpeded. The more suspended insoluble particles there are, the more light will be scattered, resulting in lower light transmittance. The other method is to evaluate the actual deposition of inorganic scale on a standardized glass matrix.

[0298] Anti-deposition screening test scheme

[0299] The anti-deposition screening test protocol is designed to simulate the cycle of a dishwashing machine. Simply put, a dishwashing machine goes through four stages, and in a simplified version, three stages: a main wash, a primary rinse, and then a secondary rinse, followed by drying.

[0300] An anti-deposition assay was developed to simulate a dishwashing cycle. Three stirring plates were set up, each at a different temperature, reflecting different stages of the washing cycle; a drying rack was also included. The washing cycle simulation was selected as follows: a main wash at 50°C to 55°C for 20 minutes, followed by a cold rinse at 25°C for 5 minutes, then a hot rinse at 50°C to 55°C for 5 minutes, followed by drying at ambient temperature. Intermediate stirring was performed in each of these three stages to simulate some mechanical motion; the stirring speed was 150 rpm for the washing cycle and 180 rpm for both rinse steps. Fifteen locations were provided on the three stirring plates for stirring beakers. Ten beakers were selected for each run to avoid time delays, such as in the pipetting step. During these runs, 150-mL glass beakers were deployed and filled with 100 mL of hard water with a hardness of 21°D. For each beaker, a microscope slide was added as a substitute for the glassware. After each given time range, the slides were subjected to different stages. Example 1 of U.S. Patent Application Nos. 63 / 587,005 and 63 / 598,263 (which are incorporated herein by reference) is shown as a photograph.

[0301] The system selected for the anti-deposition assay is based on the following assumptions: The dishwashing tablets come in 18-gram packets and have the following characteristics: - pH 10.2 to 10.5, - 30% by weight of the tablets are carbonates (anhydrous Na2CO3). - 30% by weight of the tablets are citrate (trisodium citrate·2H2O). - 5% by weight of the tablet is the selected polymer.

[0302] The order in which the sequences are added is provided in Table 2.

[0303] Table 2. Order, steps, and other information for adding information See below The washing volume for each step is five liters, maintaining a 90% replenishment volume. This means that after the main wash, 4.5 liters will be pumped out, leaving 0.5 liters, and 4.5 liters of new hard water will be added to the dishwasher. The main wash will then proceed to the cold rinse and the cold rinse will then proceed to the hot rinse.

[0304] These chemical quantities have been converted to fit a 100 ml system. Three types of stock solutions were prepared: - 10.8 g citrate dihydrate (100x citrate stock solution) in 100 mL of hard water [1] - 10.8 g sodium carbonate (100x carbonate stock solution) in 100 mL of demineralized (“demi”) water [2] - Prepare individual 100x stock solutions using 2.16 g of each polymer in 100 mL of hard water [3] In the anti-deposition setting, only 10% of the volume is transferred from the main wash beaker to the first rinse beaker.

[0305] Transmittance determination using a pipetting robot and a plate reader

[0306] The second aspect of polymer performance is its effectiveness in delaying crystal (scale) formation. Transmittance relates to the amount of turbidity a particular liquid possesses. The greater the turbidity, the more suspended particles, the lower the transmittance, and the higher the turbidity. Despite this end result, it is less relevant for the liquid to remain clear during washing, as long as suspended solids can be washed away during the rinsing phase of the dishwasher. The ability to delay crystal (scale) formation and induce stagnation in crystal growth is reflected in its improved transmittance of the liquid. Furthermore, smaller or fewer crystals are easier to wash away.

[0307] To evaluate the effectiveness of the polymer in delaying turbidity formation in liquids, a transmittance assay was developed. The assay utilized a 96-well plate. The main wash could be simulated using this assay. The preparation setup is described below. The steps on the robot and plate reader are described in Table 3. Based on assumptions similar to those used in the anti-deposition assay, the following stock solutions were selected for preparation.

[0308] Dishwashing tablets come in 18-gram packets and have the following values: - 30% by weight of the tablets are carbonates (anhydrous Na2CO3). - 30% by weight of the tablets are citrate (trisodium citrate · 2H2O). - 5% by weight of the tablet is the selected polymer.

