Esterification of alpha-glucans comprising alpha-1,6 glycosidic linkages

Abstract

This document discloses a method for producing ester derivatives of α-glucan comprising α-1,6 bonds. Such methods may include esterifying α-glucan in an esterification reaction composition comprising an increased α-glucan to total liquid ratio. Further disclosure includes α-glucan ester compositions produced by the disclosed process, and various applications using these compositions.

Description

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 603,232 (filed November 28, 2023), which is incorporated herein by reference in its entirety. Technical Field

[0002] This disclosure pertains to the field of polysaccharide derivatives and derivatization processes. For example, this disclosure relates to processes for the esterification of α-1,6-glucan, and products comprising compositions of α-1,6-glucan derivatives prepared by such processes. Background Technology

[0003] Driven by the desire to find new structural polysaccharides using enzymatic synthesis or microbial genetic engineering, researchers have discovered biodegradable oligosaccharides and polysaccharides that can be economically produced from renewable sources. Further research has shown that such polysaccharides can be chemically modified (derivatively converted) to have additional utility in fields such as personal care, home care, industrial care, pharmaceuticals, and food. For example, ethers and esters of α-glucans containing α-1,3-glycosidic bonds have been disclosed to have a variety of applications (e.g., U.S. Patent Application Publications Nos. 2016 / 0304629, 2016 / 0311935, 2017 / 0204232, 2014 / 0187767, 2020 / 0308371). Various derivatives of α-glucans containing α-1,6 glycosidic bonds and their applications have also been disclosed (e.g., U.S. Patent Application Publication Nos. 2018 / 0312781, 2018 / 0237816, 2018 / 0282385). Hydrophobically modified α-glucans have found applications in liquid formulations such as laundry, fabric care, cleaning, and personal care compositions as viscosity modifiers, emulsifiers, and film-forming agents.

[0004] Despite these advances, there remains a need for dextran derivatization processes that offer better yields and / or other efficiencies. This paper discloses, for example, a novel process for the esterification of α-1,6-glucan (dextran) to help address this need. Summary of the Invention

[0005] In one embodiment, this disclosure relates to a method / process for producing ester derivatives of α-glucan (α-glucan ester derivatives). Such a method / process for producing α-glucan ester derivatives may include:

[0006] (a) Contacting an α-glucan in a reaction composition with at least one esterifying agent containing an organic group, wherein the reaction composition comprises an organic solvent having a pH of at least about 10, wherein the ratio of α-glucan to the total liquid content of the reaction composition is based on a weight ratio of about 0.25 to about 3.0, wherein at least about 50% of the glycosidic bonds of the α-glucan are α-1,6 bonds, wherein at least one organic group is esterified to the α-glucan to produce an α-glucan ester derivative, wherein the α-glucan ester derivative has a degree of substitution (DoS) of up to about 3.0 contributed by the organic group, and

[0007] (b) Optionally, the α-glucan ester derivative can be isolated.

[0008] In another embodiment, this disclosure relates to a composition / product comprising an α-glucan ester derivative, as produced by the methods / processes disclosed herein. Detailed Implementation

[0009] All cited patent and non-patent literature publications are incorporated into this paper in their full text by reference.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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. An example of dextran in this document is α-glucan.

[0015] 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.

[0016] 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).

[0017] 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).

[0018] The branching percentage in α-glucan as used herein typically refers to the percentage of all bonds in the α-glucan representing branching points. For example, the percentage of α-1,2 branches in α-glucan as used herein refers to the percentage of all bonds in the dextran representing α-1,2 branching points. Unless otherwise stated, the bond percentages disclosed herein are based on the total bonds in the α-glucan or on the total bonds in the α-glucan portion specifically involved in this disclosure.

[0019] 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).

[0020] As used herein, the term "molar degree of substitution" (MS) refers to the number of moles of organic groups in each monomer unit of the α-glucan derivative described herein. It should be noted that the molar degree of substitution value for α-glucan derivatives can, for example, have very high upper limits, such as hundreds or even thousands.

[0021] The “molecular weight” of α-glucan or α-glucan derivatives used herein may be expressed as weight-average molecular weight (Mw) or number-average molecular weight (Mn), in 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 α-glucan polymers (such as oligosaccharides) may optionally be provided as “DP” (degree of polymerization), which refers only to the number of monomers contained within the α-glucan; “DP” may also characterize the molecular weight of the polymer based on a single molecule. Various means for calculating these various molecular weight measurements are known in the art, such as high-performance liquid chromatography (HPLC) or size exclusion (gel permeation) chromatography (SEC). As used herein, DPw and DPn can be calculated from Mw and Mn, respectively, by dividing them by the molar mass of a monomer unit M1. 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).

[0022] The term "α-glucan derivative" (and similar terms) used herein typically refers to an α-glucan that has been substituted with at least one type of organic group (e.g., an acyl group, as used herein). The degree of substitution (DoS) of the α-glucan derivatives herein can be up to about 3.0 (e.g., about 0.001 to about 3.0). The organic group acting as an acyl group in this document is linked to the α-glucan derivative via an ester bond. The precursor of the α-glucan derivative in this document typically refers to the underrivatized α-glucan used to prepare the derivative (also referred to as the α-glucan moiety of the derivative). The organic group acting as an acyl group in this document is typically hydrophobic.

[0023] As used herein, the term "degree of substitution" (DoS, or DS) refers to the average number of hydroxyl groups substituted with one or more types of organic groups in each monomer unit of an α-glucan derivative. The DoS of an α-glucan derivative herein may be stated with reference to the DoS of a specific substituent or the total DoS, which is the sum of the DoS values ​​for different substituent types (e.g., in the case of mixed esters). Unless otherwise disclosed, when the DoS is not stated with reference to a specific substituent type, it means the total DoS.

[0024] The term “ester” as used herein (e.g., α-glucan ester derivative) 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. The terms “α-glucan ester derivative,” “α-glucan ester compound,” “α-glucan ester,” etc., are used interchangeably herein. The α-glucan ester derivative as used herein is an α-glucan that has been esterified by one or more organic groups (e.g., hydrophobic organic groups) such that the derivative has a DoS of up to about 3.0 contributed by one or more organic groups. The α-glucan ester derivative herein is defined by the inclusion of the substructure C… G It is called "ester" because of OCOC, where "C" is the carbon atom. G "COC" represents the carbon atom of the monomeric unit (e.g., glucose) of the α-glucan ester derivative (where such a carbon atom is bonded to the hydroxyl group [OH] in the α-glucan precursor of the ester), and wherein "COC" is contained in the acyl group. An example of an α-glucan ester derivative in this article is benzoyl α-glucan.

[0025] The term “hydrophobic” as used herein can characterize a nonpolar organic group (substituted acyl group) that has little or no affinity for water and tends to repel water. Typically, such hydrophobicity can characterize the organic group when it is present in the aqueous compositions herein, optionally taking into account the pH of the aqueous compositions (in some respects, the pH may be 4-10 or 5-9, or any pH as disclosed herein).

[0026] The terms “esterification reaction,” “esterification reaction composition,” etc., used herein refer to a reaction comprising at least α-glucan as disclosed herein, an esterifying agent, and optionally an organic solvent (e.g., an ether, such as dimethyl ether). The reaction is carried out under suitable conditions (e.g., solvent, time, temperature, pH, pressure) for the esterification of one or more hydroxyl groups of the glucose monomer unit of α-glucan with an organic group (acyl group) provided by the esterifying agent, thereby producing an α-glucan ester derivative. A reaction that has been initiated and contains at least a certain amount of α-glucan ester product can also be referred to as an esterification reaction, or, depending on the case, a completed esterification reaction.

[0027] As used herein, the terms “aqueous liquid,” “aqueous fluid,” “aqueous condition,” “aqueous environment,” “aqueous system,” etc., can refer to water or aqueous solutions. An “aqueous solution” may contain one or more dissolved salts, wherein in some embodiments the maximum total salt concentration may be about 3.5 wt%.

[0028] 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.

[0029] As used herein, “aqueous-soluble” or “water-soluble” (and similar terms) α-glucan or its ester derivatives are soluble (or readily soluble) in water or other aqueous conditions, optionally wherein such aqueous conditions are further 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, aqueous-soluble α-glucan or its ester derivatives are soluble in water at pH 7 at 25°C at 1% by weight or higher. In contrast, “aqueous-insoluble” or “water-insoluble” (and similar terms) α-glucan or its ester derivatives are insoluble under these conditions. In some aspects, less than 1.0 g (e.g., an undetectable amount) of aqueous-insoluble α-glucan or its ester derivatives dissolves in 1000 mL of such aqueous conditions (e.g., water at 23°C).

[0030] 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 The terms "viscosity modifier," "viscosity adjusting agent," etc., used in this article refer to any substance that can change / alter the viscosity of a fluid or aqueous composition.

[0031] 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.

[0032] 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.

[0033] "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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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).

[0039] 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.

[0040] 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%.

[0041] 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.

[0042] 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).

[0043] The term "separated" means a substance (or process) in a form not found in nature or in an environment not found in nature. Non-limiting examples of separated substances include any α-glucan ester derivatives disclosed herein; non-limiting examples of separated processes include any α-glucan ester derivatization method (esterification reaction) disclosed herein. The embodiments disclosed herein are believed to be synthetic / artificial (impossible to manufacture or practice without human intervention / participation), and / or possess characteristics not naturally occurring.

[0044] 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.

[0045] Some aspects of this disclosure relate to a method / process for producing ester derivatives of α-glucan (α-glucan ester derivatives). This method may include, for example:

[0046] (a) Contacting an α-glucan in a reaction composition with at least one esterifying agent containing an organic group, wherein the reaction composition comprises an organic solvent having a pH of at least about 10, wherein the ratio of α-glucan to the total liquid content of the reaction composition is based on a weight ratio of about 0.4 to about 3.0, wherein at least about 50% of the glycosidic bonds of the α-glucan are α-1,6 bonds, wherein at least one organic group is esterified to the α-glucan to produce an α-glucan ester derivative, wherein the α-glucan ester derivative has a degree of substitution (DoS) of up to about 3.0 contributed by the organic group, and

[0047] (b) Optionally, the α-glucan ester derivative can be isolated.

[0048] This method may optionally be characterized herein as an esterification method / process. Step (a) of this method may optionally be characterized as an esterification step (or a similar step), while step (b) may optionally be characterized as a separation or treatment step (or a similar step).

[0049] For example, α-glucan can be used in the esterification reaction compositions described herein to produce α-glucan ester derivatives. Such α-glucan can optionally be characterized as an α-glucan precursor of an α-glucan ester. The glycosidic bonds of the α-glucan precursors described herein are typically about or at least 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. An example of a suitable α-glucan precursor for esterification is α-1,6-glucan (for the production of α-1,6-glucan esters [i.e., dextran esters]).

