Compositions Comprising Insoluble Alpha-Glucan

Abstract

Disclosed herein is a solution comprising at least a caustic solvent, an alpha-glucan or derivative thereof, and an additive. The additive may include a cross-linking agent, and / or an additive that is optionally chemically non-reactive with the alpha-glucan or derivative thereof. At least about 50% of the glycosidic bonds of the alpha-glucan may be alpha-1,3 glycosidic bonds. Further disclosed are methods of preparing and using the solution to prepare various solid compositions, and various solid compositions are also disclosed.

Description

[Technical field]

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 321,831 (filed March 21, 2022), U.S. Provisional Patent Application No. 63 / 321,840 (filed March 21, 2022), and U.S. Provisional Patent Application No. 63 / 334,893 (filed April 26, 2022), each of which is incorporated by reference in its entirety herein.

[0002] The present disclosure is in the field of polysaccharides. For example, the present disclosure relates to compositions comprising insoluble alpha-glucan and at least one cross-linking agent and / or additive, and the use of this material in various applications. [Background technology]

[0003] The desire to use polysaccharides in a variety of applications has led researchers to search for polysaccharides that are biodegradable and can be produced economically from renewable sources. One such polysaccharide is alpha-1,3-glucan, an insoluble glucan polymer characterized by having alpha-1,3-glycosidic linkages. This polymer has been prepared, for example, using glucosyltransferase enzymes isolated from Streptococcus salivarius (Simpson et al., Microbiology 141:1451-1460, 1995). Also, for example, U.S. Pat. No. 7,000,000 discloses the preparation of spun fibers from enzymatically produced alpha-1,3-glucan. Various other glucan materials have also been investigated to develop new or enhanced applications. For example, US Patent Application Publication No. 2015 / 0232819 discloses the enzymatic synthesis of several insoluble glucans with mixed alpha-1,3 and alpha-1,6 linkages.

[0004] New forms of insoluble alpha-glucan are desired to enhance the economic value and performance characteristics of this material in various applications. To address this need, compositions comprising insoluble alpha-glucan and one or more crosslinkers and / or additives are described herein. Summary of the Invention [Means for solving the problem]

[0005] In one embodiment, the present disclosure relates to a solution (e.g., a caustic solution / dope solution) comprising at least (a) a caustic solvent, (b) an alpha-glucan and / or a derivative thereof, and (c) an additive, wherein the additive is (i) a crosslinker, and / or (ii) an additive that does not chemically react with the alpha-glucan or a derivative thereof, at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, the weight average degree of polymerization of the alpha-glucan is at least 15, the alpha-glucan or a derivative thereof is dissolved in the caustic solvent, and the additive is either dissolved or not dissolved in the caustic solvent.

[0006] In another embodiment, the present disclosure relates to a method of producing the solution herein. Such a method may include: mixing at least the alpha-glucan and / or derivatives thereof herein and the additive herein with a caustic solvent, wherein the alpha-glucan and / or derivatives thereof dissolves in the caustic solvent.

[0007] In another embodiment, the present disclosure relates to a method of producing a solid composition. Such a method may include: (a) providing a solution herein; (b) forming the solution into a desired form / shape; and (c) removing the caustic solvent from the solution of step (b) to produce a solid composition comprising alpha-glucan or a derivative thereof and an additive.

[0008] In another embodiment, the present disclosure relates to a composition comprising a solid composition produced by the method of producing a solid composition herein, where in some cases the solid composition is a fiber (e.g., a filament), an extrudate, a fibrid, a composite, or a film / coating.

[0009] In another embodiment, the present disclosure relates to a solid composition comprising at least a water-insoluble alpha-glucan and / or a water-insoluble derivative thereof, wherein (i) the alpha-glucan and / or its derivative is crosslinked, and / or (ii) the composition further comprises an additive that is not chemically bonded to the alpha-glucan or its derivative, wherein at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, and the weight average degree of polymerization of the alpha-glucan is at least 15.

[0010] In another embodiment, the present disclosure relates to a film or coating composition comprising a water-insoluble alpha-glucan and a hydrophobic additive, wherein (i) at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds and the weight average degree of polymerization of the alpha-glucan is at least 15, and (ii) the hydrophobic additive is not chemically bonded to the alpha-glucan.

[0011] In another embodiment, the present disclosure relates to a method of producing the film or coating composition herein. Such a method may include: (a) providing a preparation comprising at least (i) a caustic solvent, (ii) a water-insoluble alpha-glucan herein, and (iii) a hydrophobic additive herein, wherein the alpha-glucan dissolves in the caustic solvent; (b) contacting the preparation with a substrate; and (c) removing the caustic solvent from the preparation of step (b) to produce a film or coating composition comprising the alpha-glucan and the hydrophobic additive. [Brief description of the drawings]

[0012] [Figure 1A]FIG. 1 shows a continuous alpha-1,3-glucan doped filament air-drawn through a meltblown die with an alpha-1,3-glucan dope solution containing a crosslinker (see Example 2). [Figure 1B] FIG. 1 shows a failed attempt to air-draw an alpha-1,3-glucan doped filament through a meltblown die using an alpha-1,3-glucan doped solution that does not contain a crosslinker (see Example 2). [Diagram 2] 1 shows alpha-1,3-glucan films with 5, 10, 15, or 20 wt% paraffin wax additive (relative to the content of alpha-1,3-glucan in the film). The film is shown on the left side of each image (the right side is not covered by the film). See Example 7C. [Diagram 3] Figure 1 shows alpha-1,3-glucan films with 10, 15, or 20 wt% rapeseed oil additive (relative to the content of alpha-1,3-glucan in the film). A drop of water was placed on either the inside or outside of the film (the inside of the 20 wt% rapeseed oil film is not shown). The contact angle of water on the inside of each film was smaller than the contact angle of water on the outside of each film. See Example 7D. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The disclosures of all cited patent and non-patent publications are incorporated herein by reference in their entirety.

[0014] Unless otherwise disclosed, as used herein, the terms "a" and "an" are intended to include one or more (i.e., at least one) of the referenced feature.

[0015] When present, all ranges are inclusive and combinable unless otherwise stated. For example, if a range of "1 to 5" (i.e., 1 to 5) is described, the described range should be interpreted as including the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. Numerical values ​​in various ranges in this disclosure are described as approximations, unless otherwise stated, as if both the minimum and maximum values ​​in the described ranges were preceded by the word "about". In this format, slight variations above and below the described ranges can typically be used to achieve substantially the same results as the values ​​within the range. Also, the disclosure of these ranges is intended as a continuous range including each and every value between the minimum and maximum values.

[0016] It is intended that every maximum numerical limitation given throughout this specification includes every lower numerical limit, as if such lower numerical limit were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limit, as if such higher numerical limits were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0017] It should be understood that, for clarity, certain features of the disclosure that are described above and below in the context of an aspect / embodiment may also be provided in combination in a single element. Conversely, various features of the disclosure that are, for brevity, described in the context of a single aspect / embodiment may also be provided separately or in any subcombination.

[0018] The term "polysaccharide" (or "glycan") refers to a polymeric carbohydrate molecule composed of long chains of monosaccharide units linked together by glycosidic bonds, which upon hydrolysis give the building blocks of the polysaccharide, monosaccharides and / or oligosaccharides. Polysaccharides herein may be linear or branched, and / or homopolysaccharides (composed of only one type of building block monosaccharide) or heteropolysaccharides (composed of two or more different building block monosaccharides). Examples of polysaccharides herein include glucan (polyglucose), fructan (polyfructose), galactan (polygalactose), mannan (polymannose), arabinan (polyarabinose), xylan (polyxylose), and soybean polysaccharides.

[0019] The term "sugar" and other similar terms herein refer to monosaccharides and / or disaccharides / oligosaccharides, unless otherwise specified. A "disaccharide" herein refers to a carbohydrate in which two monosaccharides are linked by a glycosidic bond. An "oligosaccharide" herein may refer to a carbohydrate in which, for example, 3-15 monosaccharides are linked by glycosidic bonds. An oligosaccharide may also be referred to as an "oligomer." The monosaccharides (e.g., glucose and / or fructose) contained within a disaccharide / oligosaccharide may be referred to as "monomer units," "monosaccharide units," or other similar terms.

[0020] A "glucan" herein is a type of polysaccharide that is a polymer of glucose (polyglucose). A glucan can be, for example, composed of about, or at least about, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% glucose monomer units by weight. An example of a glucan herein is alpha-glucan.

[0021] The terms "alpha-glucan", "alpha-glucan polymer" and the like are used interchangeably herein. Alpha-glucans are polymers that include glucose monomer units linked together by alpha-glycosidic bonds. In typical embodiments, the glycosidic bonds of the alpha-glucans herein are 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% alpha-glycosidic bonds. Examples of alpha-glucan polymers herein include alpha-1,3-glucans.

[0022] The terms "alpha-1,3-glucan", "poly alpha-1,3-glucan", "alpha-1,3-glucan polymer", and the like are used interchangeably herein. An alpha-1,3-glucan is an alpha-glucan that includes glucose monomer units linked together by glycosidic bonds, with at least about 50% of the glycosidic bonds being alpha-1,3. In some embodiments, an alpha-1,3-glucan includes about, or at least about 90%, 95%, or 100% alpha-1,3 glycosidic bonds. If present, most or all of the other bonds in the alpha-1,3-glucans herein are typically alpha-1,6, although some bonds may be alpha-1,2 and / or alpha-1,4. An alpha-1,3-glucan herein is typically water insoluble.