[0309] Sodium citrate 20X stock solution: 2.16 g in 100 mL of hard water [4]

[0310] Sodium carbonate 20X stock solution: 2.16 g in 100 mL of demineralized water [5]

[0311] Polymer 40X stock solution: 0.864 g of polymer in 100 mL of hard water [6] ]

[0312] Plate preparation (manual): In the first row (A) - pipette 270 μL of hard water (except for well 12).

[0313] 300 μL of demineralized water was transferred into hole 12 in row A.

[0314] Repeat the test twice on the polymer to be tested.

[0315] Add 30 μL of polymer stock solution 1 to wells 1 and 2 in row A [6]

[0316] Add 30 μL of polymer stock solution 2 to wells 3 and 4 in row A [6]

[0317] Add 30 μL of polymer stock solution 3 to wells 5 and 6 in row A. [6]

[0318] Add 30 μL of polymer stock solution 4 to wells 7 and 8 in row A [6]

[0319] Add 30 μL of polymer stock solution 5 to wells 9 and 10 in row A [6]

[0320] Add 30 μL of Acusol™ 588 stock solution to well 11 in row A. [6]

[0321] Move the liquid up and down to ensure mixing.

[0322] In all other wells, in rows B through H (except column 12), add 150 µL of hard water using a multichannel pipette. Place 150 µL of demineralized water in each of the other wells in column 12. In row A (except well 12), each well now contains a 4X equivalent concentration of the polymer present in the main wash of the dishwashing run. The plate is then sealed and placed in a BIOMEK pipetting robot.

[0323] Table 3. Steps on pipetting robots and microplate readers

[0324] Examples of the synthesis of (crosslinked) carboxymethyl α-1,3-glucan

[0325] α-glucan with approximately 100% α-1,3 bonds was added to a temperature-controlled 3-L glass laboratory reactor, followed by the addition of a mixed solvent (isopropanol, water, and methanol) under a constant nitrogen flow to form an α-1,3-glucan slurry. Then, caustic soda in the form of solid pellets and optionally a crosslinking agent were added, and the dextran was alkalized at 20°C for 60 minutes with stirring. In the next step, chloroacetic acid was added to the reactor, and the reaction mixture was heated to 70°C and allowed to react for 120 minutes. The reaction mixture was then cooled to 20°C and subsequently neutralized to pH 7.0 by adding acetic acid. The crude CMG product was separated by filtration and washed several times with a methanol / isopropanol / water mixture (50 / 30 / 20 vol%). The washed product was dried overnight in a box oven at 55°C and then milled.

[0326] The amounts of reactants and solvents used in these synthesis are listed in the following table (Table B, split into left and right sides):

[0327] Polymer crosslinking and crosslinking agents

[0328] To determine the effectiveness of the crosslinking agents and the amount / polymer weight of each applied, several prototypes with different crosslinking agents and varying amounts of them were prepared. Table 4 shows the different crosslinking agents applied. Table 5 shows the reaction schemes used to crosslink one type of α-1,3-glucan ether. In particular, increasing levels of crosslinking agent (EGDE) were applied to various carboxymethyl α-1,3-glucan ethers (CMG).

[0329] Table 4. Cross-linking agents applied to α-glucan

[0330] Table 5. Example schemes for crosslinking CMG using EGDE AGU, the dehydrated glucose unit of CMG.

[0331] UHDP refers to α-glucan with a DPw of approximately 1600 to 1800 and approximately 100% α-1,3 bonds.

[0332] Complete dishwashing test (14 cycles)

[0333] To fully evaluate the screening test results, a complete tableware test was conducted to demonstrate the rationale for the screening test. Because the test setup had different parameters than those used in the screening test, the results were not 1:1 correlated, but a similar trend was expected. Images were created after 14 washes. The tableware washing test was conducted with minimal detergent formulation to ensure that the crosslinked polymer stress was higher than normally expected. The parameters used in the run are shown in Table 6.

[0334] Table 6 Such as the dishwashing schedule and preparation of ingredients during the 14 runs. No rinsing aids are added to this detergent formulation.