[0050] The α-1,6-glucan precursor (i.e., dextran) used for esterification in this paper may contain, for example, about 40%, 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% α-1,6 glycosidic bonds. In some respects, substantially linear dextran may contain 5%, 4%, 3%, 2%, 1%, 0.5%, or less glycosidic branches (linear dextran has 100% α-1,6 bonds). If present, the glycosidic branches from dextran are typically short, with a length of one (side chain), two, or three glucose monomers. In some respects, dextran may contain about 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 exist entirely or almost entirely as branch points from dextran.

[0051] The dextran in this article may have, for example, α-1,2, α-1,3, and / or α-1,4 branches. In some respects, the branched dextran has 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% of all glycosidic bonds. 9%-11%, 10%-40%, 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 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, dextran with α-1,2-branching can be enzymatically produced according to the procedures in U.S. Patent Application Publication Nos. 2017 / 0218093 or 2018 / 0282385 (both of which are incorporated herein by reference), wherein, for example, an α-1,2-branching 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. Dextran with α-1,3-branching can be prepared, for example, as disclosed in Vuillemin et al. (2016, J. Biol Chem. 291:7687-7702) or U.S. Patent Application Publication No. 2022 / 0267745 (which is incorporated herein by reference).

[0052] For example, any of the aforementioned glycosidic bond and / or branching distribution characteristics (values ​​or ranges) of dextran can similarly characterize the dextran ester derivatives described herein.

[0053] The dextran in this article may have, for example, about, at least about, or less than about 2, 3, 4, 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, 35, 40, 45, 50, 60, 85, 90, 95, 100, 105, 110, 120, 150, 200, 250, 300, 400, 500, 600, 1000, 1500, 2000, 2500, 3000, 4000, 5000, 6000, 8-20, 8-30, 8-100, 8-500, 3-4, 3-5, 3-6, 3-7, 3- 8, 4-5, 4-6, 4-7, 4-8, 5-6, 5-7, 5-8, 6-7, 6-8, 7-8, 90-120, 95-120, 100-120, 105-120, 110-120, 115-120, 90-115, 95-115, 100-115, 105-115, 110-115 90-110, 95-110, 100-110, 105-110, 90-105, 95-105, 100-105, 90-100, 95-100, 90-95, 85-95, 85-90, 5-100, 5-250, 5-500, 5-1000, 5-1500, 5-2000, 5 -2500, 5-3000, 5-4000, 5-5000, 5-6000, 10-100, 10-250, 10-500, 10-1000, 10-1500, 10-2000, 10-2500, 10-3000, 10-4000, 10-5000, 10-6000, 25-100 25-250, 25-500, 25-1000, 25-1500, 25-2000, 25-2500, 25-3000, 25-4000, 25-5000, 25-6000, 30-60, 30-90, 30-120, 30-600, 50-100, 50-250, 50-500 50-1000, 50-1500, 50-2000, 50-2500, 50-3000, 50-4000, 50-5000, 50-6000, 60-90, 60-120, 60-600, 100-250, 100-400, 100-500, 100-1000, 100-150 0, 100-2000, 100-2500, 100-3000, 100-4000, 100-5000, 100-6000, 200-300, 250-500, 250-1000, 250-1500, 250-2000, 250-2500, 250-3000, 250-4000250-5000, 250-6000, 300-2800, 300-3000, 350-2800, 350-3000, 500-1000, 500-1500, 500-2000, 500-2500, 500-2800, 500-3000, 500-4000, 500-5000, 500-6000, 600-1550, 600-1850, 600-2000, 600-2500, 600-3000, 750-1000, 750-1250, 75 DPw, DPn, or DP for ranges of 0-1500, 750-2000, 750-2500, 750-3000, 750-4000, 750-5000, 750-6000, 900-1250, 900-1500, 900-2000, 1000-1250, 1000-1400, 1000-1500, 1000-2000, 1000-2500, 1000-3000, 1000-4000, 1000-5000, 1000-6000, or 1100-1300. In some respects, the Mw of dextran can be about, at least about, or less than about 0.1, 0.125, 0.15, 0.175, 0.2, 0.24, 0.25, 0.5, 0.75, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 18 0, 190, 200, 0.1-0.2, 0.125-0.175, 0.13-0.17, 0.135-0.165, 0.14-0.16, 0.145-0.155, 10-80, 20-70, 30-60, 40-50, 50-200, 60-200, 70-200, 80-200, 90-200, 100-200, 110-200, 1 20-200, 50-180, 60-180, 70-180, 80-180, 90-180, 100-180, 110-180, 120-180, 50-160, 60-160, 70-160, 80-160, 90-160, 100-160, 110-160, 120-160, 50-140, 60-140, 70-140, 80- 140, 90-140, 100-140, 110-140, 120-140, 50-120, 60-120, 70-120, 80-120, 90-120, 90-110, 100-120, 110-120, 50-110, 60-110, 70-110, 80-110, 90-110, 100-110, 50-100, 60-10070-100, 80-100, 90-100, or 95-105 million Daltons. In some respects, the Mw of dextran can be, for example, about, at least about, or less than about 1, 5, 7.5, 10, 12.5, 15, 20, 25, 30, 40, 50, 60, 70, 75, 80, 90, 100, 125, 150, 175, 200, 250, 300, 400, 500, 600, 700, 800, 900, 1000, 1250, 1500, 1750, 2000, 1-2000, 1-1000 1-500, 1-400, 1-300, 1-200, 1-100, 1-50, 10-2000, 10-1000, 10-500, 10-400, 10-300, 10-200, 10-100, 10-50, 20-2000, 20-1000, 20-500, 20-400, 20-300, 20-200, 20-100, 20-50, 30-2000, 30-1000, 3 0-500, 30-400, 30-300, 30-200, 30-100, 30-50, 40-2000, 40-1000, 40-500, 40-400, 40-300, 40-200, 40-100, 40-50, 50-2000, 50-1000, 50-500, 50-400, 50-300, 50-200, 100-2000, 100-1000, 100-500 100-400, 100-300, 100-200, 200-2000, 20-1000, 200-500, 200-400, 200-300, 7.5-10, 7.5-12.5, 7.5-15, 7.5-20, 7.5-30, 10-12.5, 10-15, 10-20, 10-30, 15-25, 15-30, 40-60, 45-55, 190-210, or 290-310 kDa. If desired, the molecular weight of dextran can be calculated based on any of the aforementioned dextran DPw, DPn, or DP values. For example, any of the aforementioned DPw, DPn, DP, or Dalton values / ranges can characterize the dextran described herein, which is either before or after optional branching (e.g., α-1,2 and / or α-1,3). In some aspects, any of the aforementioned DPw, DPn, DP, or Dalton values ​​or ranges can characterize the dextran ester derivatives described herein. The molecular weight of the dextran esters described herein can be calculated, for example, based on any of the aforementioned dextran DPw, DPn, DP, or Dalton values, further considering the DoS of the ester and the type of one or more ester groups.

[0054] The dextran used 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 characteristics, production methods), each of which is incorporated herein by reference. In some respects, the dextran used for esterification herein may be a dextran produced in a suitable reaction of a GTF comprising glucosyltransferase (GTF) 0768 (SEQ ID NO: 1 or 2 of US 2016 / 0122445), GTF 8117, GTF 6831, GTF 5604, GTF 1729, GTF 8845, or GTF 0088 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, GTF 5604, GTF 1729, GTF 8845, or GTF 0088. GTF enzymes 8117, 6831, and 5604 are SEQ ID NOs: 30, 32, and 33 of US 2018 / 0282385 (e.g., the mature form of GTF5604 begins at amino acid residue 37). GTF enzymes 1729, 8845, and 0088 are SEQ ID NOs: 9, 11, and 12 of US 2017 / 0218093.

[0055] The ester derivatives of α-glucan disclosed herein (e.g., α-glucan esters produced by the esterification process described herein) 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 organic group (acyl group) linked to the α-glucan ester. DoS can be, for example, about, at least about, or up to about 0.001, 0.0025, 0.005, 0.01, 0.02, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.075, 0.08, 0.09, 0.1, 0.15, 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, 0.005-1.9, 0.005-1.8, 0.005-1.7, 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, 0.01-2.0, and 0.01-1. 9, 0.01-1.8, 0.01-1.7, 0.01-1.6, 0.01-1.5, 0.01-1.25, 0.01-1.0, 0.01-0.9, 0.01-0.8, 0.01-0.7, 0.01-0.6, 0.01-0.5, 0.01-0.25, 0.01-0.1, 0.03-2.0, 0.03-1.9, 0.03-1.8, 0.03-1.7, 0.03-1 0.6, 0.03-1.5, 0.03-1.25, 0.03-1.0, 0.03-0.9, 0.03-0.8, 0.03-0.7, 0.03-0.6, 0.03-0.5, 0.03-0.25, 0.03-0.1, 0.05-2.0, 0.05-1.9, 0.05-1.8, 0.05-1.7, 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, 0.1-1.9, 0.1-1.8, 0.1-1.7, 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, 0.15-1.9, 0.15-1.8, 0.15-1.7, 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, 0.2-1.9, 0.2-1.8, 0 0.2-1.7, 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, 0.25-1.9, 0.25-1.8, 0.25-1.7, 0.25-1.6, 0.25-1.5, 0. 25-1.25, 0.25-1.0, 0.25-0.9, 0.25-0.8, 0.25-0.7, 0.25-0.6, 0.25-0.5, 0.3-2.0, 0.3-1.9, 0.3-1.8, 0.3-1.7, 0.3-1.6, 0.3-1.5, 0.3-1.25, 0.3-1.0, 0.3-0.9, 0 0.3-0.8, 0.3-0.7, 0.3-0.6, 0.3-0.5, 0.4-2.0, 0.4-1.9, 0.4-1.8, 0.4-1.7, 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. For example, the DoS of this paper can be determined using any suitable technique, such as nuclear magnetic resonance (NMR) spectroscopy (e.g., ...). 1 H-NMR) and / or gas chromatography (GC; e.g., Zeisel GC), liquid chromatography (LC) (e.g., Zeisel LC), inter-polymer chromatography (IPC), and / or any method disclosed by Liu et al. (2022, Des. MonomersPolym. [Design Monomers and Polymers] 25:75-88) (which is incorporated herein by reference).

[0056] Because there are at most three hydroxyl groups in the glucose monomer unit of α-glucan, the total DoS of the α-glucan ester derivatives herein cannot exceed 3.0. Those skilled in the art will understand that, because the α-glucan ester derivatives disclosed herein have a DoS contributed by an organic group (acyl group) of at least one type of ester bond (e.g., between about 0.001 and about 3.0), all substituents in the α-glucan ester derivatives cannot be solely hydroxyl groups.