[0023] In some embodiments herein, the terms "dextran," "dextran polymer," "dextran molecule," "alpha-1,6-glucan," and the like refer to a water-soluble alpha-glucan that contains at least 50%, 60%, 70%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or 99.5% alpha-1,6 glycosidic linkages (the remainder of the linkages are typically all or mostly alpha-1,3).

[0024] The term "copolymer" herein refers to a polymer that includes at least two different types of alpha glucans, e.g., dextran and alpha-1,3-glucan. The terms "graft copolymer," "branched copolymer," and the like, herein generally refer to a copolymer that includes a "backbone" (or "main chain") and one or more side chains branching from the backbone. The side chains are structurally distinct from the backbone. An example of a graft copolymer herein includes a dextran backbone (or a dextran backbone modified with, e.g., about 1%-35% alpha-1,2 branching and / or alpha-1,3 branching) and at least one side chain of alpha-1,3-glucan that includes at least about 50% alpha-1,3 glycosidic linkages. The alpha-1,3-glucan side chain herein can have, for example, the linkages and molecular weights of alpha-1,3-glucans disclosed herein. In some embodiments, the dextran backbone can have alpha-1,3-glucan extensions. This is because the non-reducing ends of dextran are capable of initiating alpha-1,3-glucan synthesis by glucosyltransferase enzymes.

[0025] The terms "linkage", "glycosidic linkage", "glycosidic bond" and the like refer to a covalent bond that joins sugar monomers within a sugar compound (oligosaccharides and / or polysaccharides). Examples of glycosidic bonds include the 1,6-alpha-D-glycosidic bond (also referred to herein as an "alpha-1,6" bond) and the 1,3-alpha-D-glycosidic bond (also referred to herein as an "alpha-1,3" bond).

[0026] The glycosidic linkage profile of a polysaccharide or derivative thereof can be determined using any method known in the art. For example, the linkage profile can be determined by nuclear magnetic resonance (NMR) spectroscopy (e.g., 13 C NMR and / or 1H NMR) can be used to determine the molecular weight of the carbohydrate moiety. These and other methods that can be used are disclosed, for example, in Food Carbohydrates: Chemistry, Physical Properties, and Applications (SWCui. Ed, Chapter 3, SWCui, Structural Analysis of Polysaccharides, Taylor & Francis Group LLC, Boca Raton, FL, 2005), which is incorporated herein by reference.

[0027] "Alpha-1,2 branched" (and similar terms) referred to herein typically comprises glucose that is alpha-1,2-linked to the dextran backbone; thus, alpha-1,2 branched herein may also be referred to as alpha-1,2,6 linked. Alpha-1,2 branched herein typically has one glucose group (which may also sometimes be referred to as a pendant glucose).

[0028] "Alpha-1,3 branched" (and similar terms) referred to herein typically comprises glucose that is alpha-1,3-linked to the dextran backbone; thus, alpha-1,3 branched herein may also be referred to as alpha-1,3,6 linkage. Alpha-1,3 branched herein typically has one glucose group (which may also sometimes be referred to as a pendant glucose).

[0029] The percentage of branches in a polysaccharide herein refers to the percentage of all bonds in the polysaccharide that represent branching points. For example, the percentage of alpha-1,3 branches in an alpha-glucan herein refers to the percentage of all bonds in the glucan that represent alpha-1,3 branching points. Unless otherwise stated, the percentage of bonds disclosed herein is based on the total bonds of the polysaccharide, or the portion of the polysaccharide that the disclosure specifically considers.

[0030] The "molecular weight" of a polysaccharide or polysaccharide derivative herein can be expressed as weight average molecular weight (Mw) or number average molecular weight (Mn) in units of Daltons (Da) or grams per mole. Alternatively, molecular weight can be expressed as DPw (weight average degree of polymerization) or DPn (number average degree of polymerization). The molecular weight of smaller polysaccharide polymers, such as oligosaccharides, is sometimes provided as "DP" (degree of polymerization), which simply refers to the number of monomers contained within the polysaccharide; "DP" can also characterize the molecular weight of a polymer on an individual molecule basis. Various techniques are known in the art for calculating these various molecular weight measurements, such as by high pressure liquid chromatography (HPLC), size exclusion chromatography (SEC), or gel permeation chromatography (GPC).

[0031] As used herein, Mw is defined as Mw=ΣNiMi 2 Mw of a polymer can be determined by other techniques such as static light scattering, mass spectrometry, MALDI-TOF (matrix-assisted laser desorption / ionization time-of-flight), small-angle X-ray or neutron scattering, or ultracentrifugation. Mn as used herein can be calculated as Mn=ΣNiMi / ΣNi, where Mi is the molecular weight of chain i and Ni is the number of chains of that molecular weight. In addition to SEC, Mn of a polymer can be determined by various colligative property methods, such as end group quantification by vapor pressure osmometry, proton NMR, proton FTIR, or spectroscopic methods such as UV-Vis. DPn and DPw as used herein can be calculated from Mw and Mn by dividing them by the molar mass M1 of one monomer unit, respectively. For unsubstituted glucan polymers, M1=162. For substituted (derivatized) glucan polymers, M1 = 162 + M f × DoS, where M f is the molar mass of the substituents and DoS is the degree of substitution (average number of substituents per glucose unit of the glucan polymer).

[0032] The term "cake" of insoluble alpha-glucan herein refers to a preparation in a condensed, compressed, baled, pressed, and / or compressed form that contains at least (i) about 50% to 90% by weight of water or an aqueous solution, and (ii) about 10% to 50% by weight of insoluble alpha-glucan. In some embodiments, the cake of insoluble alpha-glucan herein may contain at least (i) about 20% to 90% by weight of water or an aqueous solution, and (ii) about 10% to 80% by weight of insoluble alpha-glucan. The cake in some embodiments may be referred to as a "filter cake" or a "wet cake". The cake herein typically has a soft, solid-like consistency.

[0033] "Dry" or "dried" compositions herein typically have less than about 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1 wt% water therein.

[0034] As used herein, the terms "aqueous liquid," "aqueous fluid," "aqueous conditions," "aqueous reaction conditions," "aqueous setting," "aqueous system," and the like, may refer to water or an aqueous solution. An "aqueous solution" herein may include one or more dissolved salts, and the maximum total salt concentration may be about 3.5 wt% in some embodiments. An aqueous liquid herein typically includes water as the only solvent in the liquid, although an aqueous liquid may optionally include one or more other solvents (e.g., polar organic solvents) that are miscible in water. Thus, an aqueous solution may include a solvent having at least about 10 wt% water.

[0035] An "aqueous composition" herein has a liquid component that includes, for example, 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, some mixtures, solutions, dispersions (e.g., colloidal dispersions), suspensions, and emulsions.

[0036] The term "colloidal dispersion" as used herein refers to a heterogeneous system having a dispersed phase and a dispersion medium, i.e., microscopically dispersed insoluble particles suspended throughout another substance (e.g., an aqueous composition such as water or an aqueous solution). An example of a colloidal dispersion herein is a hydrocolloid. All or a portion of the particles of a colloidal dispersion, such as a hydrocolloid, may comprise an insoluble alpha-glucan of the present disclosure. The terms "dispersant" and "dispersion agent" are used interchangeably herein and refer to a substance that promotes the formation and / or stabilization of a dispersion. "Dispersing" as used herein refers to the act of preparing a dispersion of a material in an aqueous liquid.

[0037] An alpha-glucan or derivative thereof that is "insoluble," "aqueous-insoluble, water-insoluble" (and similar terms) herein (e.g., an alpha-1,3-glucan with a DP of 8 or greater) does not dissolve (or does not appreciably dissolve) in water or other aqueous conditions (wherein the aqueous conditions are optionally further characterized by a pH of 4-9 or 4-9.9 (e.g., pH 6-8) (i.e., non-caustic aqueous conditions) and / or a temperature of about 1-130° C. (e.g., 20-25° C.). In some embodiments, less than 1.0 gram (e.g., no detectable amount) of a water-insoluble alpha-glucan herein dissolves in 1000 milliliters of such aqueous conditions (e.g., water at 23° C.). In contrast, glucans such as certain oligosaccharides herein that are "soluble," "aqueous-soluble," "water-soluble," etc. (e.g., alpha-1,3-glucans having a DP less than 8) will appreciably dissolve under these conditions. Water-insoluble alpha-glucans or derivatives thereof herein are typically soluble in caustic aqueous conditions (e.g., aqueous solutions having a pH of ≧11, 10.5, or 10.0, at temperatures of about 1-130° C. [e.g., 20-25° C.], as the case may be).

[0038] The term "viscosity" as used herein refers to a measure of the degree to which a fluid (whether aqueous or non-aqueous) resists forces tending to cause it to flow. Various units of viscosity that may be used herein include, for example, centipoise (cP, cps) and Pascal seconds (Pa s). One centipoise is 1 / 100 poise; one poise is 0.100 kg m -1 ·s -1 Viscosity may in some embodiments be reported as "intrinsic viscosity" (IV, η, in dL / g); this term refers to a measure of the contribution of the glucan polymer to the viscosity of a liquid (e.g., a solution) containing the glucan polymer. The IV measurements herein can be obtained using any suitable method, such as those disclosed in, for example, U.S. Patent Application Publication No. 2017 / 0002335, U.S. Patent Application Publication No. 2017 / 0002336, or U.S. Patent Application Publication No. 2018 / 0340199, or Weaver et al. (J. Appl. Polym. Sci. 35:1631-1637) or Chun and Park (Macromol. Chem. Phys. 195:701-711), all of which are incorporated herein by reference. For example, the IV can be measured in part by dissolving the glucan polymer in DMSO containing about 0.9-2.5 wt % (e.g., 1, 2, 1-2 wt %) LiCl (optionally dissolving at about 100° C. for at least 2, 4, or 8 hours). The IV herein can optionally be used as a relative measure of molecular weight.