[0335] result

[0336] Anti-deposition effects of different cross-linked α-glucan derivatives

[0337] More than sixty different crosslinked polymer prototypes were tested, both at common polymer concentrations and with dose-response (indicating overdosing of the crosslinked polymer to see the effect). The following trends were observed.

[0338] 1. The more charge added to the water, the better the performance in providing the "glossy" benefit. Charge can be added in two ways: by adding more polymer to the water or by the degree of substitution (chemically adding charged groups to the polymer backbone).

[0339] 2. These results apply to crosslinked carboxymethyl α-1,2-branched α-1,6-glucan ethers and crosslinked carboxymethyl α-1,3-glucan ethers, particularly when crosslinked with EGDE. The results are shown below.

[0340] 3. Moderate crosslinking of α-glucan ether derivatives has a surprisingly positive effect on gloss benefits, with very little crosslinking having no effect and high crosslinking reducing gloss benefits. The results are shown below.

[0341] 4. The results summarized in point 2 are reinforced by testing with carboxymethylated cellulose with increased molecular weight, demonstrating the improved gloss benefit with increasing molecular weight.

[0342] 5. The positive effects of crosslinking were observed only when using the crosslinking agent ethylene glycol diglycidyl ether (EGDE). Other crosslinking agents (1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diethylene glycol diglycidyl ether) had little to no effect, or even no negative effect, on the gloss benefit of crosslinked α-glucan ether derivatives. Only EGDE showed significantly improved performance within a narrow range of crosslinking agent contents.

[0343] 6. The increased charge density on the α-1,3-glucan polymer backbone (e.g., provided by carboxyl ether groups such as carboxymethyl ether groups) combined with moderate crosslinking—in particular with EGDE crosslinking agents (where the ratio of EGDE to charged α-1,3-glucan derivative is about 0.04 to 0.06 moles of EGDE to about 1 mole of α-glucan derivative) achieves the positive effects noted in point 5.

[0344] 7. The charged groups on α-glucan derivatives, such as α-1,3-glucan derivatives, can be carboxylate groups (e.g., as contained in carboxyl alkyl groups such as carboxymethyl), sulfonate groups, or oxidizing groups.

[0345] 8. Other types of functionalization, such as hydrophobic modification (e.g., hydrophobic etherification such as by benzylation), are shown to positively contribute to providing gloss benefits to α-glucan derivatives substituted with charged groups.

[0346] 9. The more charge an α-glucan derivative has, the better it is at delaying the formation of turbidity (i.e., providing a gloss benefit). This is illustrated, for example, using derivative I (which is an α-1,2-branched α-1,6-glucan (DoS 2.3 to 2.6) derived from carboxymethyl groups).

[0347] The result of the increased charge of α-1,3-glucan derivatives

[0348] In the same anti-deposition study, a group of carboxymethylated α-1,3-glucan ether (CMG) derivatives were tested to examine the effect of increasing the charge of the anionic derivatives. The results are shown in Figure 1 The results of three concentration runs with increased charge density and crosslinking of the three polymers are shown in the figure. Figure 1 CMG derivatives are as follows: - OPE 36B: DPw approximately 1600-1800, non-crosslinked, DoS 0.86 contributed by carboxymethyl groups.

[0349] - OPE 97: DPw approximately 1600-1800, crosslinked (0.05 mol EGDE to 1 mol CMG), DoS 0.56 contributed by carboxymethyl groups.

[0350] - OPE 149: DPw approximately 1600-1800, crosslinked (0.08 mol EGDE to 1 mol CMG), DoS 0.97 contributed by carboxymethyl groups.

[0351] Each series increases (doubles) the polymer concentration (equivalent concentration). 2X equivalent concentration The concentration was 4X equivalent. ACUSOL 420 was used as an industrial positive control.

[0352] The result of moderate crosslinking on CMG

[0353] To demonstrate the effect of moderate crosslinking, a series of CMG derivatives with increased levels of EGDE crosslinking were prepared (produced according to Table 5). The crosslinked CMGs exhibited DoS values ​​of approximately 0.54 to 0.56, contributed by the carboxymethyl group. The relative amounts (mol / mol) of EGDE to CMG used herein are... Figure 2 Listed below each image. The method used is an anti-deposition test. Figure 2 It can be observed that there is an optimal value for functionality with a crosslinking agent level of 0.04 to 0.05 moles of crosslinking agent per mole of CMG.