[0057] In some aspects, the DoS value of the α-glucan ester in the composition represents the DoS of the α-glucan ester derivatives of a unimodal population in the composition. A unimodal population is typically characterized by all α-glucan compounds therein containing similar / uniform amounts of ester functionality. In some aspects, the DoS value of the α-glucan ester in the composition represents the average DoS of the α-glucan ester derivatives of a bimodal or multimodal population overall in the composition. For example, the composition may contain at least (i) α-glucan esters having a DoS of about 0.001, 0.005, 0.01, 0.025, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.001-0.05, 0.001-0.025, 0.005-0.05, or 0.005-0.025, and / or (ii) α-glucan esters having a DoS of approximately 0.8, 0.9, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 1.25-2.5, 1.25-2.25, 1.25-2.0, 1.5-2.5, 1.5-2.25, 1.5-2.0, 1.75-2.5, 1.75-2.25, or 1.75-2.0. For example, the content of (i) in the total α-glucan ester component of the composition may be about 40 wt%-90 wt%, 40 wt%-80 wt%, 40 wt%-70 wt%, 40 wt%-60 wt%, 50 wt%-90 wt%, 50 wt%-80 wt%, 50 wt%-70 wt%, 50 wt%-60 wt%, 60 wt%-90 wt%, 60 wt%-80 wt%, or 60 wt%-70 wt%, 40 wt%-60 wt%, and / or the content of (ii) in the total α-glucan ester component of the composition may be about 10 wt%-50 wt%, 10 wt%-40 wt%, 10 wt%-30 wt%, 10 wt%-20 wt%, 20 wt%-50 wt%, 20 wt%-40 wt%, 20 wt%-30 wt%. wt%, 30 wt%-50 wt%, 30 wt%-40 wt%, or 40 wt%-50 wt%. By way of example only, (i) may be about 50 wt%-80 wt% or about 60 wt%-70 wt%, and (ii) may be about 20 wt%-50 wt% or about 30 wt%-40 wt%. The total DoS of the total α-glucan ester component of the composition may be calculated based on the relative content (e.g., wt%) of each of (i) and (ii). In some respects, the α-glucan esters of (i) and (ii) may be water-soluble and water-insoluble, respectively; however, in some other respects, both (i) and (ii) may be water-soluble or water-insoluble.Typically, the molecular weight and / or bond distribution characteristics of the α-glucan esters in (i) and (ii) are the same; for example, the α-glucan ester precursors in (i) and (ii) may be the same. The bimodal or multimodal groups of α-glucan ester compounds described herein are generally characterized by the presence of varying amounts of one or more ester functional groups within the group, as illustrated by the examples above. The modalities (single-peak vs. bimodal or multimodal) described herein can optionally be determined by fractionation with solvents of different polarities. For example, α-glucan ester products can be extracted sequentially with water, water:IPA (90:10 v / v), water:IPA (75:25 v / v), water:IPA (50:50 v / v), water:IPA (25:75 v / v), and IPA. For α-glucan esters with a single-peak distribution, the amount of extracted product will be concentrated around solvents of similar polarity. For example, α-glucan ester derivatives with a DoS of 0.01–0.3 will be predominantly present in water, water:IPA (90:10 v / v), water:IPA (75:25 v / v), water:IPA (50:50 v / v), and / or water:IPA (25:75 v / v), while ester products with a DoS of 0.7–2.0 will be predominantly present in water:IPA (50:50 v / v), water:IPA (25:75 v / v), and / or IPA. Bimodal or multimodal α-glucan ester products will be present in one or more solvents of different polarities. For example, a bimodal α-glucan ester product consisting of 50% low-DoS and 50% high-DoS components will have product in both water and IPA. Other solvent mixtures may be optionally used for fractionation, and the choice of solvent mixture will depend on the total DoS.

[0058] In some respects, the polydispersity (polydispersity index, PDI) of α-1,6-glucan ester products can be less than 2.2, 2.1, or 2.0. Such polydispersity can optionally characterize α-1,6-glucan ester products having any particular DoS value or range as disclosed herein.

[0059] The ester derivatives of α-glucan disclosed herein (e.g., α-glucan esters produced by the esterification process described herein) may be substituted with at least one hydrophobic organic group (hydrophobic acyl group) linked to the α-glucan ester. For example, the α-glucan derivatives disclosed herein may be derivatized with one, two, three, or more different types of hydrophobic acyl groups described herein. The hydrophobic acyl group may be represented as COR', where R' is hydrophobic and comprises a chain having at least one carbon atom (i.e., one or more carbon atoms); the carbonyl group (CO) of the acyl group is linked to the α-glucan monomer (e.g., glucose) via the oxygen atom of the monomer. R' may be, for example, linear, branched, or cyclic. R' may be saturated or unsaturated, and / or comprises, for example, up to 29 carbon atoms.

[0060] In some respects, the hydrophobic acyl group can be called "C". n Acyl group (or other similar term), where n is an integer of 2 or greater and represents the number of carbon atoms in the acyl group, including carbonyl carbon atoms. C n Acyl groups are typically linear and can be saturated or unsaturated. C n The first carbon (carbon-1) of the acyl group is its carbonyl carbon. In some respects, C n The acyl group can be acetyl (C2), propionyl (C3), butyryl (C4), valeryl (C5), hexanoyl (C6), heptayl (C7), octanoyl (C8), nonanoyl (C9), or decanoyl (C1). 10 ), undecanoyl (C 11 ), dodecyl (C 12 ), tridecyl (C 13 ), tetradecyl (C 14 ), pentadecyl (C 15 ), hexadecyl (C 16 ), heptadecanoyl (C 17 ), octadecyl (C 18 ), nonadecanoyl (C 19 ), eicosyl (C 20 ), icosyl (C 21 ), icosyl (C 22 ), triacyl (C 23 ), tetracosyl (C 24 ), 2,5-pentacyl (C 25 ), 2,6-hexadecyl (C 26 C 27 C 28 C 29 or C 30 Acyl groups. These specific C groups nThe acyl group is saturated. Some of the acyl groups listed above are commonly known as acetyl (acetyl or ethanoyl group), propionyl (propionyl or propanoyl group), butyryl (butanoyl group), valeryl (valeryl or pentanoyl group), caproyl (caproyl or hexanoyl group), enanthyl (enanthyl or heptanoyl group), caprylyl (captanoyl group), pelargonyl (pelargonyl or nonanoyl group), capryl (decanoyl group), lauroyl (dodecanoyl), myristyl (tetradecanoyl), palmityl (hexadecanoyl), stearyl (octadecanoyl), arachidyl (eicosyl), behenyl (dodecanoyl), creosyl (tetradecanoyl), and waxyl (hexadecanoyl). In some respects, the acyl group can be C 10 To C 14 Acyl group, meaning that the acyl group can be C 10 C 11 C 12 C 13 or C 14 Any of the acyl groups (that particular C) n Range naming conventions are accordingly applied to other C in this paper. n (Range). In some respects, the acyl group can be C2 to C3. 26 C4 to C 20 C6 to C 18 C8 to C 18 C 10 To C 18 C 12 To C 18 C6 to C 16 C8 to C 16 C 10 To C 16 C 12 To C 16 C6 to C 14 C8 to C 14 C 10 To C 14 C 12 To C 14 C6 to C 12 C8 to C 12 or C 10 To C 12 Acyl group.

[0061] In some respects, the hydrophobic acyl group can be unsaturated. An unsaturated acyl group can contain, for example, one, two, three, four, five, six, or more double bonds. In some respects, an unsaturated acyl group can contain one or more double bonds across the carbons of the acyl group: (i) 4 and 5, (ii) 5 and 6, (iii) 6 and 7, (iv) 8 and 9, (v) 9 and 10, (vi) 11 and 12, (vii) 12 and 13, (viii) 14 and 15, (ix) 15 and 16, (x) 16 and 17, (xi) 17 and 18, and / or (xii) 18 and 19, wherein the number of carbons is counted starting from the carbonyl carbon of the acyl group (i.e., carbon-1). Some suitable combinations of double bonds in the acyl group are reflected in the following list of unsaturated acyl groups. Although the double bonds of the acyl group can be cis or trans oriented, they are typically cis oriented. In some respects, unsaturated acyl groups can be derived from (or may be derived from) fatty acids. Examples of unsaturated acyl groups in this article include (11Z,14Z)-eicosadienoyl, (11Z,14Z,17Z)-eicostrienoyl, (4Z)-hexadecenoyl, (4Z,7Z,10Z,13Z,16Z)-docosapentaenoyl, (4Z,7Z,10Z,13Z,16Z,19Z)-docosahexaenoyl, (5Z,8Z,11Z,14Z,17Z)-eicospentaenoyl, and (5Z,9Z,12Z)-decanoyl. Octadectrienoyl, (5Z,9Z,12Z,15Z)-Octadectraenoyl, (6Z,9Z,12Z,15Z)-Octadectraenoyl, (7Z,10Z)-Hexadecadienoyl, (7Z,10Z,13Z)-Hexadectrienoyl, (7Z,10Z,13Z,16Z)-Tyrocetraenoyl, (7Z,10Z,13Z,16Z)-Tyrocetraenoyl, (7Z,10Z,13Z,16Z,19Z)-Tyrocepentaenoyl, (8E,10E,12Z)-Octadectrienoyl (8Z,11Z,14Z)-Eicosatetrienoyl, (8Z,11Z,14Z,17Z)-Eicosatetraenoyl, (9Z)-Octadeca-9-en-12-ynyl, (9Z,11E,13E)-Octadeca-trienoyl, (9Z,11E,13Z)-Octadeca-9,11,13-trienoyl, (9Z,12E)-Hexadecadienoyl, (9Z,12E)-Octadecadienoyl, (9Z,12Z)-Octadeca-9,1 2-Diene-6-yneylyl, (9Z,12Z,15Z)-octadec-9,12,15-triene-6-yneylyl, (Z)-tetradec-7-enoyl, cis, cis-tetradec-5,8-dieneyl, cis-tetradec-5-enoyl, arachidonic, dodecenoyl, dodecenoyl, tungyl, heptatrienyl, eicosenoyl, linoleyl, myristenoyl, octadec-9-yneylyl, octadecenoyl, palmitoyl, and oleyl.

[0062] In some aspects, the hydrophobic acyl group may comprise an aryl group. For example, the aryl acyl group may comprise 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 I(a) to I(r):

[0063]

[0064] Structure I(a) - I(r).

[0065] In some respects, the hydrophobic acyl group may contain a branched group. Examples of branched acyl groups in this article include 2-methylpropionyl, 2-methylbutyryl, 2,2-dimethylpropionyl, 3-methylbutyryl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 2,2-dimethylbutyryl, 2,3-dimethylbutyryl, 3,3-dimethylbutyryl, 2-ethylbutyryl, and 2-ethylhexanoyl.

[0066] In some respects, the α-glucan ester derivatives of this disclosure can be characterized as mixed esters by comprising two or more different types of esterified acyl groups (such as any of those disclosed herein). By way of example only, mixed α-glucan esters may comprise at least (i) an acetyl, propionyl, or butyryl acyl group (e.g., about 0.05-0.15 or 0.05-0.2 DoS) and (ii) an aryl acyl group (e.g., benzoyl) (e.g., about 0.2-1.0, 0.2-0.5, 0.2-0.4, 0.2-0.3, 0.3-1.0, 0.3-0.5, or 0.3-0.4 DoS). In some respects, such α-glucan esters may contain α-1,2- and / or α-1,3-branched (e.g., about 15%-25% branched) α-1,6-glucan (e.g., about 10-70, 20-60, or 30-50 kDa) as their dextran component. While in some respects, α-glucan ester derivatives do not contain any other type of substituent group besides the ester group, in other respects one or more other types of substituent groups may be present.