[0039] As used herein, the terms "contact angle," "wetting angle," and similar terms refer to the angle formed when a drop of water or an aqueous solution is placed on a material surface and the drop forms a dome shape on the surface. The angle formed between the material surface and a line tangent to the edge of the drop is the contact angle. For example, as a drop of water spreads across the material surface and the drop dome flattens, the contact angle decreases. If the drop beaded up on the material surface (e.g., when surface tension is high), the higher the drop dome, the larger the contact angle.

[0040] The term "zeta potential" as used herein refers to the potential difference between a dispersion medium and a stationary layer of fluid attached to a particle dispersed in the dispersion medium. In general, dispersed particles with a high zeta potential (negative or positive) are more electrically stable compared to dispersed materials with a low zeta potential (close to 0). The repulsive forces of high zeta potential materials in a dispersion tend to exceed their attractive forces, so such dispersions are relatively more stable than dispersions of low zeta potential materials, which tend to aggregate / coagulate more easily. The zeta potential herein can be measured, for example, as disclosed in U.S. Pat. No. 6,109,098 or U.S. Pat. No. 4,602,989, U.S. Patent Application Publication No. 2020 / 0131281, or International Patent Application Publication No. WO 2014 / 097402 or European Patent Application No. 0,869,357, which are incorporated herein by reference.

[0041] The terms "crosslinking", "crosslinked" and the like herein refer to one or more bonds (typically covalent bonds) linking polymers such as the insoluble alpha-glucan or derivatives thereof of the present disclosure. Crosslinks having multiple bonds typically include one or more atoms that are part of the crosslinking agent used to form the crosslinks. The terms "crosslinking agent", "crosslinker" and the like herein refer to atoms or compounds that can cause crosslinking. The terms "crosslinking reaction" and similar terms (e.g., "crosslinking composition", "crosslinking preparation") herein typically refer to a reaction that includes at least a solvent, a crosslinking agent, and a water-insoluble alpha-glucan or derivatives thereof, and optionally non-crosslinking agent additives; the crosslinking reaction herein can be maintained under caustic conditions herein or non-caustic conditions herein.

[0042] As used herein, the terms "dope," "dope," "caustic solution," "basic solution," "alkaline solution," and the like refer to a solution (typically water soluble at pH > 11) in which one or more of water-insoluble alpha-glucans, water-insoluble derivatives thereof, and / or water-insoluble cross-linked alpha-glucans (e.g., all of which are insoluble in aqueous solutions of pH 4-9) are dissolved. Additives herein may or may not be soluble in the caustic solutions herein.

[0043] "Dope filaments" (and similar terms) herein refer to filaments of a dope solution. Typically, the dope filaments are formed by passing the dope solution herein through holes or nozzles, such as from a spinneret, die, or other device useful for forming dope filaments. For example, the dope filaments can be exposed to an acid to solidify the dissolved components thereof into fiber filaments. As another example, fiber filaments of previously dissolved components can be formed by blowing air through the dope filaments to remove the liquid.

[0044] A "polysaccharide derivative" (and similar terms) herein (e.g., a glucan derivative, such as an alpha- or beta-glucan derivative) typically refers to a polysaccharide substituted with at least one organic group. The degree of substitution (DoS) of the polysaccharide derivatives herein can be up to about 3.0 (e.g., from about 0.001 to about 3.0). The organic group can be attached to the polysaccharide derivatives herein via, for example, an ether, ester, carbamate / carbamoyl, or sulfonyl bond. A precursor of a polysaccharide derivative herein refers to the underivatized polysaccharide used to make the derivative (which may also be referred to as the polysaccharide portion of the derivative). An organic group herein can be, for example, uncharged (neutral) or charged (anionic or cationic); generally, such charge can be present when the organic group is in the aqueous composition herein, further taking into account the pH of the aqueous composition (in some embodiments, the pH can be 4-10 or 5-9, or any pH disclosed herein).

[0045] The term "degree of substitution" (DoS or DS) as used herein refers to the average number of hydroxyl groups substituted with organic groups (e.g., via ether, ester, or other linkages herein) in each monomer unit of a polysaccharide derivative. The DoS of a polysaccharide derivative herein may be stated with reference to the DoS of a particular substituent, or to an overall DoS, which is the sum of the DoS values ​​of different substituent types (e.g., in the case of mixed ethers or mixed esters). Unless otherwise disclosed, the overall DoS is meant when the DoS is not stated with reference to a particular substituent type. The DoS in some embodiments herein (e.g., for hybrid solid compositions) may, in some cases, be characterized as an "effective DoS", where DoS measurements are made on a polysaccharide sample having two or more populations of the same polysaccharide (e.g., of the same molecular weight and bond profile), but where each polysaccharide population has the same organic group and a different DoS. For example, the effective DoS can be measured for a hybrid solid composition herein having some amount of ether-derivatized alpha-glucan (e.g., DoS of 0.001-3.0 per particular organic group) and some amount of underivatized alpha-glucan (DoS of 0.0). Any DoS value / range disclosed herein can be an effective DoS in some embodiments.

[0046] The term "ether" as used herein (e.g., polysaccharide ether derivatives) may be used in any of the following applications: U.S. Patent Application Publication No. 2014 / 179913, U.S. Patent Application Publication No. 2016 / 0304629, U.S. Patent Application Publication No. 2016 / 0311935, U.S. Patent Application Publication No. 2015 / 0239995, U.S. Patent Application Publication No. 2018 / 0230241, U.S. Patent Application Publication No. 2019 / 0230303, U.S. Patent Application Publication No. 2020 / 0230241, U.S. Patent Application Publication No. 2020 / 0230 ... The polysaccharide ether derivative may be one disclosed in US Patent Publication No. 18 / 0237816, or US Patent Publication No. 2020 / 0002646, or WO 2021 / 252569, WO 2021 / 247810, or WO 2021 / 257786, or US Patent Application No. 63 / 276,163, each of which is incorporated herein by reference. The terms "polysaccharide ether derivative", "polysaccharide ether compound", "polysaccharide ether", and the like are used interchangeably herein. A polysaccharide ether derivative herein is a polysaccharide that has been etherified with one or more organic groups such that the DoS of the derivative by one or more organic groups is up to about 3.0 (e.g., about 0.001 to about 3.0). A polysaccharide ether derivative may be a polysaccharide having a partial structure -C G The inclusion of -OC refers to it herein as an "ether" and includes the formula "-C G " represents a carbon atom of a monomer unit (e.g., glucose) of the polysaccharide ether derivative (such carbon atom was bonded to a hydroxyl group [-OH] in the polysaccharide precursor of the ether), and "-C-" is a carbon atom of an organic group. Examples of polysaccharide ethers herein include glucan ethers (e.g., alpha- or beta-glucan ethers).

[0047] In some embodiments, the organic group is represented by the formula: n H 2n+1It may refer to a chain of one or more carbons having either an alkyl group (i.e., an alkyl group that is fully saturated) or (ii) that is mostly saturated, but in which one or more hydrogen atoms have been replaced with another atom or functional group (i.e., a "substituted alkyl group"). Such substitution may be with one or more hydroxyl groups, oxygen atoms (thereby forming an aldehyde or ketone group), carboxyl groups, or other alkyl groups. Thus, by way of example, the organic groups herein may be alkyl groups, carboxyalkyl groups, or hydroxyalkyl groups.

[0048] A "carboxyalkyl" group herein refers to a substituted alkyl group in which one or more hydrogen atoms of the alkyl group are replaced with a carboxyl group. A "hydroxyalkyl" group herein refers to a substituted alkyl group in which one or more hydrogen atoms of the alkyl group are replaced with a hydroxyl group. Carboxyalkyl groups (e.g., carboxymethyl) are typically anionic under aqueous conditions.

[0049] An organic group may be referred to as a "positively charged organic group." As used herein, a positively charged organic group refers to one or more chains of carbons ("carbon chains") in which one or more hydrogen atoms have been replaced with another atom or functional group (i.e., a "substituted alkyl group"), where one or more of the replacements are with a positively charged group. When a positively charged organic group has replacements in addition to replacements with a positively charged group, such additional replacements may be with one or more hydroxyl groups, oxygen atoms (thereby forming an aldehyde or ketone group), alkyl groups, and / or additional positively charged groups. A positively charged organic group has a net positive charge because it contains one or more positively charged groups. The terms "positively charged group," "positively charged ionic group," "cationic group," and the like are used interchangeably herein. A positively charged group includes a cation (a positively charged ion). Examples of positively charged groups include substituted ammonium groups, carbocationic groups, and acylcationic groups.

[0050] The terms "substituted ammonium group," "substituted ammonium ion," and "substituted ammonium cation" are used interchangeably herein. A "substituted ammonium group" herein refers to a group having the structure I: [ka] wherein R2, R3, and R4 in Structure I each independently represent a hydrogen atom or an alkyl, aryl, cycloalkyl, aralkyl, or alkaryl group. The arrangement of R2, R3, and R4 in Structure I is generally not critical and is not intended to cite any particular stereochemistry. The carbon atom (C) in Structure I is part of a chain of one or more carbons ("carbon chain") of a positively charged organic group. The carbon atom is either directly ether-linked to a monomeric unit (e.g., glucose) of the polysaccharide (e.g., alpha-glucan) herein or is part of a chain of two or more carbon atoms ether-linked to a monomeric unit. The carbon atom in Structure I can be -CH2-, -CH- (where one H is replaced with another group, such as a hydroxy group), or -C- (where both H are replaced).