[0354] Results using carboxymethyl cellulose

[0355] In addition, a series of carboxymethyl cellulose (CMC) derivatives were tested to demonstrate the effect of increasing polymer molecular weight on inhibiting scale formation. The results are shown in... Figure 3 In this study, CMC with a DoS of 0.7 or 0.9 was applied in the same manner as CMG. However, the CMC samples had increased molecular weight and were uncrosslinked. An increase in performance was observed with increasing molecular size.

[0356] The result of adding more anionic charge to α-1,3-glucan

[0357] To demonstrate the effect of anionic charge addition on α-1,3-glucan, a group of CMG derivatives (each based on a DPw of approximately 1600-1800, approximately 100% α-1,3-linked dextran polymer) were selected for anti-deposition testing. Table 7 represents the selected CMG compounds, all of which were uncrosslinked. The results of the anti-deposition run are shown in... Figure 4 In the middle, it can be observed that the more anionic charges added to the polymer, the better the anti-deposition behavior (i.e., the more transparent the slide). This result is consistent with the data above ( Figure 1 Related to this, adding an increased amount of polymer to the study container resulted in increased gloss benefits. OPE 97 (which is a moderately crosslinked CMG (above)) was included for reference and similarly demonstrated the advantages of moderate crosslinking. Figure 4 ).

[0358] Table 7. Selected CMG compounds with increased anionic charge levels

[0359] The result of using other crosslinking agents to crosslink CMG

[0360] As shown above, most EGDE-crosslinked CMG compounds exhibit improved results compared to uncrosslinked CMG samples when the crosslinking level is correctly selected. To evaluate the effectiveness of alternative crosslinking agents besides EGDE, anti-deposition tests were performed on CMG samples crosslinked with other crosslinking agents (listed in Table 8). The CMG compounds used for crosslinking were selected based on charge density levels similar to one of the CMG compounds used for EGDE-crosslinking and exhibiting improved performance (OPE 97) (Table 8). OPE 97 was selected as a reference for this study. The results of the anti-deposition tests are shown in... Figure 5 The figure shows that using other crosslinking agents did not result in the same improvement in gloss as when CMG was crosslinked with EGDE. When crosslinked with 1,4-butanediol diglycidyl ether, large dendritic flocs appeared, which precipitated as large crystals on the slide. All crosslinked (non-EGDE) samples unexpectedly gave properties similar to the unpolymer-free control. However, the EGDE-crosslinked samples exhibited anti-deposition activity, consistent with the above results.

[0361] Table 8. CMG crosslinked with other types of crosslinking agents Due to crosslinking agent efficiency , Changes in crosslinking dosage.

[0362] Molar crosslinker ratio to molar CMG

[0363] Results using other types of α-glucan derivatives

[0364] Anti-deposition tests were performed using α-glucans derivatized with (i) carboxymethyl and hydrophobic (benzyl) groups, (ii) by sulfonation derivatization, or (iii) by oxidizing already carboxymethylated α-glucans. Other derivatized α-glucan backbones were tested, such as derivatized α-1,2-branched α-1,6-glucan (α-1,2-1,6-glucan). Data on these different polymers are provided in Table 9. Results on the gloss benefits of using these polymers in the anti-deposition tests are provided in... Figure 6 , 7 In 8, it can be observed that highly anionicly charged carboxymethylated α-1,2-1,6-glucan (containing or not containing oxidatively derivatized carboxylate groups in addition to carboxymethyl carboxylate groups) provides a significant improvement in anti-deposition compared to the polymer-free control. Figure 6 The same results apply similarly to the use of carboxymethyl benzyl α-1,3-glucan ether derivatives ( Figure 7 ).

[0365] Table 9. Alternative polymers for anti-deposition tests

[0366] Results of transmittance test

[0367] (See above: Transmittance Measurement Using a Pipettor and Plate Reader)

[0368] To determine the extent to which the (crosslinked) dextran polymers in the examples could reduce turbidity formation, a transmittance assay was developed. Some results from this work are provided. Figure 9-13 Medium. An optical density of 600 nm (OD600) was applied. These analyses provide a good indication of the level of suspended particles in the liquid. Tests were also performed at 21°D (hardness) and 55°C. Similar amounts of polymer were used as in the anti-deposition test.