[0067] The hydrophobic acyl groups of the α-glucan ester derivatives described herein may be disclosed, for example, in U.S. Patent Application 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).

[0068] In some respects, the hydrophobic acyl group of the α-glucan ester derivative may contain one or more hydroxyl groups. Typically, such hydroxyl groups themselves can be esterified during the esterification reaction of this disclosure; this may optionally produce α-glucan esters with high molar substitution (e.g., no upper limit) of hydroxyl-containing acyl groups.

[0069] The esterifying agent used in the ester derivatization methods of this disclosure can be, for example, an acyl halide (acid halide) containing any acyl group as disclosed herein. The halides of acyl halides herein can be, for example, chlorides, fluorides, or bromides. Some illustrative examples of acyl halides include aromatic acyl halides (e.g., benzoyl halides such as benzoyl chloride), acetyl halides (e.g., acetyl chloride), propionyl halides (e.g., propionyl chloride), butyryl halides (e.g., butyryl chloride), and lauroyl halides (e.g., lauroyl chloride).

[0070] In some aspects, the esterifying agent used in ester derivatization methods can be, for example, an acid anhydride containing any acyl group as disclosed herein (or a precursor containing the acyl group herein). Some illustrative examples of acid anhydrides include aryl anhydrides (arnesoyl anhydrides) (e.g., benzoic anhydride [benzoic anhydride]), acetic anhydride, propionic anhydride, and butyric anhydride. However, in some aspects, the esterifying agent can be an acrylate, such as vinyl benzoate.

[0071] In some aspects, the molar amount of the esterifying agent in the esterification reaction composition may be approximately equimolar to the molar amount of α-glucan (approximately 1:1). In other aspects, the molar amount of the esterifying agent relative to the molar amount of α-glucan in the reaction may be less than or equal to approximately 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, or 1.05:1, and / or greater than or equal to 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 0.95:1. However, in some respects, the molar amount of the esterifying agent relative to the molar amount of α-glucan in the reaction can be less than or equal to about 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1.2:1, 1.1:1, or 1.05:1, and greater than or equal to 0.4:1, 0.6:1, 0.8:1, 0.9:1, or 0.95:1. The aforementioned molar ratios are typically those initially used in the reaction. Any of the aforementioned molar ratios can also optionally characterize the amount of alkalizing agent used herein relative to the molar amount of α-glucan in the reaction.

[0072] For example, one, two, or more esterifying agents may be present in the esterification reaction composition. When two or more esterifying agents are used, they may all be added simultaneously (or approximately simultaneously, such as within about 5, 10, 15, or 20 minutes) or sequentially (e.g., where a second or any subsequent agent is added after α-glucan esterification is completed (or at least about 90% or 95% completed) by the previously added agent).

[0073] The esterification reaction compositions described herein typically contain an organic solvent with a pH of at least about 10 (optionally characterized as an organic solvent already adjusted to a pH of at least 10). The organic solvents described herein are typically stable under alkaline conditions at pH 10 or higher and remain nonreactive with one or more selected esterifying agents and α-glucan. In some aspects, the organic solvent contains ethers such as dimethyl ether (methoxymethane), diethyl ether (ethoxyethane), methyl ethyl ether (methoxyethane), methyl tert-butyl ether (2-methoxy-2-methylpropane), divinyl ether (ethyleneoxyethylene), cyclopropyl methyl ether (methoxycyclopropane), or furans (e.g., tetrahydrofuran). In some aspects, the organic solvent contains alkanes such as propane, butane, or pentane. In some aspects, the organic solvent contains only the ethers (and / or alkanes described herein) as its organic solvent component. However, in some aspects, the organic solvent contains aldehydes or ketones (particularly because the ketone does not have a CH group at the α-position of its carbonyl group, rather than being an acidic ketone). The organic solvents described herein typically do not contain esters, lactones, or carbonates. Organic solvents may contain one or two or more organic solvents (e.g., two or more ethers or alkanes).

[0074] The organic solvents described herein may have boiling points of, for example, about or less than about 150°C, 140°C, 130°C, 120°C, 110°C, 100°C, 90°C, 80°C, 70°C, 60°C, 50°C, 40°C, 30°C, 25°C, 20°C, 15°C, 10°C, 5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, or 30°C, or 30°C to 30°C, 30°C to 20°C, 30°C to 10°C, 30°C to 0°C, 30°C to 10°C, or 30°C to 20°C at a pressure of about 1 bar (approximately atmospheric pressure). The organic solvents described herein are generally able to remain liquid when placed under elevated pressures (such as about or at least about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 bar) and optionally at elevated temperatures (such as about 50°C–90°C, 50°C–80°C, 60°C–90°C, or 60°C–80°C).

[0075] In some respects, the pH of the organic solvent of the esterification composition disclosed herein (or optionally characterized as the pH of the esterification composition) may be about or at least about 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 10⁻¹³, ​​10⁻¹².5, 10⁻¹², 10⁻¹¹.5, 10.5-13, 10.5-12.5, 10.5-12, 10.5-11.5, 11-13, 11-12.5, 11-12, or 11-11.5. The pH can be adjusted to the values ​​disclosed herein by adding a suitable base. Examples of suitable bases are alkali metal hydroxides (e.g., alkali metal hydroxides such as NaOH, KOH, or LiOH). Typically, a suitable base is mixed with the organic solvent to raise its pH to at least 10. For example, the base can be added purely or as an aqueous solution, such as an aqueous solution of alkali metal hydroxide (e.g., containing 40 wt%-60 wt% alkali metal hydroxide and 40 wt%-60 wt% water).

[0076] The organic solvents described herein typically contain water (e.g., due to being adjusted to have a pH). In some aspects, the organic solvents may contain about or at least about 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 5 wt%–25 wt%, 5 wt%–20 wt%, 5 wt%–15 wt%, 5 wt%–10 wt%, 10 wt%–25 wt%, 10 wt%–20%, or 10 wt%–15 wt% of water. In this respect, the organic solvents described herein may optionally be characterized as partially aqueous or semi-aqueous.

[0077] The concentration / content of α-glucan in the esterification reaction composition described herein may be, for example, about or at least about 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, 15 wt%-50 wt%, 15 wt%-45 wt%, 15 wt%-40 wt%, 20 wt%-50 wt%, 20 wt%-45 wt%, 20 wt%-40 wt%, 25 wt%-50 wt%, 25 wt%-45 wt%, or 25 wt%-40 wt%. The temperature of the esterification reaction composition described herein can be, for example, about or at least about 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 40°C-90°C, 40°C-80°C, 40°C-70°C, 50°C-90°C, 50°C-80°C, 50°C-70°C, 60°C-90°C, 60°C-80°C, or 60°C-70°C. In some aspects, the esterification reaction composition can be subjected to a pressure of about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 6-16, 8-16, 10-16, 12-16, or 14-16 bar. In some respects, the atmosphere surrounding the esterification reaction composition may be an inert gas, such as nitrogen. In some respects, the esterification reaction may be carried out for about or at least about 0.5, 1, 1.5, 2, 3, 4, 0.5-3, 0.5-2, 0.5-1.5, 1-3, 1-2, or 1-1.5 hours.

[0078] Typically, all components of the esterification reaction composition described herein (at least α-glucan, esterifying agent, and organic solvent [already at pH ≥ 10, or adjusted to pH ≥ 10 by additives during the preparation of the reaction]) are mixed together before heating to the aforementioned reaction temperature. The initial preparation of the esterification reaction composition can typically be carried out under ambient conditions / room temperature (e.g., 15°C–30°C, 15°C–25°C, 20°C–30°C, or 20°C–25°C) (however, in some other respects, the mixing temperature can be about or up to about 5°C, 0°C, 5°C, 10°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C). 100°C, 110°C, 120°C, 30°C-60°C, 40°C-60°C, 5°C-50°C, 0°C-50°C, 10°C-50°C, 20°C-50°C, 30°C-50°C, 40°C-50°C, or 70°C-80°C, and / or the mixing temperature may be below the α-glucan decomposition temperature or below the boiling point of the esterifying agent. In some respects, (i) the α-glucan is mixed with an organic solvent before adding (mixing into) the alkalizing agent of this article, such as an alkali metal hydroxide, or (ii) the α-glucan is mixed with a mixture (premix) comprising an organic solvent and an alkalizing agent (i.e., the pH of the organic solvent has been adjusted to ≥ 10 before being added to the α-glucan). Depending on the organic solvent used, the pressure can be increased to above atmospheric pressure (e.g., at least 4 bar) during the preparation of the esterification composition.

[0079] For example, the ratio of α-glucan to the total liquid content of the esterification reaction composition can be from about 0.25 to about 3.0 by weight. The ratio can be, for example, about or at least about 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 0.25-0.7, 0.25-0.6, 0.25-0.5, 0.3-0.7. The ratios are typically determined immediately after each reactive component has been added. The total liquid component of the esterification reaction typically refers to all actual liquid components initially present in the esterification reaction composition, which typically includes one or more organic solvents, water (e.g., water from the alkaline aqueous solution described herein, sometimes present as residual water in the α-glucan material), and one or more esterifying agents. Given the relatively high content of α-glucan relative to liquid in the esterification reaction described herein, the reaction may optionally be characterized as a high-solids reaction. However, in some alternative aspects, the ratio of α-glucan to the total liquid in the esterification reaction composition can be based on less than 0.25 by weight (e.g., the reaction does not necessarily have to have high solids); such embodiments may use any relevant parameters herein as appropriate, such as the use of organic solvents with low boiling points (e.g., less than 25°C or 30°C) and / or increased pressure during the reaction.

[0080] Contacting two or more esterification reaction components during reaction preparation can be performed using a mixer capable of powder mixing (e.g., a shear mixer). Mixing can be performed, for example, at a rate of about or at least about 50, 100, 150, 200, 250, 300, 100-300, 100-250, 100-200, 150-300, 150-250, or 150-200 rpm. Any mixing prior to the start of the reaction can be performed, for example, for at least about 10, 20, 30, 45, or 60 minutes. Examples of suitable mixers include plowshare mixers, centrifugal mixers, agglomerators, and granulators. A plowshare mixer typically comprises a cylindrical drum equipped with plow-shaped mixing elements mounted on a horizontal central drive shaft. Typically, the contact (mixing) of this material is carried out in a vessel capable of maintaining / sustaining the elevated pressure of this material, such as an autoclave reactor vessel (equipped with a mixer). In some respects, the α-glucan is first mixed with an organic solvent, followed by the addition of an alkalizing agent (or the α-glucan is mixed with an organic solvent that has been premixed with an alkalizing agent), and then the addition of an esterifying agent. Throughout the entire reaction, or for most of the reaction, the esterification reaction prepared and initiated herein is typically subjected to any of the aforementioned mixing conditions (e.g., rpm).