[0051] A substituted ammonium group can be a "primary ammonium group," a "secondary ammonium group," a "tertiary ammonium group," or a "quaternary ammonium group," depending on the composition of R2, R3, and R4 in structure I. A "primary ammonium group" herein refers to a group of structure I (i.e., -C-NH3 + ) A secondary ammonium group herein refers to structure I in which R2 and R3 are each a hydrogen atom and R4 is an alkyl, aryl, cycloalkyl, aralkyl, or alkaryl group. A tertiary ammonium group herein refers to structure I in which R2 is a hydrogen atom and R3 and R4 are each independently an alkyl, aryl, cycloalkyl, aralkyl, or alkaryl group. A quaternary ammonium group herein refers to structure I in which R2, R3, and R4 are each independently an alkyl, aryl, cycloalkyl, aralkyl, or alkaryl group (i.e., none of R2, R3, and R4 are hydrogen atoms). It will be understood that the four members (i.e., R1) referred to by the above nomenclature are one or more carbons (e.g., chains) of a positively charged organic group ether-linked to a monomeric unit (e.g., glucose) of a polysaccharide (e.g., alpha-glucan) herein.

[0052] The quaternary ammonium polysaccharide ethers (e.g., alpha-glucan ethers) herein may, for example, include trialkylammonium groups (wherein each of R2, R3, and R4 is an alkyl group). A trimethylammonium group is an example of a trialkylammonium group, where each of R2, R3, and R4 is a methyl group. It will be understood that the four members (i.e., R1) referred to in this nomenclature by "quaternary" are one or more carbon chains of positively charged organic groups ether-linked to the monomeric units of the polysaccharide.

[0053] An example of a quaternary ammonium polysaccharide ether is trimethylammonium hydroxypropyl polysaccharide. The positively charged organic group of this ether compound has the structure II: [ka] where R2, R3, and R4 are each a methyl group. Structure II is an example of a quaternary ammonium hydroxypropyl group.

[0054] The term "ester" as used herein (e.g., polysaccharide ester derivatives) may be those disclosed, for example, in US Patent Application Publication No. 2014 / 0187767, US Patent Application Publication No. 2018 / 0155455, or US Patent Application Publication No. 2020 / 0308371, or WO 2021 / 252575, each of which is incorporated herein by reference. The terms "polysaccharide ester derivative", "polysaccharide ester compound", "polysaccharide ester", and the like are used interchangeably herein. A polysaccharide ester derivative herein is a polysaccharide esterified with one or more organic groups (i.e., acyl groups) (e.g., charged organic groups, such as anionic or cationic) such that the derivative has a DoS of up to about 3.0 (e.g., about 0.001 to about 3.0) with one or more organic groups. A polysaccharide ester derivative may be a polysaccharide having a partial structure -C G They are referred to herein as "esters" by containing -O-CO-C-, G"-" represents a carbon atom of a monomer unit (e.g., glucose) of the polysaccharide ester derivative (such carbon atom was bonded to a hydroxyl group [-OH] in the polysaccharide precursor of the ester), and "-CO-C-" is included in the acyl group. Examples of polysaccharide esters herein include glucan esters (e.g., alpha- or beta-glucan esters).

[0055] The terms "polysaccharide carbamate derivatives," "polysaccharide carbamates," "carbamoyl polysaccharides," and the like are used interchangeably herein. Polysaccharide carbamate derivatives include those having a linking moiety -OCONH- or [ka] Since it contains the partial structure, -C G -OCONH-C R -or-C G -OCON-C R2 -, wherein "-C G "-" represents a carbon of a monomer unit (e.g., glucose) of a polysaccharide carbamate derivative, and "-C R -" is included in the organic group. In some embodiments, the nitrogen atom of the carbamate / carbamoyl moiety is bonded to a hydrogen atom and an organic group. However, in some embodiments, the nitrogen atom of the carbamate / carbamoyl moiety is bonded to two organic groups (see "-C" above) that can be the same (e.g., two methyl groups, two ethyl groups) or different (e.g., one methyl group and one ethyl group). R2 -"). Examples of polysaccharide carbamates herein include glucan carbamates (e.g., alpha- or beta-glucan carbamates). Carbamate groups herein can be, for example, those disclosed in WO 2021 / 252569, which is incorporated herein by reference.

[0056] The terms "polysaccharide sulfonyl derivative", "sulfonyl polysaccharide" and the like are used interchangeably herein. A polysaccharide sulfonyl derivative contains a linking moiety -OSO2- and thus has the moiety -C G -O-SO2-CR -, wherein "-C G -" represents a carbon of a monomer unit of a polysaccharide sulfonyl derivative (e.g., glucose), and "-C R "-" is included in the organic group. The sulfonyl bond herein is not ionizable. The sulfonyl group of the polysaccharide sulfonyl derivative herein may be, for example, one disclosed in WO 2021 / 252569, which is incorporated herein by reference.

[0057] The "sulfonate" group in this specification may be, for example, those disclosed in WO 2019 / 246228 A1 or U.S. Patent Application Publication No. 2021 / 0253977 A1, which are incorporated by reference herein.

[0058] An additive (and similar terms) that is "chemically unreactive" with alpha-glucan or alpha-glucan derivatives does not change the chemical structure of alpha-glucan or alpha-glucan derivatives. The presence of an additive in some embodiments does not result in the replacement of one or more hydrogens (of the hydroxyl groups of glucose monomers) with groups (e.g., ether or ester groups, such as any of those disclosed herein) derived from the additive. The presence of an additive in some embodiments does not result in the hydrolysis (or other cleavage) of one or more (i) glycosidic bonds and / or (ii) carbon-carbon bonds of glucose monomers; however, in some embodiments, the additive may have either of both of these degradative effects. However, in some embodiments, the additive does chemically react with alpha-glucan or alpha-glucan derivatives.

[0059] The term "hydrophobic" herein refers to molecules / compounds (e.g., additives herein) or substituents that are non-polar and have little or no affinity for water and tend to repel water. The term "hydrophilic" herein refers to molecules / compounds (e.g., additives herein) or substituents that are polar and have an affinity to interact with polar solvents (e.g., water) and / or other polar groups. Hydrophilic molecules or substituents tend to attract water.

[0060] The terms "fiber, fibers" and the like herein may refer to, for example, staple length fibers or continuous fibers (filaments). The fibers of the present disclosure may include, for example, alpha-1,3-glucan and additives. The fibers may be included in a fiber-containing composition, article, material, or product, such as a woven or nonwoven product.

[0061] As used herein, the term "woven product" and similar terms refer to products formed by weaving, knitting, interlacing, or otherwise intertwining yarns or fibers in an organized, consistent, and / or repetitive manner.

[0062] The terms "nonwoven fabric", "nonwoven product", "nonwoven web", and the like herein refer to a web of individual fibers (e.g., filament or staple fibers) that are typically interspersed in a random or indefinable manner. This is in contrast to knitted or woven fabrics, which have a definable network of fibers. In some embodiments, the nonwoven product comprises a nonwoven web that is bonded or attached to another material, such as a substrate or backing. The nonwoven fabric in some embodiments may further contain a binder or adhesive (reinforcement agent) that bonds adjacent nonwoven fibers together. The nonwoven binder or adhesive may be applied to the nonwoven fabric, for example, in the form of a dispersion / latex, solution, or solid, and the treated nonwoven fabric is typically allowed to dry.

[0063] The terms "fabric," "textile," "cloth," and the like are used interchangeably herein and refer to a woven fabric having a network of fibers. Such fibers may be in the form of, for example, yarns or threads. However, in some embodiments, a fabric may include nonwoven fibers.

[0064] As used herein, the terms "fibrids," "fibrillar glucan," and the like, may refer to non-granular, fibrous, or film-like particles in which at least one of the three dimensions is a small fraction of the largest dimension. Fibrids of the present disclosure may include, for example, alpha-1,3-glucan and additives. In some embodiments, fibrids may have a fiber-like and / or sheet-like structure with a relatively large surface area when compared to fibers. The surface area of ​​fibrids herein may be, for example, about 5-50 m of material. 2 / gram, with a maximum dimension of about 10-1000 microns and a minimum dimension of 0.05-0.25 microns (aspect ratio of maximum dimension to minimum dimension of 40-20000). Fibrids in some embodiments may be defined as the material produced when a caustic solution herein containing water insoluble alpha-glucan (or water insoluble alpha-glucan derivative) and additives is subjected to shear forces and simultaneously subjected to conditions that cause the glucan and additive contents of the caustic solution to precipitate.

[0065] The terms "film," "sheet," and similar terms herein refer to a generally thin, visually continuous material. A film may be configured as a layer or coating on a material, or may be standalone (e.g., not attached to a material surface; freestanding). As used herein, a "coating" (and similar terms) refers to a layer that covers the surface of a material. A film, sheet, or coating of the present disclosure may include, for example, alpha-1,3-glucan and an additive. The term "uniform thickness" used to characterize a film or coating herein may refer to a continuous area that is (i) at least 20% of the total area of ​​the film / coating, and (ii) has a standard deviation in thickness of, for example, less than about 50 nm. The term "continuous layer" refers, for example, to a layer of a composition applied to at least a portion of a substrate, where the dried layer of the composition covers ≧99% of the surface to which it is applied, and where there are less than 1% pores in the layer exposing the substrate surface. The ≧99% of the surface to which the layer is applied excludes any areas of the substrate to which the layer is not applied. The coatings herein may in some embodiments form a continuous layer.