[0369] Results of an automatic dishwashing test (14 cycles)

[0370] A full-scale automatic dishwashing machine test was conducted in which the polymer described herein was used in detergent formulations. The gloss benefits of the polymer were evaluated accordingly. The detergent formulations and the methods for conducting the full-scale dishwashing test are as described above (including Table 6). Examples of results after 14 washes are provided in… Figure 14-16 Three tableware substrates were selected for this study: MEPAL tubing, melamine plates, and LIBBEY long beverage cups. It should be noted that the complete tableware washing test partially corresponds to the anti-deposition test, and performance improvement is expected in the case of biopolymers when rinsing aids are added to the formulations used.

[0371] Example 2

[0372] Summary of Example 2

[0373] Crosslinked carboxymethyl α-1,3-glucan (CMG) has demonstrated suitable properties as a rheology modifier in personal care applications. Crosslinked CMG compounds were characterized in terms of viscosity and rheological properties in aqueous suspensions, showing viscosity and yield stress ranges comparable to and significantly higher than those of natural gums, similar to synthetic carbomers. When formulated in model personal care oil-in-water (O / W) emulsions, the positive rheological properties of crosslinked CMG translate into improved emulsion stability, yield stress, and more uniform emulsion droplet dispersions, allowing for the use of significantly lower levels of the polymer in personal care formulations compared to widely used synthetic carbomers.

[0374] Representative methods for preparing cross-linked CMG

[0375] A slurry powder of α-1,3-glucan (DPw approx. 1600-1800) with a particle size < 100 µm was adjusted to an 8% w / v water content and added to the reactor at a loading of 7% w / v in IPA / water. The dextran slurry was activated by adding a suitable amount of 50% NaOH at a molar ratio ranging from 0.5 to 3.0 under continuous overhead mixing. The formulation was held at room temperature for 45 minutes, and then a desired amount of crosslinking agent was added at a molar ratio ranging from 0.01 to 0.2. Suitable crosslinking agents include those listed in Table 4, etc. The crosslinking formulation was stirred at room temperature for 15 minutes, and then, using a feed pump, a desired amount of chloroacetic acid (CAA) dissolved in IPA was added over a 40-minute period at a CAA:dextran molar ratio ranging from 0.5 to 2.0 (to initiate carboxymethylation). Heating was performed simultaneously with the CAA feeding. After all the CAA had been fed and the reactor temperature had reached 70°C, the temperature was maintained for 2 hours. The reactor was then cooled to 50°C and the reaction was neutralized to pH 7 using acetic acid (ice) to obtain a white to off-white polymer slurry. The polymer slurry was purified by continuous vacuum filtration and washed with a mixture of IPA, methanol, and water, followed by a final wash and filtration with methanol. Finally, the purified slurry was dried overnight under vacuum at 60°C to obtain a white to off-white crosslinked CMG powder.

[0376] In the following tests, ethylene glycol diglycidyl ether (EGDE) was used as a crosslinking agent to prepare crosslinked CMG samples. EGDE was added for crosslinking at a molar ratio of 0.01 to 0.1 mol relative to CMG, and the selected candidate used for testing had an EGDE to CMG molar ratio of approximately 0.08 mol.

[0377] Preparation of cross-linked CMG dispersions

[0378] Crosslinked CMG powder was dispersed in deionized water at concentrations ranging from 0.25% w / v to 2.00% w / v using a DLS digital overhead stirrer (Thermo Fisher Scientific, Waltham, MA) with continuous stirring at 500 rpm until homogeneity was achieved; heating, up to 60°C, may be used if necessary. After homogeneity was achieved, the pH of the formulation was adjusted to 6.5 using sodium hydroxide (5 N) or hydrochloric acid (5 N). The crosslinked CMG dispersions exhibited different viscosity ranges from semifluid to thick gel, depending on the final concentration. Xanthan gum (Clariant, Louisville, Kentucky) and carbomer (ULTREZ 30, Lubrizol, Wycliffe, OH) were used as reference polymers for comparative analysis of viscosity, emulsion stability, and yield stress. Control dispersions were prepared according to the protocol described for the crosslinked CMG samples. The samples were stored at 23°C for at least 3 days before viscosity and rheological characterization.