[0081] The esterified α-glucan derivatives generated in the esterification reaction composition described herein may optionally be isolated.

[0082] Product separation may include the removal of all or most (e.g., ≥ 90 wt% or 95 wt%) of the organic solvent from the completed reaction composition. For example, evaporation can be used to remove the organic solvent. If the esterification reaction described herein is carried out under elevated pressure, that pressure can be released at the time when the reaction is complete or when it is desired to end. In some aspects, such as those using organic solvents with low boiling points (e.g., less than 30°C or 25°C), reducing the pressure can accelerate solvent removal via evaporation. In some aspects, the removal of organic solvent by evaporation can be carried out by applying heat and / or vacuum. In some aspects, the organic solvent can be removed by means such as filtration, optionally followed by evaporation.

[0083] Typically, one or more washing steps may be performed, such as with an ester product from which the organic solvent has been largely or completely removed. In some aspects, washing may include washing the α-glucan ester product with one or more polar organic solvents. In some aspects, the α-glucan ester product may be bimodal and may be washed, for example, with water to remove any unesterified α-glucan and / or low-DoS α-glucan esters. Following washing, liquid is typically removed from the solid, such as by using a filter funnel, centrifuge, filter press, or any other method or apparatus that allows for the removal of liquid from the solid. Washing may be performed, for example, once, twice, three times, four times, five times, or more. In some aspects, the volume of the polar organic solvent used for washing may be about or at least about 0.5 times, 1 time, 1.5 times, 2 times, 2.5 times, or 3 times the volume of the esterification reaction composition. In some aspects, one or more washes may include applying high shear (e.g., about 5000 rpm for about 30 seconds) to a suspension of the solid in the polar organic solvent. The separated / washed solids can then be optionally dried, such as by vacuum drying, air drying, or freeze drying, optionally with heat applied (e.g., any suitable temperature disclosed herein). The dried product can optionally be ground or granulated.

[0084] The polar organic solvents described herein (such as those used for washing or precipitation) typically contain one type of polar organic solvent, but may optionally contain two, three, or more polar organic solvents. The polar organic solvents described herein typically contain only one or more polar organic solvents, but in some cases may contain about 30 wt%, 20 wt%, 10 wt%, 5 wt%, or 1 wt% water. In some aspects, the polar organic solvent may be proton. Examples of proton polar organic solvents described herein include alcohols such as methanol, ethanol, isopropanol, 1-propanol, tert-butanol, n-butanol, and isobutanol.

[0085] The yield of the α-glucan ester derivative produced in the esterification reaction described herein can be, for example, about or at least about 50%, 55%, 60%, 65%, 70%, 50%-70%, 50%-65%, 55%-70%, 55%-65%, 60%-70%, or 60%-65%. In some aspects, the yield can be based on the level of acyl incorporation in the α-glucan ester product, taking into account the amount of esterifying agent (i.e., acyl source) initially used in the esterification reaction. In some aspects, the yield can be based on the amount of α-glucan ester produced relative to the amount of non-derivatively used α-glucan precursor initially used in the esterification reaction.

[0086] Some aspects of this disclosure relate to products / compositions comprising α-glucan ester derivatives as disclosed herein. For example, the product / composition may comprise an α-glucan ester derivative produced by a method / process as disclosed herein. For example, the product / composition may comprise a hydrophobic α-glucan ester derivative (i.e., an α-glucan substituted with one or more different hydrophobic ester / acyl groups herein). For example, the α-glucan ester of the product / composition herein may have any of the glycosidic bond, molecular weight, DoS, and / or acyl substitution distribution characteristics as disclosed herein, and any other disclosed characteristics. The α-glucan ester derivative product may be provided as a purified product (e.g., ≥ 99 wt% or 99.5 wt%) or in an unpurified form (e.g., crude esterification reaction product); either of these forms may be used accordingly to produce a product / composition comprising an α-glucan ester derivative.

[0087] The compositions disclosed herein can be, for example, aqueous compositions (e.g., solutions, or mixtures such as colloidal dispersions or emulsions) or dry compositions (e.g., dry powders). In some aspects, the compositions herein may contain 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, 2 9, 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, 94, 95, 96, 97, 98, 99, or 99.5 wt% or w / v% of the α-glucan ester derivatives described herein. The composition may comprise, for example, a range between any two of these wt% or w / v% values ​​(e.g., 5-50, 5-45, 5-40, 5-35, 5-30, 5-25, 5-20, 5-15, or 5-10 wt% or w / v%). The liquid component of the aqueous composition may be an aqueous fluid such as water or an aqueous solution. The solvent of the aqueous solution 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.

[0088] 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).

[0089] In some aspects, the aqueous component of the aqueous composition does not have (detectable) soluble sugars, or has about 0.1-1.5, 0.1-1.25, 0.1-1.0, 0.1-0.75, 0.1-0.5, 0.2-0.6, 0.3-0.5, 0.2, 0.3, 0.4, 0.5, or 0.6 wt% soluble sugars. Such soluble sugars may include, for example, sucrose, fructose, Leuconostose, and / or soluble glucose-oligosaccharides. In some aspects, the aqueous component of the aqueous composition may have, for example, one or more salt / buffer solutions (e.g., Na+). + Cl - (e.g., ≤0.1, 0.5, 1.0, 2.0, or 3.0 wt%), NaCl, phosphate, tris, citrate, and / or pH values ​​of 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, 4.0-10.0, 4.0-9.0, 4.0-8.0, 5.0-10.0, 5.0-9.0, 5.0-8.0, 6.0-10.0, 6.0-9.0, or 6.0-8.0.

[0090] The temperature of the composition described herein can be, for example, about, at least about, or up to 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, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 5°C-50°C, 20°C-25°C, 20°C-30°C. , 20°C-40°C, 30°C-40°C, 40°C-130°C, 40°C-125°C, 40°C-120°C, 70°C-130°C, 70°C-125°C, 70°C-120°C, 80°C-130°C , 80°C-125°C, 80°C-120°C, 60°C-100°C, 60°C-90°C, 70°C-100°C, 70°C-90°C, 75°C-100°C, 75°C-90°C, or 75°C-85°C.

[0091] In some respects, the compositions 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 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.

[0092] In some respects, the compositions herein may be detergent compositions. Examples of such compositions as detergents for washing dishes and detergents for fabric care are disclosed herein.

[0093] In some respects, the compositions herein may comprise one or more salts, such as sodium salts (e.g., NaCl, Na₂SO₄). Other non-limiting examples of salts include those having the following cations: (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) Acetates, 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, nitrides, oxalates, oxides, perchlorates, permanganates, peroxides, phosphates, phosphides, phosphites, silicates, stannates, stansites, sulfates, sulfides, sulfites, tartrates, or thiocyanate anions. 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).

[0094] The compositions described herein may optionally contain one or more enzymes (active enzymes). Examples of suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipases (e.g., metallolipases), xylanases, lipases, phospholipases, esterases (e.g., aryl esterases, polyesterases), peroxyhydrolases, keratins, pectins, pectinases, 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 at, for example, about 0.0001-0.1 wt% (e.g., 0.01-0.03 wt%) of active enzyme (e.g., calculated as pure enzyme protein). In fabric care or automatic dishwashing applications, the enzymes herein (e.g., any of the above, such as cellulase, protease, amylase, and / or lipase) may be present in the aqueous compositions (e.g., detergents, greywater) in which fabrics or tableware are treated, for example, at a concentration of at least about 0.01-0.1 ppm total enzyme protein, or about 0.1-10 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.

[0095] In some respects, α-glucan ester 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.

[0096] The composition may comprise one, two, three, four or more different α-glucan ester derivatives as described herein and optionally at least one non-derivative α-glucan (e.g., as disclosed herein). For example, the composition may comprise at least one type of α-glucan ester derivative and at least one type of α-glucan; in some aspects, the latter may be (or can be) a precursor compound of the former. In some aspects, a non-derivative α-glucan (e.g., a precursor compound) is not present.

[0097] The compositions disclosed herein may be in the form of, for example, home care (family care) products, personal care products, industrial products, medical products, or pharmaceutical products, such as those 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, all of which are incorporated herein by reference. In some aspects, the composition may contain at least one component / ingredient of a home care product, personal care product, industrial product, or pharmaceutical product as disclosed in any of the foregoing disclosures and / or as disclosed herein.

[0098] 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, home care products, or industrial products: for example, thickening, freeze / thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, adhesion, suspension, dispersion, gelation, or reduced mineral hardness.

[0099] 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, pastes, balms, ointments, hair oils, gels, liquids, 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 intended pharmacological effect.

[0100] 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 roughness and / or dryness while improving skin softness and micro-refinement). Typically, skin care products may 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, glycosphingolipids, 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).

[0101] 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 care products, bath gel, shower gel, body wash, facial cleanser, lip balm, skin care products, cold cream, moisturizer, body spray, soap, body scrub, exfoliant, astringent, scruffing lotion, hair removal products, permanent waving solution, anti-dandruff formulations, antiperspirant compositions, deodorants, shaving products, pre-shaving products, after-shaving products, cleansers, skin gels, rinses, 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.

[0102] In some respects, personal care products can be hair care products. Examples of hair care products in this document include shampoos, hair bleaching agents (leave-in or rinse-out), cream bleaching agents, hair dyes, hair coloring products, hair shine products, hair serums, anti-frizz products, split end repair products, mousses (e.g., hair styling mousses), hair sprays (e.g., hair setting sprays), and styling gels (e.g., hair setting gels). In some embodiments, hair care products may be in the form of liquids, pastes, gels, 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.

[0103] In some respects, the composition can be a hair care composition, such as a hair styling or setting composition (e.g., hair spray, hair gel or shampoo, hair mousse / foam) (e.g., aerosol hairspray, non-aerosol pump hairspray, spray, foam, cream, paste, non-runny gel, mousse, hair oil, lacquer, hair wax). Hair styling / compositions / formulations that can be adapted to include at least one α-glucan ester derivative described herein may be, for example, US 20090074697, WO 1999048462, US20130068849, JPH0454116 A, US 5304368, AU 667246 B2, US 5413775, US 5441728, US5939058, JP 2001302458 A, US 6346234, US 20020085988, US 7169380, US 20090060858, 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). urea), butylcarbamate iodopropynyl ester), emollients (e.g., panthenol, isopropyl myristate), rheology-modified or thickening polymers (e.g., acrylate / methacrylamide copolymer, polyacrylic acid [e.g., CARBOMER]), emulsified oil phase, 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), aerosol propellants (e.g., C3-C5 alkanes, such as propane, isobutane, or n-butane, monoalkyl ethers, dialkyl ethers, such as di(C1-C4 alkyl) ethers [e.g., dimethyl ether]), and / or any other suitable materials described herein. In some respects, α-glucan ester derivatives, as used in hair styling / fixing compositions, can act as hair fixation / setting agents (typically non-permanent hair fixation, but long-lasting), and optionally be the sole hair fixation agent in the composition. Additional 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 listed above.