[0066] A "composite" herein is a composition that includes two or more components of the present disclosure (e.g., alpha-1,3-glucan and an additive). Typically, the components of a composite resist separation and one or more of the components exhibit enhanced and / or different properties compared to their properties alone, not the composite (i.e., a composite is not simply a mixture that is generally easily separable relative to its original components). Composites herein are generally solid materials (typically dry) and can be manufactured, for example, via extrusion or molding processes.

[0067] "Wax" herein typically refers to an ester of a single fatty acid with a single long chain alcohol. Generally, waxes are solid at temperatures below 45 or 50° C. and / or are aqueous insoluble under both caustic and non-caustic conditions.

[0068] The term "oil" as used herein refers to a lipid that is typically liquid at 25°C and is hydrophobic and soluble in organic solvents. Oils are typically composed primarily of triacylglycerols, but may also contain other neutral lipids, as well as phospholipids and free fatty acids. Oils may be derived, for example, from vegetable, animal, or mineral sources.

[0069] As used herein, with respect to polypeptide amino acid sequences (e.g., of glucosyltransferases), the terms "sequence identity," "identity," and the like, are as defined and determined in U.S. Patent Application Publication No. 2017 / 0002336, which is incorporated herein by reference.

[0070] Various polypeptide amino acid sequences are disclosed herein as features of certain embodiments. Variants of these sequences can be used or referenced that are at least about 70-85%, 85-90%, or 90-95% identical to the sequences disclosed herein. Alternatively, variant amino acid sequences can have at least 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% identity to the sequences disclosed herein. The variant amino acid sequences have the same function / activity as the disclosed sequences or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% of the function / activity of the disclosed sequences.

[0071] The terms "percent by volume," "volume percent," "vol%," "v / v%," and the like are used interchangeably herein. The percent by volume of a solute in a solution is calculated according to the formula: [(volume of solute) / (volume of solution)]×100%. It can be calculated using:

[0072] The terms "percent by weight", "weight percentage (wt%)", "weight-to-weight percentage (% w / w)", etc. are used interchangeably herein. Percent by weight refers to the percentage of a substance by mass when contained in a composition, mixture, or solution.

[0073] The terms "weight / volume percent", "w / v%", etc. are used interchangeably herein. Weight / volume percent can be calculated as follows: ((mass of material [g]) / (total volume of material + liquid in which material is found [mL])) x 100%. A material may be insoluble in the liquid (i.e., a solid phase in a liquid phase, e.g., a dispersion) or soluble in the liquid (i.e., a solute that is dissolved in the liquid).

[0074] The term "isolated" refers to a substance (or process) in a form or environment that does not occur in nature. Non-limiting examples of isolated substances include any of the alpha-glucan compositions disclosed herein. The embodiments disclosed herein are considered to be synthetic / artificial (not capable of being made or performed without human intervention / involvement) and / or have non-naturally occurring properties.

[0075] The term "enhancement" as used herein can refer to an amount or activity that is 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% greater than the amount or activity to which the increase in amount or activity is being compared. The terms "enhancement," "elevation," "enhancement," "super," "improvement," and the like are used interchangeably herein.

[0076] Some aspects of the present disclosure include at least (a) a caustic solvent; (b) alpha-glucan and / or derivatives thereof (or alpha-glucan that has been cross-linked prior to entering the caustic solvent); (c) an additive comprising: (i) a cross-linking agent (e.g., if the alpha-glucan was not cross-linked prior to entering the caustic solvent), and / or (ii) optionally with an additive, which is an additive that does not chemically react with alpha-glucan or its derivatives; Including, at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, and the weight average degree of polymerization of the alpha-glucan is at least 15; The alpha-glucan or derivative thereof is dissolved in a caustic solvent, and the additive is either dissolved or not dissolved in the caustic solvent, in the solution (caustic solution, dope solution).

[0077] Such caustic solutions have several advantageous characteristics. For example, they can be used to produce dope solution filaments comprising the alpha-glucan herein and a cross-linking agent (or cross-linked alpha-glucan), which are more suitable for drawing or other types of operations compared to dope solution filaments lacking the cross-linking agent or cross-linked alpha-glucan. As another example, the caustic solutions herein can be used to produce solid compositions of insoluble alpha-glucan or derivatives thereof in which a water-soluble additive is embedded and / or adsorbed; the presence of the water-soluble additive is durable in that it is not easily removed by contacting the solid composition with a non-caustic aqueous liquid.

[0078] The alpha-glucans of the present disclosure are typically water-insoluble under non-caustic conditions herein. Generally, at least about 50% of the glycosidic bonds of the alpha-glucans herein are alpha-1,3 glycosidic bonds. In some embodiments, about, or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% of the glycosidic bonds of the alpha-glucans are alpha-1,3 glycosidic bonds. Typically, the glycosidic bonds that are not alpha-1,3 are mostly or entirely alpha-1,6. It should be understood that the higher the percentage of alpha-1,3 bonds present in the alpha-glucan, the higher the probability that the glucan is linear, since the occurrence of certain bonds that may be part of branch points is lower. In some embodiments, the alpha-glucan has no branch points or has less than about 5%, 4%, 3%, 2%, or 1% branch points as a percentage of the glycosidic bonds in the alpha-glucan.

[0079] The alpha-glucans of the present disclosure can have, for example, a DPw, DPn, or DP of at least about 15. In some embodiments, the DPw, DPn, or DP of the alpha-glucan is about 10, 15, 20, 25, 30, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 65, 70, 75, 80, 85, 90, 95, 100, DPw, DPn, or DP may, in some cases, be expressed as a range between any two of these values. By way of example only, the DPw, DPn, or DP of the alpha-glucans herein may be from about 15 to 1600, 50 to 1600, 100 to 1600, 200 to 1600, 300 to 1600, 400 to 1600, 500 to 1600, 600 to 1600, 700 to 1600, 15 to 1250, 50 to 1250, 100 to 1250, 200 to 1250, 300 to 1250, 400 to 1250, 500 to 1250, 600 to 1250, It can be 50, 700-1250, 15-1000, 50-1000, 100-1000, 200-1000, 300-1000, 400-1000, 500-1000, 600-1000, 700-1000, 15-900, 50-900, 100-900, 200-900, 300-900, 400-900, 500-900, 600-900, 700-900, 600-800, or 600-750. By way of further example only, the DPw, DPn, or DP of the alpha-glucans herein may be about 15-100, 25-100, 35-100, 15-80, 25-80, 35-80, 15-60, 25-60, 35-60, 15-55, 25-55, 35-55, 15-50, 25-50, 35-50, 35-45, 35-40, 40-100, 40-80, 40-60, 40-55, 40-50, 45-60, 45-55, 45-50, 15-35, 20-35, 15-30, or 20-30.By way of further example only, DPw, DPn, or DP may be from about 100 to 600, 100 to 500, 100 to 400, 100 to 300, 200 to 600, 200 to 500, 200 to 400, or 200 to 300. In some embodiments, the alpha-glucan may have a high molecular weight reflected by a high intrinsic viscosity (IV); for example, the IV may be about, or at least about, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 6-8, 6-7, 6-22, 6-20, 6-17, 6-15, 6-12, 10-22, 10-20, 10-17, 10-15, 10-12, 12-22, 12-20, 12-17, or 12-15 dL / g (for comparison purposes, note that an insoluble alpha-glucan having at least 90% (e.g., about 99% or 100%) alpha-1,3 linkages and a DPw of about 800 has an IV of about 2-2.5 dL / g). The IV herein can be, for example, that measured with insoluble alpha-glucan polymer dissolved in DMSO with about 0.9-2.5 wt % (eg, 1, 2, 1-2 wt %) LiCl.

[0080] The alpha-glucans herein (e.g., molecular weight, binding profile, and / or production method) may be any of the compositions described in, for example, U.S. Patent No. 7,000,000, U.S. Patent No. 8,871,474, U.S. Patent No. 10,301,604, or U.S. Patent No. 10,260,053, or U.S. Patent Application Publication No. 2019 / 0112456, U.S. Patent Application Publication No. 2019 / 0078062, U.S. Patent Application Publication No. 2019 / 0078063, U.S. Patent Application Publication No. 2018 / 0340199, U.S. Patent Application Publication No. 2018 / 0340209, U.S. Patent Application Publication No. 2018 / 0340300, U.S. Patent Application Publication No. 2018 / 0340402, U.S. Patent Application Publication No. 2018 / 0340502, U.S. Patent Application Publication No. 2018 / 0340503 ... US Patent Publication No. 2018 / 0021238, US Patent Publication No. 2018 / 0273731, US Patent Publication No. 2017 / 0002335, US Patent Publication No. 2015 / 0232819, US Patent Publication No. 2015 / 0064748, US Patent Publication No. 2020 / 0165360, US Patent Publication No. 2020 / 0131281, or US Patent Publication No. 2019 / 0185893, each of which is incorporated herein by reference. Alpha-glucan can be produced, for example, by an enzymatic reaction including at least water, sucrose, and a glucosyltransferase enzyme that synthesizes alpha-glucan. Glucosyltransferases, reaction conditions, and / or processes believed to be useful for producing alpha-glucan can be those disclosed in any of the aforementioned references.