[0379] Effects of crosslinked CMG on relative viscosity and rheological behavior in aqueous dispersions

[0380] The relative viscosity of each polymer dispersion was determined at a range of shear rates from 10 to 250 rpm using a Brookfield DV2T viscometer (Middleborough, Massachusetts) equipped with a recirculation bath for temperature control (20°C) and an RV-6 rotor. For each determined shear rate value, the RV value for each sample was recorded, and the average time period for each determined shear rate value was 60 seconds. Results (in...) Figure 17 As shown in the figure, crosslinked CMG (0.46 DoS) showed that the dispersion viscosity increased with increasing polymer concentration, with a relative viscosity value significantly higher than that of natural gum (xanthan gum) and slightly lower than that of synthetic carbomer (ULTREZ 30), but similar relative viscosity values ​​were achieved at higher polymer concentrations (2% w / v).

[0381] The effect of crosslinked CMG on maintaining dispersion stability despite the addition of sodium chloride was determined compared to a synthetic carbomer control (ULTREZ 30). Polymer dispersions with a concentration of 1% w / v were prepared as described above and mixed with varying amounts of sodium chloride to final salt concentrations ranging from 0.1% to 4% w / v. The relative viscosity of the dispersions after varying the salt concentration was determined using a Brookfield DV2T viscometer as described above. Results (in...) Figure 18As shown in the figure, crosslinked CMG (0.46 DoS) demonstrates a significant advantage over synthetic carbomer (ULTREZ 30) in maintaining viscosity stability, despite increased salt content, a crucial characteristic in the formulation of personal care products and others. When a small amount of salt (0.1%) is added to the system, the synthetic carbomer dispersion shows a significant decrease in relative viscosity, while at the same polymer concentration, crosslinked CMG maintains a significantly higher viscosity; this phenomenon is still observed even with the addition of up to 4% w / v sodium chloride. Figure 18 ).

[0382] The rheological behavior of polymer dispersions was evaluated using a Rheometer Discovery HR-20 (TA Instruments, Newcastle, Delaware) equipped with an ARES G2 40-mm geometry with a fixed gap (0.098 mm), under continuous and oscillating flow programs. All measurements were performed at a controlled temperature of 23°C. Figure 19A -D indicates the effect of increasing concentration (0.25% to 2% w / v) of crosslinked CMG polymers (DoS 0.4-0.5, Figure 19C -D) The viscosity curve changes with shear rate, and is compared with that of synthetic carbomer (ULTREZ 10 or 30, Figure 19A The results show that, for carbomer, the vertical gaps in the viscosity curves separating each polymer concentration tend to narrow with increasing concentration, compared to the case of -B). Figure 17 The results obtained for the Brinell viscosity are consistent, indicating that the viscosity value plateaus at concentrations above 1% w / v, while the gaps between crosslinked CMGs tend to widen at the highest concentrations, suggesting a more efficient linear increase in viscosity.

[0383] Yield strength is important because it characterizes the highest stress a material can withstand before permanent deformation occurs. In the chemical and cosmetic industries, viscosity testing and yield stress determination are crucial parameters for quality control and performance evaluation, allowing manufacturers to predict how products will perform once they reach consumers. Figure 20 The rheological behavior (shear stress versus shear rate) is shown, and Figure 21 The storage modulus and yield stress in aqueous dispersions of crosslinked CMG (DoS 0.4–0.5) at slightly higher concentrations (1.5x–2x) compared to carbomer (ULTREZ 30, highlighted with an asterisk in each figure) are shown without pH adjustment. The variation of yield stress of crosslinked CMG in aqueous dispersions with DoS is shown in the figure. Figure 22This indicates that the yield stress increases directly and linearly with increasing DoS until it reaches a maximum value of about DoS 0.5, and then the yield stress appears to decrease.

[0384] Effects of cross-linked CMG on the rheological behavior and emulsion stability of formulated model personal care products

[0385] Rheology modifiers were added to formulations to increase viscosity, promote yield stress, and control the properties and characteristics of the finished product in a desired manner. Model personal care oil-in-water (O / W) emulsions containing crosslinked CMG were formulated according to the formulation compositions detailed in Table 10 to evaluate the effects of crosslinked CMG on rheological behavior and emulsion stability.