[0104] The total content of one or more α-glucan ester derivatives in hair care compositions such as the hair styling / styling compositions described herein may be, for example, about, at least about, or less than about 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 0.5 wt%-15 wt%, 0.5 wt%-10 wt%, 0.5 wt%-5 wt%, 0.5 wt%-2 wt%, 1 wt%-15 wt%, 1 wt%-10 wt%, 1 wt%-5 wt%, 1 wt%-2 wt%, 2.5 wt%-7.5 wt%, 3 wt%-7 wt%, or 4 wt%-6 wt%. 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%.

[0105] Examples of hair styling gel formulations described herein may contain approximately 90 wt%-95 wt% (e.g., approximately 92 wt%) of solvent (e.g., water), 0.3 wt%-1.0 wt% (e.g., approximately 0.5 wt%) of thickener (e.g., polyacrylic acid), 0.1 wt%-0.3 wt% (e.g., approximately 0.2 wt%) of chelating agent (e.g., EDTA) (optional), 0.2 wt%-1.0 wt% (e.g., approximately 0.5 wt%) of humectant (e.g., glycerin), 0.01 wt%-0.05 wt% (e.g., approximately 0.02 wt%) of UV blocker (e.g., benzophenone-4) (optional), 0.05 wt%-0.3 wt% (e.g., approximately 0.1 wt%) of preservative (e.g., diazolidinyl urea) (optional), and 0.5 wt%-1.2 wt% (e.g., approximately 0.8 wt%) of humectant. 0.1 wt% emulsifier (e.g., oleyl alcohol polyether-20), 0.1 wt%-0.3 wt% (e.g., about 0.2 wt%) fragrance / perfume (optional), 0.2 wt%-1.0 wt% (e.g., about 0.5 wt%) pH stabilizing compound (e.g., aminomethylpropanol), and 3 wt%-7 wt% (e.g., about 5 wt%) α-glucan ester derivatives herein (e.g., as hair fixation / styling agents).

[0106] Examples of hair styling gel formulations described herein may contain approximately 0.2 wt% to 1.0 wt% (e.g., approximately 0.5 wt%) of a pH-stabilizing compound (e.g., aminomethylpropanol), 0.1 wt% to 0.3 wt% (e.g., approximately 0.2 wt%) of a fragrance / perfume (optional), 0.05 wt% to 0.12 wt% (e.g., approximately 0.08 wt%) of a surfactant (e.g., ethoxylated dimethicone polyol), 0.05 wt% to 0.12 wt% (e.g., approximately 0.08 wt%) of a conditioning agent (e.g., cyclic dimethylsiloxane) (optional), 0.05 wt% to 0.3 wt% (e.g., approximately 0.2 wt%) of a preservative (e.g., sodium benzoate) (optional), 15 wt% to 20 wt% (e.g., approximately 17 wt%) of water, and 30 wt% to 40 wt% (e.g., approximately 65 wt%) of water. 40 wt% of alcohols (e.g., ethanol), 40 wt%-60 wt% (e.g., about 45 wt%) of propellants (e.g., dimethyl ether, or a mixture of dimethyl ether and C3-C5 alkanes in a ratio of about 2:1 [e.g., a mixture of propane and isobutane]), and 2 wt%-4 wt% (e.g., about 2.75 wt%) of α-glucan ester derivatives herein (e.g., as hair fixation / styling agents).

[0107] Some aspects of this disclosure relate to hair that has been treated with the hair care compositions described herein (e.g., hair styling / composition compositions, shampoos, or conditioning agents). For example, the hair may contain α-glucan ester derivatives on its surface, such as in a film / coating of the hair, and / or adsorbed or otherwise deposited on the hair surface; alternatively, one or more other ingredients of the hair care compositions described herein may also be present. Typically, hair as disclosed herein, such as hair with a coating containing α-glucan esters, does not exhibit visible flaking (i.e., little or no noticeable flaking).

[0108] Various examples of personal care formulations comprising at least one α-glucan ester derivative as disclosed herein are disclosed below (1-3).

[0109] (1) A hair conditioning composition comprising: cetyl alcohol (1%-3%), isopropyl myristate (1%-3%), hydroxyethyl cellulose (Natrosol® 250 HHR, 0.1%-1%), α-glucan ester derivative (0.1%-2%), potassium salt (0.1%-0.5%), Germaben® II preservative (0.5%, obtained from International Specialty Products), and the balance being water.

[0110] (2) A hair shampoo composition comprising: 5%-20% sodium lauryl ether sulfate (SLES), 1 wt%-2 wt% cocamidopropyl betaine, 1 wt%-2 wt% sodium chloride, 0.1%-2% α-glucan ester derivative, preservative (0.1%-0.5%), and the balance being water.

[0111] (3) A skin lotion composition comprising: 1%-5% glycerin, 1%-5% ethylene glycol stearate, 1%-5% stearic acid, 1%-5% mineral oil, 0.5%-1% acetylated lanolin (Lipolan® 98), 0.1%-0.5% cetyl alcohol, 0.2%-1% triethanolamine, 0.1 wt%-1 wt% Germaben® II preservative, 0.5 wt%-2 wt% α-glucan ester derivative, and the balance being water.

[0112] The pharmaceutical products described herein may be in the form of, for example, emulsions, liquids, elixirs, gels, suspensions, solutions, creams, 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, for example, in capsules, tablets, tablet coatings, and as excipients for pharmaceutical preparations and drugs.

[0113] The household 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, for example, downhole operations / fluids (e.g., hydraulic fracturing and enhanced oil recovery).

[0114] 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), having at least one water-soluble α-glucan ester derivative as disclosed herein. The concentration of the α-glucan ester derivative in such water (i) or (ii) may, for example, be 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 contemplated that the α-glucan ester derivative may, in some respects, remain completely or substantially in the solution and provide viscosity. Such a solution (i) or (ii), with viscosity adjusted by the α-glucan ester derivative described herein, may be used in systems in which such a solution is used (e.g., any system described herein, such as downhole operations).

[0115] In some aspects, the compositions described herein may be in the form of or comprise 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 detergent; fabric conditioner; 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 form, such as granular detergents or fabric softener sheets added to a dryer. Other non-limiting examples of fabric care compositions may include: general or heavy-duty detergents in granular or powder form; general or heavy-duty detergents in liquid, gel, or paste form; liquid or dry detergents for delicate fabrics (e.g., delicate clothing); cleaning aids such as bleach additives, “stain remover sticks,” or pretreatments; products containing a base material, 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, block, bead or lozenge, single-compartment bag, multi-compartment bag, single-compartment sachet or multi-compartment sachet.

[0116] 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.

[0117] 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 polysaccharide, 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).

[0118] The detergent compositions described herein may optionally comprise one or more detergent builders or builder systems. In some aspects, oxidized α-1,3-glucan may be included as a co-builder; the oxidized α-1,3-glucan compound used herein is disclosed in U.S. Patent Application Publication No. 2015 / 0259439. In some aspects incorporating at least one builder, 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 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).

[0119] 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).

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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); nitrotriacetic 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% by weight of the composition of the at least one dye transfer inhibitor.

[0124] 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.

[0125] 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.

[0126] 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).

[0127] In some respects, in addition to α-glucan ester 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.

[0128] 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.

[0129] 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).

[0130] 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.

[0131] Specific forms of detergent compositions suitable for the purposes of this document are, for example, US 20090209445 A1, US20100081598 A1, US 7001878 B2, EP 1504994 B1, WO 2001085888 A2, WO 2003089562 A1, WO 2009098659 A1, WO 2009098660 A1, WO 2009112992 A1, WO 2009124160 A1, WO2009152031 A1, WO 2010059483 A1, WO 2010088112 A1, WO 2010090915 A1, WO2010135238 A1, and WO 2011094687. All of the information disclosed in A1, WO 2011094690 A1, WO 2011127102 A1, WO2011163428 A1, WO 2008000567 A1, WO 2006045391 A1, WO 2006007911 A1, WO2012027404 A1, EP 1740690 B1, WO 2012059336 A1, US 6730646 B1, WO 2008087426 A1, WO 2010116139 A1 and WO 2012104613 A1 are incorporated herein by reference in their entirety.

[0132] 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.

[0133] 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).

[0134] 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).

[0135] 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).

[0136] Detergent compositions such as heavy-duty laundry detergents described herein may optionally further include at least one dye transfer inhibitor, examples of which are described above.

[0137] 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.

[0138] 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)).

[0139] Detergents as described herein, such as those used for fabric care (e.g., clothing), may be contained in, for example, unit doses (e.g., pouches or sachets, blocks). The unit dose may consist 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 doses described herein are typically closed structures of any form / shape suitable for containing and protecting their contents without allowing the contents to dissipate before contact with water. In some aspects, the unit dose may contain water-dispersible fibers.

[0140] The compositions disclosed herein may be in the form of, for example, dishwashing detergent compositions or may comprise dishwashing detergent compositions. Examples of dishwashing detergents include automatic dishwashing detergents (typically used in dishwashing machines) and hand-washing dishwashing detergents. Dishwashing detergent compositions may be in any dry or liquid / aqueous form as disclosed herein. Components that may be included in some aspects of dishwashing detergent compositions 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).

[0141] Dishwashing detergents, such as those for automatic dishwashing machines or liquid dishwashing, 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) about 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 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 suitable to include the α-glucan ester derivatives described herein) may be as disclosed in U.S. Patent Nos. 8,575,083 or 9,796,951, or U.S. Patent Application Publication No. 2017 / 0044468, each of which is incorporated herein by reference.

[0142] Detergents described herein, such as detergents for dishwashing, may be contained in, for example, unit doses (e.g., pouches or sachets, blocks) (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.

[0143] It is believed that many commercially available detergent formulations are suitable for use with α-glucan ester derivatives, including those 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).

[0144] The compositions disclosed herein may be in the form of, for example, oral care compositions or may comprise 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., 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” as used 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).

[0145] The oral care compositions described herein may contain, for example, about 0.01-15.0 wt% (e.g., about 0.1-10 wt% or about 0.1-5.0 wt%, about 0.1-2.0 wt%) of an α-glucan ester derivative as disclosed herein. The α-glucan ester derivative contained in the oral care compositions may sometimes be provided therein as a thickener and / or dispersant 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.

[0146] 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 α-glucan ester 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.

[0147] 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.

[0148] 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 hexachlorobenzene). Phenols (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, such as triclosan and triclosan monophosphate); copper(II) compounds (e.g., copper(II) chlorides, fluorides, sulfates). (and hydroxides); zinc ion sources (e.g., zinc acetate, citrate, gluconate, glycine, oxides and sulfates); phthalic acid and its salts (e.g., magnesium monopotassium phthalate); dioctylhydrochloride; otetinib; sanguisorbide; benzalkonium chloride; duloxetine bromide; alkylpyridine chlorides (e.g., hexadecylpyridine chloride, tetradecylpyridine chloride, N-tetradecyl-4-ethylpyridine chloride); iodine; sulfonamides; biguanides (e.g., arazide, chlorhexidine, etc.). Hexidine, chlorhexidine digluconate); azacyclohexane derivatives (e.g., dimopistol, 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.