[0081] In some embodiments, the glucosyltransferase enzyme for producing alpha-glucan herein may comprise an amino acid sequence that is 100% identical to, or at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 98.5%, 99%, or 99.5% identical to, SEQ ID NO:2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 26, 28, 30, 34, or 59, or amino acid residues 55-960 of SEQ ID NO:4, residues 54-957 of SEQ ID NO:65, residues 55-960 of SEQ ID NO:30, residues 55-960 of SEQ ID NO:28, or residues 55-960 of SEQ ID NO:20, and may have glucosyltransferase activity; these amino acid sequences are disclosed in U.S. Patent Application Publication No. 2019 / 0078063, which is incorporated herein by reference. In addition, a glucosyltransferase enzyme containing amino acid residues 55 to 960 of SEQ ID NO: 2, 4, 8, 10, 14, 20, 26, 28, 30, 34, or SEQ ID NO: 4, residues 54 to 957 of SEQ ID NO: 65, residues 55 to 960 of SEQ ID NO: 30, residues 55 to 960 of SEQ ID NO: 28, or residues 55 to 960 of SEQ ID NO: 20 can synthesize an alpha-glucan containing at least about 90% (about 100%) alpha-1,3 bonds.

[0082] In some embodiments, the alpha-glucan can be in the form of a graft copolymer as disclosed in WO 2017 / 079595, or US 2020 / 0165360, US 2019 / 0185893, or US 2020 / 0131281, which are incorporated herein by reference. The graft copolymer can include dextran (as the backbone) and alpha-1,3-glucan (as one or more side chains), the latter component being grafted to the former component; typically, the graft copolymer is produced using dextran or alpha-1,2-branched dextran and / or alpha-1,3-branched dextran as a primer for alpha-1,3-glucan synthesis by an alpha-1,3-glucan-generating glucosyltransferase as described above. The alpha-1,3-glucan side chains of the alpha-glucan graft copolymers herein can be the alpha-1,3-glucans of the present disclosure. The dextran backbone of the alpha-glucan graft copolymers herein can comprise about 100% alpha-1,6 glycosidic linkages (i.e., a completely linear dextran backbone) or about, or at least about, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 99.5% alpha-1,6 glycosidic linkages (i.e., a substantially linear dextran backbone), and / or can have a DP, DPw, or DPn of, for example, about 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, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 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, 85, 28, 29, 30, 35, 40, 45, 50, 85, 90, 95, 100, 105, 110, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, 1000, 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,It may be 100-110, 105-110, 90-105, 95-105, 100-105, 90-100, 95-100, 90-95, 85-95, or 85-90, or at least about those, or less than those. In some embodiments, the molecular weight of the dextran backbone is about, or at least about, 100,000, 125,000, 150,000, 175,000, 200,000, 240,000, 250,000, 500,000, 750,000, 1 million, 2 million, 3 million, 4 million, 5 million, 6 million, 7 million, 8 million, 9 million, 10 million, 20 million, 30 million, 40 million, 50 million, 60 million, 70 million, 80 million, 90 million, 100 million, 110 million, 120 million, 130 million, 140 million, 150 million, 160 million, 170 million, 180 million, 190 million, 200 million, 100,000-200,000, 125,000-175,000, 130,000-170,000, 135,000-165,000, 140,000-160,000, 145,000-155, 5 million-15 million, 10 million-80 million, 20 million-70 million, 30 million-60 million, 40 million-50 million, 50 million-200 million, 60 million-200 million, 70 million-200 million, 80 million-200 million, 90 million-200 million, 100 million-200 million, 110 million-200 million, 120 million-200 million, 50 million Million to 180 million, 60 million to 180 million, 70 million to 180 million, 80 million to 180 million, 90 million to 180 million, 100 million to 180 million, 110 million to 180 million, 120 million to 180 million, 50 million to 160 million, 60 million to 160 million, 70 million to 160 million, 80 million to 160 million, 90 million to 160 million, 100 million to 160 million, 110 million to 160 million, 120 million to 160 million, 5 0 million to 140 million, 60 million to 140 million, 70 million to 140 million, 80 million to 140 million, 90 million to 140 million, 100 million to 140 million, 110 million to 140 million, 120 million to 140 million, 50 million to 120 million, 60 million to 120 million, 70 million to 120 million, 80 million to 120 million, 90 million to 120 million, 90 million to 110 million, 100 million to 120 million, 110 million to 120 million,It may be 50 to 110 million, 60 to 110 million, 70 to 110 million, 80 to 110 million, 90 to 110 million, 100 to 110 million, 50 to 100 million, 60 to 100 million, 70 to 100 million, 80 to 100 million, 90 to 100 million, or 95 to 105 million Daltons. In some embodiments, the dextran backbone (prior to incorporation into the graft copolymer) is alpha-1,2-branched and / or alpha-1,3-branched; the alpha-1,2 branched and / or alpha-1,3 branched percent of the backbone of the graft copolymers herein is, for example, about 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%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 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%, 100%, 102%, 104%, 106%, 108%, 109%, 110%, , 21%, 22%, 23%, 24%, 25%, 30%, 35%, 40%, 45%, 50%, 2-25%, 2-20%, 2-15%, 2-10%, 5-25%, 5-20, 5-15%, 5-10%, 7-13%, 8-12%, 9-11%, 10-25%, 10-20%, 10-15%, 10-22%, 12-20%, 12-18%, 14-20%, 14-18%, 15-18%, or 15-17%, or may be at least about those or less. The dextran portion (e.g., molecular weight, conjugation / branching profile, method of manufacture) of the graft copolymers herein can be those disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0122445, U.S. Patent Application Publication No. 2017 / 0218093, U.S. Patent Application Publication No. 2018 / 0282385, U.S. Patent Application Publication No. 2020 / 0165360, or U.S. Patent Application Publication No. 2019 / 0185893, each of which is incorporated herein by reference. In some embodiments, the dextran is selected from the group consisting of glucosyltransferase (GTF) 0768 (SEQ ID NO: 1 or 2 in U.S. Patent Application Publication No. 2016 / 0122445), GTF8117, GTF6831, or GTF5604 (these latter three GTF enzymes are SEQ ID NO: 30, 32, and 33, respectively, in U.S. Patent Application Publication No. 2018 / 0282385), or GTF0768, GTF8117, GTF6831,or may be produced in a suitable reaction, including a GTF that contains 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 GTF5604.

[0083] The caustic solutions herein may contain one, two, three or more different alpha-glucans herein (eg, differing in DPw and / or alpha-1,3 bond percentage).

[0084] Any alpha-glucan of the present disclosure may be derivatized and used in the caustic solution herein or other compositions herein (e.g., fibers, fibrids, composites, or films / coatings). For example, the alpha-glucan portion of the alpha-glucan derivatives herein may have a molecular weight (e.g., DP, DPw, or DPn) and / or glycosidic bond profile disclosed herein for alpha-glucans. By way of example only, the alpha-glucans herein that may be derivatized may include (i) alpha-glucans with a DPw of greater than 15 (e.g., having ≧about 50%, 90%, 95%, 99%, or 100% alpha-1,3 bonds) (e.g., ≧100, 400, 600) or (ii) alpha-glucan graft copolymers herein. The alpha-glucan derivatives in some embodiments may have a degree of substitution (DoS) of up to about 3.0 with at least one substituent (e.g., organic group) presently disclosed. The organic groups herein can be uncharged (nonionic) or charged (e.g., cationic [positively charged] or anionic [negatively charged]). The degree of substitution (DoS) in some embodiments can be about, at least about, or up to about 0.001, 0.0025, 0.005, 0.01, 0.025, 0.05, 0.075, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0 (DoS can, in some cases, be expressed as a range between any two of these values).Some examples of DoS ranges used herein are: 0.001-3.0, 0.001-2.0, 0.001-1.5, 0.001-1.25, 0.001-1.0, 0.001-0.9, 0.001-0.8, 0.001-0.7, 0.001-0.6, 0.001-0.5, 0.005-3.0, 0.005-2.0, 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, 0.01-3. 0, 0.01~2.0, 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, 0.05~3.0, 0.05~2.0, 0.05~1.5, 0.05~1.25, 0.05~1.0, 0.05~0.9, 0.05~0.8, 0.05~0.7, 0.05~0.6, 0.05~0.5, 0.1~3.0, 0.1~2.0, 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, 0.15~3.0, 0.15~2.0, 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, 0.2~3.0, 0.2~2.0, 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, 0.25~3.0, 0.25~2.0, 0.25~1.5, 0.25 0.3 to 3.0, 0.3 to 2.0, 0.3 to 1.5, 0.3 to 1.25, 0.3 to 1.0, 0.25 to 0.9, 0.25 to 0.8, 0.25 to 0.7, 0.25 to 0.6, 0.25 to 0.5, 0.3 to 3.0, 0.3 to 2.0, 0.3 to 1.5, 0.3 to 1.25, 0.3 to 1.0, 0.3 to 0.9, 0.3 to 0.8, 0.3 to 0.7, 0.3 to 0.6, 0.3 to 0.5, 0.4 to 3.0, 0.4 to 2.0, 0.4 to 1.5, 0.4 to 1.25, 0.4 to 1.0, 0.4 to 0.9, 0.4 to 0.8, 0.4 to 0.7, 0.4 to 0.6, and 0.4 to 0.5.