[0386] Table 10. Formulations used for testing oil-in-water emulsions containing 0.5% w / v crosslinked CMG as a rheology modifier composition

[0387] The preliminary physicochemical stability of formulated O / W emulsions containing crosslinked CMG was evaluated by 24-hour freezing (-5°C ± 2°C) and thawing (40°C ± 2°C) cycles over 12 days, covering a total of three cycles. At the beginning and end of each study, sedimentation of the formulations was tested by centrifugation using a LUMiSizer device (LUM GmbH, Berlin, Germany). Samples were placed in cuvettes with a 2 mm optical path and centrifuged at 4000 rpm (5976 g) for 60 minutes. Near-infrared lamps were used to illuminate the cuvettes while the samples were exposed to centrifugal force, allowing for the measurement of transmitted light intensity. This measurement was obtained as a function of sample position over time and along the entire length of the cuvette, providing a transmittance profile. The instability index (I) was determined from the transmittance profile using SepView 6.0 software (LUM GmbH, Berlin, Germany). The results of emulsion stability are summarized in Table 11, showing that crosslinked CMG polymers with a wide range of DoS (0.2–0.5) have improved stabilizing activity for O / W emulsions at 0.5% polymer content after continuous freeze-thaw cycles, compared with carbomer (ULTREZ 10 and ULTREZ 30) and natural gum (xanthan gum).

[0388] Table 11. Compared with synthetic carbomer (ULTREZ 10 and 30) and natural gum (xanthan gum), containing 0.5% w / v crosslinking Changes in the instability index of O / W emulsions with combined CMG (DoS 0.2 to 0.5) at 23°C with continuous freeze-thaw cycles.

[0389] The droplet size variation of an O / W emulsion containing 0.5% w / v crosslinked CMG was evaluated using an optical microscope (Olympus BX41, Tokyo, Japan) and compared with that of carbomer (ULTREZ 30). The O / W emulsion was diluted tenfold in deionized water and applied to a glass slide, then observed under a microscope; the results are shown in... Figure 23Microscopic imaging (20X) showed that crosslinked CMG (DoS 0.4–0.5) exhibited a more uniform droplet distribution than carbomer, and the results were consistent with the instability index obtained by LUMiSizer analysis, suggesting that the smaller and more uniform droplet size observed in CMG samples compared to carbomer may be the reason for its lower instability index and improved emulsion stability.

[0390] Figure 24A -B shows the rheological analysis of the model O / W emulsion containing crosslinked CMG (DoS 0.4-0.5) according to the above scheme. These results indicate that the yield stress and rheological behavior are significantly improved compared to carbomer (ULTREZ 30) formulations with the same polymer content (0.5% w / v). Figure 24A The difference in the range of rheological profiles between crosslinked CMG and carbomer allows for a reduction of its polymer content by half to 0.25% w / v. Figure 24B At the same time, it maintains enhanced rheological properties when compared with higher concentrations of carbomer (0.5% w / v, highlighted with an asterisk).

Claims

1. A composition comprising a cross-linked α-glucan derivative, The cross-linked α-glucan derivative is generated by contacting ethylene glycol diglycidyl ether (EGDE) with a first α-glucan derivative, thereby cross-linking the first α-glucan derivative, wherein the ratio of EGDE to the first α-glucan derivative is about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative.

2. The composition of claim 1, wherein, At least about 50% of the glycosidic bonds in the cross-linked α-glucan derivative are α-1,3 bonds.

3. The composition of claim 2, wherein, At least about 90% of the glycosidic bonds in the cross-linked α-glucan derivative are α-1,3 bonds.

4. The composition of claim 1, wherein, At least about 50% of the glycosidic bonds in the cross-linked α-glucan derivative are α-1,6 bonds.

5. The composition of claim 4, wherein, The cross-linked α-glucan derivative contains at least 1% α-1,2 and / or α-1,3 branches.

6. The composition of claim 1, wherein, The dextran from which the first α-glucan derivative is derived has a weight-average degree of polymerization (DPw) of at least about 200.