[0149] 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, ethane-1-hydroxy-1,1-bisphosphonic acid (EHDP), ethane-1-amino-1,1-bisphosphonate, and / or phosphonoalkylcarboxylic 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.

[0150] 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.

[0151] 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).

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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%).

[0158] 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%).

[0159] 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.

[0160] 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.

[0161] This disclosure also relates to a method of treating a material. The method includes contacting the material with an aqueous composition comprising at least one α-glucan ester derivative disclosed herein.

[0162] 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.

[0163] 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, colorfastness, 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.

[0164] 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).

[0165] 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 injecting, bonding, coloring, coating, applying, pasting, and / or communicating an effective amount of the α-glucan ester 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"]).

[0166] In some aspects of treating materials containing fabrics, α-glucan ester derivatives of aqueous compositions are adsorbed onto the fabric. This characteristic is believed to enable the α-glucan ester derivatives described herein to be used as anti-redeposition agents and / or anti-ashing agents in fabric care compositions (e.g., in addition to their viscosity-modifying effects). The anti-redeposition or anti-ashing agents described herein help 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 α-glucan ester derivatives described herein onto the fabric enhances the mechanical properties of the fabric.

[0167] The adsorption of α-glucan ester derivatives onto the fabrics described herein can be achieved, for example, using colorimetric techniques (e.g., Dubois et al., 1956, Anal. Chem. [Analytical Chemistry] 28:350-356; Zemlji). Lenzinger Berichte et al., 2006, [Linz Chemical Fibers Company Report] 85:68-76; both are measured by reference (incorporated herein) or by any other method known in the art.

[0168] Other materials that may be accessed in the above-described processing methods include surfaces that can be treated with dishwashing detergents (e.g., detergents for automatic dishwashing or hand dishwashing). 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 materials, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, polystyrene, melamine, etc.), and wood. Thus, in some embodiments, the processing method may be considered, for example, a dishwashing method or a tableware washing method. Other surfaces that may be accessed in a dishwashing method include surfaces of internal dishwashing machine components, such as the 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 dishwashing 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.

[0169] 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 (i.e., any tissue or material containing keratin).

[0170] Therefore, some aspects of this disclosure relate to materials comprising the α-glucan ester derivatives described herein (e.g., fabrics or fibers comprising products as disclosed herein, or any other materials described herein, such as hair, skin, or other materials containing keratin). Such materials can be prepared according to, for example, material processing methods disclosed herein. In some aspects, the material may comprise the α-glucan ester derivative if the α-glucan ester derivative is adsorbed onto the surface of the material or otherwise contacts the surface of the material (e.g., α-glucan ester contained in a coating of the material).

[0171] 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, tableware, or hair 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.

[0172] 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, water-based dental cleaning agents (such as toothpaste), and hair care products (such as hair styling, hair cleaning, or hair conditioning products).

[0173] Some aspects of this article relate to a method for styling hair. This method may include, for example, at least steps (a) and (b), or steps (c) or (d), as follows:

[0174] (a) Contacting (e.g., coating) hair with a composition containing the α-glucan ester derivative described herein, thereby providing treated hair (or coated hair), and

[0175] (b) To bring the treated hair (or the coated hair) into the desired form; or

[0176] (c) To bring the hair into the desired shape, and

[0177] (d) Contacting (e.g., coating) the hair from step (c) with a composition containing the α-glucan ester derivative described herein, thereby providing treated hair (or coated hair); and

[0178] (e) Optionally, remove the solvent (if present) used in step (a) or (d) to deliver the α-glucan ester derivative to the hair.

[0179] This method can optionally be characterized as a hair styling method. For example, contact in a hair styling method can be made by applying / treating hair with a hair styling composition (e.g., gel, mousse, spray) comprising at least one α-glucan ester derivative as described herein. The hair to be treated in the hair styling method, particularly in step (a) or (d), is typically wet or dry. The solvent removal step (e) can be performed, for example, by drying, such as by drying methods disclosed herein (e.g., air drying or blow-drying with room temperature or heated air). Drying can be performed with or without agitation of the treated hair, such as by combing or brushing while drying. Alternatively, the styling method herein may include the step of applying steam to the treated hair after step (b) or step (d) (but before optional step [e]). In some respects, step (b) or (c) of bringing the hair to the desired shape can be performed by straightening, curling, or otherwise bringing the hair to a shape different from the hair that existed prior to step (a), (b), or (c). Hair styled by the styling method described herein can optionally maintain the desired shape for a period of time, for example, at least 1, 2, 3, 4, 5, or more days, without the application of any apparatus and / or additional materials to the styled hair (i.e., while in its independent state). This styling retention can be under conditions of, for example, dry air (e.g., relative humidity ≤ 50%) or humid air (e.g., relative humidity > 50%) (typically for a period of time during styling without washing or rinsing the styled hair).

[0180] Non-limiting examples of the compositions and methods disclosed herein include:

[0181] 1. A method / process for producing an ester derivative of α-glucan (α-glucan ester derivative), the method comprising: (a) contacting an α-glucan in a reaction composition (e.g., a partially aqueous or semi-aqueous reaction composition) with at least one esterifying agent comprising an organic group, wherein the reaction composition comprises an organic solvent having a pH (adjusted to pH) of at least about 10, wherein the ratio of the α-glucan to the total liquid of the reaction composition is based on a weight ratio of about 0.25 to about 3.0, wherein at least about 50% (e.g., at least about 90% or 95%) of the glycosidic bonds of the α-glucan are α-1,6 bonds, wherein at least one organic group is esterified to the α-glucan to produce an α-glucan ester derivative, wherein the α-glucan ester derivative has a degree of substitution (DoS) of up to about 3.0 contributed by the organic group, and (b) optionally separating the α-glucan ester derivative.

[0182] 2. The method as described in Example 1, wherein the contact is carried out (implemented / operated) at a pressure of at least about 4 bar, and the organic solvent has a boiling point of less than about 80°C at a pressure of 1 bar.

[0183] 3. The method as described in Example 1 or 2, wherein the boiling point of the organic solvent is less than about 25°C (e.g., less than about 0°C, less than about 10°C, less than about 20°C).

[0184] 4. The method as described in Examples 1, 2, or 3, wherein the organic solvent comprises an ether.

[0185] 5. The method as described in Example 4, wherein the ether is dimethyl ether.

[0186] 6. The method as described in Examples 1, 2, 3, 4, or 5, wherein the contact comprises heating the reaction composition to about 50°C to about 90°C (e.g., 60°C-90°C or 60°C-80°C) (wherein such heating is performed after each of the components of the reaction composition has been added / mixed [or in some respects, before this]).

[0187] 7. The method as described in Examples 1, 2, 3, 4, 5, or 6, wherein the pH of the reaction composition is achieved using an alkali metal hydroxide (e.g., an alkali metal hydroxide such as NaOH, KOH, or LiOH) (e.g., an aqueous solution of an alkali metal hydroxide) (typically, the alkali metal hydroxide is mixed with the organic solvent to raise its pH to at least 10).

[0188] 8. The method of Example 7, wherein the contact comprises: (i) mixing the α-glucan with the organic solvent (or a liquid containing the organic solvent) and then adding the alkali metal hydroxide (or a liquid containing the alkali metal hydroxide) (mixed therein), or (ii) mixing the α-glucan with a mixture (premix) containing the organic solvent and the alkali metal hydroxide; wherein the mixing of (i) or (ii) is carried out (implemented) at room temperature or at about 15°C to 30°C (or at about -5°C to 50°C).

[0189] 9. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, or 8, wherein the contact comprises mixing the reactive composition with a mixer capable of mixing powders (e.g., a shear mixer), optionally wherein the mixer is a plowshare mixer.

[0190] 10. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, or 9, further comprising evaporating the organic solvent from the reaction composition after the esterification of the α-glucan.

[0191] 11. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein the ratio of the α-glucan to the total liquid content of the reaction composition is from about 0.4 to about 0.9 by weight, or from about 1.0 to about 1.5 by weight.

[0192] 12. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the organic group is a hydrophobic organic group.

[0193] 13. The method as described in Example 12, wherein the hydrophobic organic group comprises C2 to C3. 26 Acyl groups (e.g., C6 to C5) 18 Acyl, C8 to C 16 Acyl group, C 10 To C 14 Acyl or C 12 Acyl group).

[0194] 14. The method as described in Example 12, wherein the hydrophobic organic group comprises an aryl group (e.g., benzoyl or a substituted benzoyl group).

[0195] 15. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, wherein the α-glucan comprises at least 1% of α-1,2 and / or α-1,3 branches (e.g., about or at least about 5%, 10%, 20%, 30%, 40%, 10-40%, or 20-40% of α-1,2 branches, typically without α-1,3 branches) (e.g., only α-1,2 branches, without α-1,3 branches).

[0196] 16. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, wherein the α-glucan has a weight-average degree of polymerization (DPw) of at least 6 (e.g., 30-60, 30-90, 30-120, 30-600, 60-90, 60-120, or 60-600 DPw).

[0197] 17. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, wherein the DoS contributed by the organic group is at least about 0.005 (e.g., about 0.005-1.5, 0.005-1.0, 0.1-1.0, 0.2-0.7, or 0.3-0.6).

[0198] 18. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, wherein the yield of the α-glucan ester derivative is at least about 55%.

[0199] 19. A composition (product) comprising an α-glucan ester derivative produced by means of the method described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 27.

[0200] 20. The composition as described in Example 19, wherein the composition is a home care product, personal care product, industrial product, medical product, or pharmaceutical product.

[0201] 21. The composition as described in Example 19 or 20, wherein the composition is an aqueous composition.

[0202] 22. The composition as described in Examples 19, 20, or 21, further comprising at least one surfactant.

[0203] 23. The composition as described in Examples 19, 20, 21, or 22, further comprising at least one enzyme.

[0204] 24. The composition as described in Example 23, wherein the enzyme is a cellulase, protease, amylase, lipase, or nuclease.

[0205] 25. The composition as described in Examples 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 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 signaling component, a defoamer, a structuring agent, a thickener, an anti-caking agent, starch, sand, or a gelling agent.

[0206] 26. The composition as described in Examples 19, 20, 21, 22, 23, 24, or 25, wherein the composition is in or contained therein as a liquid, gel, powder, hydrocolloid, granules, tablet, capsule, block, bead or lozenge, single-compartment bag, multi-compartment bag, single-compartment pouch, multi-compartment pouch, 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).

[0207] 27. The method as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, or 18, except that, alternatively, the ratio of the α-glucan to the total liquid of the reaction composition is based on a weight of less than 0.25. Example

[0208] 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.

[0209] Materials / Methods

[0210] Representative preparation of α-1,6-glucan with α-1,2 branches

[0211] 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.

[0212] 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.

[0213] 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).

[0214] 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.

[0215] 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.

[0216] Table 1

[0217] α-1,2-branched α-1,6-glucan

[0218]

[0219] 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 esterification procedures as described below.