[0085] The alpha-glucan derivatives may be used in place of or in addition to the underivatized alpha-glucan used in part (b) of the caustic solution. Also, for example, the alpha-glucan derivatives may be used as additives in part (c) of the caustic solution. The alpha-glucan derivatives in part (b) of the caustic solution herein are typically water-insoluble under non-caustic aqueous conditions. The alpha-glucan derivatives may be, for example, charged (e.g., cationic or anionic) (when used as an additive, they are an example of a charged additive). The degree of substitution (DoS) of the charged water-insoluble alpha-glucan derivative under non-caustic aqueous conditions is typically about 0.29, 0.25, 0.2, 0.15, 0.1, 0.05, 0.05-0.29, 0.05-0.25, 0.05-0.2, 0.05-0.15, 0.1-0.29, 0.1-0.25, 0.1-0.2, or 0.1-0.15, or less (generally, the higher the DoS (greater than 0.3), the more water-soluble it is under non-caustic aqueous conditions). In some embodiments, any of the aforementioned characteristics can similarly characterize the alpha-glucan derivatives (part of the caustic solution [c]) used as additives herein. The type of derivative (e.g., water-insoluble or water-soluble under non-caustic aqueous conditions) (e.g., as used in part [b] or part [c] of the caustic solution herein) can be, for example, any derivative disclosed herein (e.g., ether, ester).

[0086] In some embodiments, the water-soluble (under non-caustic conditions) alpha-glucan derivative (e.g., which may be an additive in part [c] of the caustic solution herein) may have a degree of substitution (DoS) of up to about 3.0 (e.g., 0.3 to 3.0) with at least one presently disclosed organic group / substituent. Such organic groups are typically charged; that is, the organic groups may be cationic or anionic. The DoS may be, for example, about or at least about 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 may, in some cases, be expressed as a range between any two of these values). Some examples of DoS ranges herein for alpha-glucan derivatives soluble under non-caustic aqueous conditions include: 0.3-3.0, 0.3-2.5, 0.3-2.0, 0.3-1.75, 0.3-1.5, 0.3-1.25, 0.3-1.0, 0.3-0.9, 0.3-0.8, 0.3-0.7, 0.3-0.6, 0.3-0.5, 0.4-3.0, 0.4-2.5, 0.4-2.0, 0.4-1.75, 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, 0.4-0.5, Examples of the stoichiometric ratio include 0.5 to 3.0, 0.5 to 2.5, 0.5 to 2.0, 0.5 to 1.75, 0.5 to 1.5, 0.5 to 1.25, 0.5 to 1.0, 0.5 to 0.9, 0.5 to 0.8, 0.5 to 0.7, 0.5 to 0.6, 0.6 to 3.0, 0.6 to 2.5, 0.6 to 2.0, 0.6 to 1.75, 0.6 to 1.5, 0.6 to 1.25, 0.6 to 1.0, 0.6 to 0.9, 0.6 to 0.8, 0.6 to 0.7, 0.8 to 3.0, 0.8 to 2.5, 0.8 to 2.0, 0.8 to 1.75, 0.8 to 1.5, 0.8 to 1.25, 0.8 to 1.0, and 0.8 to 0.9.

[0087] Typically, an alpha-glucan derivative that is insoluble under non-caustic aqueous conditions may be used in part (b) and / or part (c) of the caustic solution herein (if both part [b] and / or part [c], typically two different derivatives are used). Typically, an alpha-glucan derivative that is soluble under non-caustic aqueous conditions may be used as an additive in part (c) of the caustic solution herein. In some embodiments, if part (b) contains a water-insoluble alpha-glucan, the part (c) additive contains an alpha-glucan derivative. In some embodiments, if part (c) additive contains an alpha-glucan derivative, part (b) does not contain an alpha-glucan derivative (or polysaccharide derivative).

[0088] In some embodiments, the alpha-glucan derivative (e.g., either insoluble or soluble in non-caustic aqueous conditions depending on the DoS and type of derivative) is substituted with at least one organic group herein via an ether bond, an ester bond, a carbamate bond, or a sulfonyl bond.Thus, the alpha-glucan derivative herein can be, for example, an alpha-glucan ether, ester, carbamate, or sulfonyl derivative.All of the various linking groups disclosed herein are examples of organic groups; an organic group can be considered to include, for example, at least one carbon atom and at least one hydrogen atom.

[0089] The alpha-glucan derivative, in some embodiments, may be an ether derivative.

[0090] The organic group ether-linked to the alpha-glucan herein can, for example, comprise or consist of a positively charged (cationic) group. The positively charged group can be, for example, any of those disclosed in US Patent Publication No. 2016 / 0311935 or US Patent Publication No. 2020 / 0002646, or WO 2021 / 247810 or WO 2021 / 257786, or US Patent Application No. 63 / 276,163, which are incorporated herein by reference. The positively charged group can, for example, comprise a substituted ammonium group. Examples of substituted ammonium groups include primary, secondary, tertiary, and quaternary ammonium groups, such as those represented by structures I and II. The ammonium group can, for example, be substituted with an alkyl group and / or an aryl group. In some embodiments, there can be one, two, or three alkyl and / or aryl groups. The alkyl group of the substituted ammonium group herein may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, C 25 , C 26 , C 27 , C 28 , C 29 , or C 30 Groups C1 to C 30 Each alkyl group may be the same in embodiments having two or three alkyl substitutions, or may be different. The alkyl groups may in some embodiments be C1 to C6 24 , C1~C 18 , C6~C 20 , C 10 ~C 16 An aryl group can be, for example, C6, C6-C, or C1-C4, optionally substituted with one or more alkyl substituents (e.g., any of the alkyl groups disclosed herein). 24 , C 12 ~C 24 , or C6~C 18It may be an aryl group.

[0091] The secondary ammonium alpha-glucan ether herein may, in some embodiments, include a monoalkylammonium group (e.g., based on structure I). The secondary ammonium alpha-glucan ether may, in some embodiments, be a monoalkylammonium alpha-glucan ether, such as a monomethyl-, monoethyl-, monopropyl-, monobutyl-, monopentyl-, monohexyl-, monoheptyl-, monooctyl-, monononyl-, monodecyl-, monoundecyl-, monododecyl-, monotridecyl-, monotetradecyl-, monopentadecyl-, monohexadecyl-, monoheptadecyl-, or monooctadecyl ammonium alpha-glucan ether. These alpha-glucan ethers may also be referred to as methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl-, or octadecyl-ammonium alpha-glucan ethers, respectively.

[0092] The tertiary ammonium alpha-glucan ether herein may, in some embodiments, include a dialkylammonium group (e.g., based on structure I). The tertiary ammonium alpha-glucan ether may, in some embodiments, be a dialkylammonium alpha-glucan ether, such as a dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, dinonyl-, didecyl-, diundecyl-, didodecyl-, ditridecyl-, ditetradecyl-, dipentadecyl-, dihexadecyl-, diheptadecyl-, or dioctadecyl-ammonium alpha-glucan ether.

[0093] The quaternary ammonium alpha-glucan ether herein may, in some embodiments, include a trialkylammonium group (e.g., based on structure I). The quaternary ammonium alpha-glucan ether compound may, in some embodiments, be a trialkylammonium alpha-glucan ether, such as a trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, trihexyl-, triheptyl-, trioctyl-, trinonyl-, tridecyl-, triundecyl-, tridodecyl-, tritridecyl-, tritetradecyl-, tripentadecyl-, trihexadecyl-, triheptadecyl-, or trioctadecyl-ammonium alpha-glucan ether.

[0094] One of the groups of the substituted ammonium group contains one carbon or a chain of carbons (e.g., up to 30) in an ether linkage to the alpha-glucan. A carbon chain in this context can be, for example, linear. Such a carbon or carbon chain can be, for example, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH 2( CH2)2CH2-, -CH 2( CH2)3CH2-, -CH 2( CH2)4CH2-, -CH 2( CH2)5CH2-, -CH 2( CH2)6CH2-, -CH 2( CH2)7CH2-, -CH 2( CH2)8CH2-, -CH 2( CH2)9CH2- or -CH 2( CH2) 10The carbon chain in this context may be represented by CH2-. In some embodiments, the carbon chain in this context may be branched, such as by substitution with one or more alkyl groups (e.g., any of those disclosed above, such as methyl, ethyl, propyl, or butyl). The substitution point may be anywhere along the carbon chain. Examples of branched carbon chains include -CH(CH3)CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -CH(CH2CH3)CH2-, -CH(CH2CH3)CH2CH2-, -CH2CH(CH2CH3)CH2-, -CH(CH2CH2CH3)CH2-, -CH(CH2CH2CH3)CH2CH2-, -CH(CH2CH2CH3)CH2CH2-, and -CH2CH(CH2CH2CH3)CH2-; longer branched carbon chains may be used if desired. In some embodiments, one or more carbon chains (e.g., any of the above straight or branched chains) are further substituted with one or more hydroxyl groups. Examples of hydroxy or dihydroxy (diol) substituted chains include -CH(OH)-, -CH(OH)CH2-, -C(OH)2CH2-, -CH2CH(OH)CH2-, -CH(OH)CH2CH2-, -CH(OH)CH(OH)CH2-, -CH2CH2CH(OH)CH2-, -CH2CH2CH(OH)CH2-, -CH2CH(OH)CH2CH2-, -CH2CH(OH)CH2CH2-, -CH2CH(OH)CH2CH2-, -CH2CH(OH)CH2CH2-, -CH2CH(OH)CH(OH)CH2-, -CH(OH)CH(OH)CH2CH2-, -CH(OH)CH(OH)CH2CH2, and -CH(OH)CH2CH(OH)CH2-. In each of the foregoing examples, the first carbon atom of the chain is ether-linked to a glucose monomer of the alpha-glucan and the last carbon atom of the chain is linked to a positively charged group (e.g., a substituted ammonium group as disclosed herein). In some embodiments, the one or more positively charged organic groups can include a trimethylammonium hydroxypropyl group (structure II, where each of R2, R3, and R4 is a methyl group).