7. The composition of claim 1, wherein, The first α-glucan derivative has a degree of substitution (DoS) of up to about 3.0 contributed by at least one organic group.

8. The composition of claim 7, wherein, The organic group is ether-linked to the first α-glucan derivative.

9. The composition of claim 8, wherein, The organic groups include carboxyl, alkyl, hydroxyalkyl, or aryl groups.

10. The composition of claim 8, wherein, The organic group includes carboxymethyl.

11. The composition of claim 8, wherein, The organic group includes benzyl.

12. The composition of claim 9, wherein, The first α-glucan derivative comprises the carboxyl group and the aryl group.

13. The composition of claim 1, wherein, The first α-glucan derivative has a DoS of up to about 3.0 contributed by at least one sulfonate group.

14. The composition of claim 1, wherein, The first α-glucan derivative has been oxidized.

15. The composition of claim 1, wherein, The first α-glucan derivative has a DoS of about 0.35 to 2.5, and wherein at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,3 bonds.

16. The composition of claim 1, wherein, The first α-glucan derivative has a DoS of at least about 2.0, and at least about 50% of the glycosidic bonds of the crosslinked α-glucan derivative are α-1,6 bonds, optionally wherein the first α-glucan derivative contains at least 1% α-1,2 and / or α-1,3 branches.

17. The composition of claim 1, wherein, The ratio of EGDE to the first α-glucan derivative is approximately 0.04 to 0.06 moles of EGDE to approximately 1 mole of the first α-glucan derivative.

18. The composition of claim 1, wherein, The composition is an aqueous composition.

19. The composition of claim 18, wherein, The aqueous composition further comprises at least one cation, and the cross-linked polysaccharide derivative is bound to the cation.

20. The composition of claim 1, wherein, The composition is a home care product, personal care product, industrial product, medical product, or pharmaceutical product.

21. The composition of claim 1, wherein, The composition is in the form of a liquid, gel, powder, hydrocolloid, granules, tablet, capsule, bead or lozenge, single-compartment bag, multi-compartment bag, single-compartment sachet or multi-compartment sachet, or contained therein.

22. The composition of claim 1, further comprising at least one surfactant.

23. The composition of claim 1, further comprising at least one enzyme.

24. The composition of claim 23, wherein, The enzyme is a cellulase, protease, amylase, lipase, or nuclease.

25. The composition of claim 1, further comprising at least one of the following: a complexing agent, a detergency polymer, a surfactant-enhancing polymer, a bleaching agent, a bleaching activator, a bleaching catalyst, a fabric conditioner, clay, a foam promoter, a foam inhibitor, an anti-corrosion agent, a dirt suspending agent, an anti-dirt redeposition agent, a dye, a bactericide, a dulling inhibitor, an optical brightener, a fragrance, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a tinting dye, a visual signal transducer, a defoamer, a structuring agent, a thickener, an anti-caking agent, starch, sand, or a gelling agent.

26. The composition of claim 1, wherein, The composition is in the form of a dishwashing detergent composition or is contained therein.

27. A method for washing or treating a hard surface, the method comprising: (a) Contacting the hard surface with a washing / treatment composition comprising the composition as described in claim 1, and (b) Removing all or part of the washing / treatment composition from the hard surface; This washes or treats the hard surface, wherein the washed / treated hard surface has reduced film formation, spots, turbidity, or other deposits. Optionally, the hard surface is a hard surface of glass, plastic, ceramic, porcelain, metal, or stone.

28. The method of claim 27, wherein, Step (b) includes rinsing the hard surface.

29. The method of claim 27, wherein, The hard surface refers to the hard surface of the tableware.

30. The method of claim 27, wherein it is performed in an automatic dishwashing machine.

31. A method for producing cross-linked α-glucan derivatives, the method comprising: (a) Contacting ethylene glycol diglycidyl ether (EGDE) with a first α-glucan derivative to crosslink the first α-glucan derivative, wherein the ratio of EGDE to the first α-glucan derivative is about 0.03 to 0.07 moles of EGDE to about 1 mole of the first α-glucan derivative, and (b) Optionally, the cross-linked α-glucan derivative produced in step (a) is separated.

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