[0220] Determination of DoS of α-glucan ester

[0221] DoS of α-glucan esters via 1Identification was performed using 1H-NMR (nuclear magnetic resonance) spectroscopy. Dry α-glucan ester (7 to 8 mg) was dissolved in 0.75 mL of 3 wt% lithium chloride (LiCl) in deuterated dimethyl sulfoxide (DMSO-d6) with stirring at 80°C until a clear, homogeneous solution was formed. Deuterated water (D2O) (0.05 mL) was then added, and the sample was heated and stirred at 80°C for approximately one hour. The sample was transferred to a 5-mm NMR tube. Data were collected at 80°C and processed on a Bruker Neo 500 MHz or Avance III 600 MHz NMR spectrometer, the latter equipped with a proton-optimized helium-cooled cryogenic probe. 2D NMR was used. 1 H, 13 C10 NMR experiments were used to identify spectral composition regions. 1 The normalized integral area of ​​the H NMR spectrum was used to quantify the molar ratio of the grafted derivative to the dehydrated glucose unit (AGU) to give the DoS.

[0222] Example 1

[0223] Synthesis of α-1,2-branched α-1,6-glucan ester derivatives via high-solids esterification reaction

[0224] An α-1,6-glucan starting material (40 kDa, powder with 20% α-1,2-branching and 3.1 wt% water content; 418.3 g, 2.5 mol) was added to a 5-L horizontal autoclave reactor equipped with a plowshare mixer. The preparation was placed under a nitrogen atmosphere at room temperature. Dimethyl ether (DME) (403.1 g, 3.5 mol / mol glucan) was added, followed by a 50% aqueous sodium hydroxide solution (200.0 g, 1.0 mol / mol glucan), resulting in a positive pressure of 7 bar in the autoclave reactor. After 5 minutes, additional DME (57.6 g, 0.5 mol / mol glucan) was added. The preparation was mixed at 100 rpm for 30 minutes at 27°C using a plowshare mixer, followed by the addition of benzoyl chloride (351.4 g, 1.0 mol / mol dextran) (it was found in this study that benzoyl chloride can be added optimally at temperatures between 20°C and 30°C). The initial α-glucan to liquid ratio of the reaction preparation was approximately 0.44 (calculated as: 405.33 g α-glucan / (460.7 g DME + 100 g water [from NaOH solution] + 12.97 g water [from α-glucan powder] + 351.4 g benzyl chloride)). After the addition of benzoyl chloride, the mixing speed was increased to 200 rpm, and the reaction was heated to 60°C for 50 minutes (typically, esterification occurs at temperatures between approximately 60°C and 80°C), while the pressure was increased from 7 bar to 15 bar. The reaction was allowed to continue for 1 hour, after which the positive pressure was released and the reactor was cooled to ambient temperature.

[0225] For product analysis, a portion (325 g) of the crude solid product was transferred to a washing beaker containing 3 L of isopropanol (100%) and subjected to high shear (ULTRA TURRAX T50 DPX) at 5000 rpm for 30 seconds. The resulting suspension was filtered, washed five times under high shear with a 2 L isopropanol / water mixture (90 / 10 vol%), and then washed again with 0.5 L of isopropanol (100%). Filtration was used for each intermediate washing step. After final filtration, the material was dried overnight in a box oven at 55°C and ground in a laboratory mill. While the aforementioned washing process with isopropanol-water offers convenience and cost-effectiveness, washing with, for example, water and / or an ethanol-water mixture can also be effectively applied.

[0226] The yield of the α-glucan ester product was 205 g. (This was achieved through...) 1¹H NMR spectroscopy determined the total degree of substitution (DoS) of the α-glucan product, contributed by the benzoyl group, to be 0.63. The yield of 63% (based on benzoyl incorporation) was unexpectedly high; although the above process utilized a high-solids reaction scheme, a more homogeneous or slurry-type benzoylation reaction scheme using a significantly higher liquid environment provided lower yields (data not shown). Further analysis revealed a bimodal distribution of esterified and non-esterified dextran throughout the product; the water-soluble fraction (67 wt%) had a DoS of 0.01, while the water-insoluble fraction (33 wt%) had a DoS of 1.94. The dry content of the product material was 95.9%. The NaCl content of the product material was 14.3%.

[0227] Based on this work and comparative works (below), it is evident that dimethyl ether (DME) acts as a flow aid to prevent clogging of the plowshare mixer, which would otherwise occur when the α-glucan is heated with alkali. DME also helps manage the heat of the reaction. Another advantage of using DME in this work compared to other solvents is its low boiling point of 24°C, which makes it easy to remove after esterification.

[0228] Comparison Example 1

[0229] Alkaliization pretreatment

[0230] α-1,6-glucan starting material (40 kDa, powder with 20% α-1,2-branching and 3.1 wt% water content; 432.6 g, 2.5 mol) was added to a 5-L horizontal autoclave reactor equipped with a plowshare mixer. The preparation was placed under a nitrogen atmosphere at room temperature. A 50% aqueous sodium hydroxide solution (201.4 g, 1.0 mol / mol dextran) was added, and the preparation was mixed at 250 rpm. After 2 minutes of mixing, the mixer became clogged and automatically stopped due to a built-in safety feature. The reactor was opened, revealing a sticky, alkaline dextran residue between the reactor wall and the plowshare mixer, which caused the mixer to clog. Comparing this result with Example 1, it was concluded that, in some cases, a solvent (such as dimethyl ether) should be added before the addition of NaOH during the preparation of the esterification reaction described herein to avoid the deposition of harmful residues on the reactor surface.

[0231] Comparison Example 2

[0232] Heating after alkalization

[0233] α-1,6-glucan starting material (40 kDa, powder with 20% α-1,2-branching and 3.1 wt% water content; 418.3 g, 2.5 mol) was added to a 5-L horizontal autoclave reactor equipped with a plowshare mixer. The preparation was placed at room temperature under a nitrogen atmosphere. Then, dimethyl ether (575.9 g, 5.0 mol / mol dextran) was added. The preparation was heated to 66°C over a 90-minute period, during which additional dimethyl ether (230.4 g, 2.0 mol / mol dextran) was added after 60 minutes at 56°C. Then, a 50% aqueous sodium hydroxide solution (150.1 g, 0.75 mol / mol dextran) was added. Immediately after the addition of NaOH, the mixer became clogged and automatically stopped due to a built-in safety feature. When this result is compared with Example 1, it is concluded that, in some cases, solvent alkalization should be carried out at ambient temperature to avoid the deposition of harmful residues on the reactor surface.

[0234] Comparison Example 3

[0235] Triethylamine used for solvent alkalization

[0236] α-1,6-glucan starting material (40 kDa, powder with 20% α-1,2-branching and 3.1 wt% water content; 432.6 g, 2.5 mol) was added to a 5-L horizontal autoclave reactor equipped with a plowshare mixer. The preparation was placed under a nitrogen atmosphere at room temperature. Triethylamine (506.0 g, 2.0 mol / mol glucan) was then added. The preparation was mixed at 250 rpm for 30 minutes at 27°C, followed by the addition of benzoyl chloride (351.4 g, 1.0 mol / mol glucan). The reaction preparation was then heated to 68°C over a 50-minute period, during which time the pressure increased from 2.0 bar to 2.8 bar. The reaction was allowed to continue for 1 hour, after which the pressure was released and the reactor was cooled to ambient temperature.

[0237] A portion (469 g) of the crude solid product was transferred to a washing beaker containing 3 L of isopropanol (100%) and subjected to high shear (ULTRA TURRAX T50 DPX) at 5000 rpm for 30 seconds. The suspension was filtered and washed four times under high shear with a 2 L isopropanol / water mixture (90 / 10 vol%), and twice with 0.5 L of isopropanol (100%). Filtration was used for each intermediate washing step. After final filtration, the material was dried overnight in a box oven at 55°C. Grinding was not required.

[0238] DoS of α-glucan products via1 ¹H NMR spectroscopy determined the result to be 0 (i.e., the product is not an ester product, and therefore not a product in itself). Comparing this result with Example 1, it was concluded that in some cases, solvent alkalization should be carried out with an alkali metal hydroxide such as NaOH.

Claims

1. A method for producing an ester derivative of α-glucan, the method comprising: (a) Contacting the α-glucan in the reaction composition with at least one esterifying agent containing an organic group, The reaction composition described herein contains an organic solvent with a pH of at least about 10. The ratio of α-glucan to the total liquid content of the reaction composition is based on a weight ratio of about 0.25 to about 3.

0. In the case of said α-glucan, at least about 50% of the glycosidic bonds are α-1,6 bonds. At least one organic group is esterified to the α-glucan to produce an α-glucan ester derivative, wherein the α-glucan ester derivative has a degree of substitution (DoS) of up to about 3.0 contributed by the organic group, and (b) Optionally, the α-glucan ester derivative may be isolated.

2. The method as described in claim 1, wherein, The contact is carried out at a pressure of at least about 4 bar, and the organic solvent has a boiling point of less than about 80°C at a pressure of 1 bar.

3. The method as described in claim 2, wherein, The boiling point is less than about 25°C.

4. The method of claim 1, wherein, The organic solvent includes ethers.

5. The method of claim 4, wherein, The ether is dimethyl ether.

6. The method of claim 1, wherein, The contact involves heating the reaction composition to about 50°C to about 90°C (e.g., 60°C-90°C or 60°C-80°C).

7. The method of claim 1, wherein, The pH of the reaction composition is achieved using an alkali metal hydroxide.

8. The method of claim 7, wherein, The contact includes: (i) Mixing the α-glucan with the organic solvent, and then adding the alkali metal hydroxide, or (ii) Mix the α-glucan with a mixture comprising the organic solvent and the alkali metal hydroxide; The mixing of (i) or (ii) is carried out at room temperature or between about 15°C and 30°C.

9. The method of claim 1, wherein, The contact includes mixing the reaction composition using a mixer capable of mixing powders, optionally wherein the mixer is a plowshare mixer.

10. The method of claim 1, further comprising evaporating the organic solvent from the reaction composition after the esterification of the α-glucan.

11. The method of claim 1, wherein, The ratio of the α-glucan to the total liquid of the reaction composition is from about 0.4 to about 0.9 by weight, or from about 1.0 to about 1.5 by weight.

12. The method of claim 1, wherein, The organic group is a hydrophobic organic group.

13. The method of claim 12, wherein, The hydrophobic organic groups comprise C2 to C3. 26 Acyl group.

14. The method of claim 12, wherein, The hydrophobic organic group includes an aryl group.

15. The method of claim 1, wherein, The α-glucan contains at least 1% α-1,2 and / or α-1,3 branches.

16. The method of claim 1, wherein, The α-glucan has a weight-average degree of polymerization of at least 6.

17. The method of claim 1, wherein, The DoS contributed by the organic groups is at least about 0.

005.

18. The method of claim 1, wherein, The yield of the α-glucan ester derivative is at least about 55%.

19. A composition comprising an α-glucan ester derivative as produced by the method of claim 1.

20. The composition of claim 19, wherein, The composition is a home care product, personal care product, industrial product, medical product, or pharmaceutical product.

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