[0095] In embodiments where the carbon chain of the positively charged organic group has substitutions in addition to substitutions with positively charged groups, such additional substitutions can be, for example, with one or more hydroxyl groups, oxygen atoms (thereby forming aldehyde or ketone groups), alkyl groups (e.g., methyl, ethyl, propyl, butyl), and / or additional positively charged groups. The positively charged groups are typically attached to the terminal carbon atoms of the carbon chain. The positively charged groups can also include, in some embodiments, imidazoline ring-containing compounds.

[0096] The counterion for the positively charged organic groups herein can be any suitable anion, such as acetate, borate, bromate, bromide, carbonate, chlorate, chloride, chlorite, dihydrogen phosphate, fluoride, bicarbonate, hydrogen phosphate, hydrogen sulfate, hydrogen sulfide, hydrogen sulfite, hydroxide, hypochlorite, iodate, iodide, nitrate, nitride, nitrite, oxalate, oxide, perchlorate, permanganate, phosphate, phosphide, phosphite, silicate, stannate, stannate, sulfate, sulfide, sulfite, tartrate, or thiocyanate.

[0097] The organic group ether-linked to the alpha-glucan herein can, for example, comprise or consist of a negatively charged (anionic) group. The anionic group can be, for example, any of those disclosed in US Patent Publication No. 2016 / 0311935 or US Patent Publication No. 2020 / 0002646, or WO 2021 / 252569 or WO 2021 / 247810, which are incorporated herein by reference. The anionic group herein can include a substituted alkyl group, where the alkyl group has one, two, or more substitutions with at least one anionic group. The substituted alkyl group may be a substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl, heptadecanyl, or octadecanyl group. The anionic group of the substituted alkyl group may be, for example, a carboxy group; that is, the anionic group herein may include a carboxyalkyl group. Examples of suitable carboxyalkyl groups herein include carboxymethyl (-CH2COOH), carboxyethyl (e.g., -CH2CH2COOH, -CH(COOH)CH3), carboxypropyl (e.g., -CH2CH2CH2COOH, -CH2CH(COOH)CH3, -CH(COOH)CH2CH3), carboxybutyl, and carboxypentyl groups. Apart from being substituted with at least one anionic group, the substituted alkyl group may also be optionally further substituted with at least one other group, such as an alkyl group or a hydroxyl group.

[0098] The organic group ether-linked to the alpha-glucan herein can comprise or consist of, for example, an alkyl group. The alkyl group can, in some embodiments, be linear, branched, or cyclic ("cycloalkyl" or "alicyclic"). In some embodiments, the alkyl group can be any of the C4 to C6 18 Alkyl group or C1-C 10 Alkyl group ("C #", # indicates the number of carbon atoms in the alkyl group, etc. 18 It is an alkyl group. The alkyl group can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl, heptadecanyl, or octadecanyl; such alkyl groups are typically linear. In some embodiments, one or more carbons of the alkyl group can be replaced with another alkyl group to make the alkyl group branched. Suitable examples of branched chain isomers of linear alkyl groups include isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, neopentyl, isohexyl, neohexyl, 2-ethylhexyl, 2-propylheptyl, and isooctyl. In some embodiments, the alkyl group is a cycloalkyl group, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl groups.

[0099] In some cases, the etherified alkyl groups herein may contain one or more heteroatoms, such as oxygen, sulfur, and / or nitrogen, in the hydrocarbon chain. Examples include alkyl glycerol alkoxylate moieties (-alkylene-OCH2CH(OH)CH2OH), moieties derived from ring-opening of 2-ethylhexyl glycidyl ether, and alkyl groups containing tetrahydropyranyl groups (e.g., from dihydropyran). Further examples include alkyl groups substituted at the end with a cyano group (-C≡N); such substituted alkyl groups may in some cases be referred to as nitrile or cyanoalkyl groups. Examples of cyanoalkyl groups herein include cyanomethyl, cyanoethyl, cyanopropyl, and cyanobutyl groups.

[0100] In some embodiments, the etherified organic group is a C-C 18 (For example, C4~C 18) alkenyl groups, which may be linear, branched, or cyclic. The term "alkenyl group" as used herein refers to a hydrocarbon group containing at least one carbon-carbon double bond. Examples of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexyl, and allyl groups. In some embodiments, one or more carbons of the alkenyl group may have substitution with an alkyl group, a hydroxyalkyl group, or a dihydroxyalkyl group as disclosed herein. Examples of such substituent alkyl groups include methyl, ethyl, and propyl groups. In some cases, the alkenyl groups herein may contain one or more heteroatoms, such as oxygen, sulfur, and / or nitrogen, in the hydrocarbon chain; for example, the alkenyl group may contain a moiety derived from the ring opening of an allyl glycidyl ether.

[0101] In some embodiments, the etherified organic group is a C-C 18 It comprises or consists of an alkynyl group. The term "alkynyl" as used herein refers to straight-chain and branched hydrocarbon groups containing at least one carbon-carbon triple bond. The alkynyl group herein can be, for example, propynyl, butynyl, pentynyl, or hexynyl. The alkynyl group can optionally be substituted with alkyl, hydroxyalkyl, and / or dihydroxyalkyl groups, and the like. The alkynyl group can optionally contain one or more heteroatoms, such as oxygen, sulfur, and / or nitrogen, in the hydrocarbon chain.

[0102] In some embodiments, the etherified organic group is (-CH2CH2O-). 、 In some embodiments, the organic group comprises or consists of a polyether comprising repeat units of (-CH2CH(CH3)O-), or mixtures thereof, the total number of repeat units being in the range of 2 to 100. 3~100 or (-CH2CH2O-) 4~100 In some embodiments, the organic group is a polyether group comprising (-CH2CH(CH3)O-) 3~100or (-CH2CH(CH3)O-) 4~100 As used herein, for polyether groups, subscripts designating a range of values ​​designate the potential number of repeating units; for example, (CH2CH2O). 2~100 means a polyether group containing 2 to 100 repeat units. In some embodiments, the polyether groups herein can be capped, such as with methoxy, ethoxy, or propoxy groups.

[0103] In some embodiments, the etherified organic group comprises or consists of an aryl group. As used herein, the term "aryl" refers to an aromatic / carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple condensed rings, at least one of which is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl), which is optionally mono-, di-, or tri-substituted with an alkyl group, such as a methyl, ethyl, or propyl group (or any other alkyl group herein). In some embodiments, an aryl group is a C6-C 20 It is an aryl group. In some embodiments, the aryl group is a methyl-substituted aryl group, such as a tolyl (-CHCH) or xylyl [-CH(CH)] group. For example, the tolyl group can be a p-tolyl group. In some embodiments, the aryl group is a benzyl group (-CH-phenyl). The benzyl group herein can be optionally substituted (typically on the phenyl ring) with one or more of halogen, cyano, ester, amide, ether, alkyl (e.g., C1-C6), aryl (e.g., phenyl), alkenyl (e.g., C2-C6), or alkynyl (e.g., C2-C6) groups.

[0104] In some embodiments, the alpha-glucan ether may contain one type of etherified organic group herein. However, in some embodiments, the alpha-glucan ether may contain two or more different types of etherified organic groups herein (i.e., mixed ethers of alpha-glucans). Examples of such alpha-glucan ethers include (i) two different alkyl groups as the etherified organic group, (ii) an alkyl group and a hydroxyalkyl group as the etherified organic group (alkylhydroxyalkyl alpha-glucan), (iii) an alkyl group and a carboxyalkyl group as the etherified organic group (alkylcarboxyalkyl alpha-glucan), (iv) a hydroxyalkyl group and a carboxyalkyl group as the etherified organic group (hydroxyalkylcarboxyalkyl alpha-glucan), (v) two different hydroxyalkyl groups as the etherified organic group, (vi) two different carboxyalkyl groups as the etherified organic group, (vii) a carboxyalkyl group and an aryl (e.g., benzyl) group. Some non-limiting examples of these types of mixed ethers include ethyl hydroxyethyl alpha-glucan, hydroxyalkylmethyl (e.g., hydroxypropylmethyl) alpha-glucan, carboxymethyl hydroxyethyl alpha-glucan, carboxymethyl hydroxypropyl alpha-glucan, and carboxymethyl benzyl alpha-glucan. Mixed alpha-glucan ethers may, in some cases, be disclosed in U.S. Patent Application Publication No. 2020 / 0002646, which is incorporated herein by reference.

[0105] The alpha-glucan derivative may be an ester derivative in some embodiments. The acyl group of the alpha-glucan ester derivative herein may be, for example, those disclosed in US Patent Application Publication No. 2014 / 0187767, US Patent Application Publication No. 2018 / 0155455, or US Patent Application Publication No. 2020 / 0308371, or International Publication No. WO 2021 / 252575 (each of which is incorporated herein by reference).

[0106] The alpha-glucan derivatives herein may be, in some embodiments, alpha-glucan carbamates.The alpha-glucan carbamate derivatives may include, for example, carbamate groups derived from aliphatic, alicyclic, or aromatic monoisocyanates.In some embodiments, the substituents of the alpha-glucan carbamate derivatives may be carbamate-linked phenyl, benzyl, diphenylmethyl, or diphenylethyl groups; these groups may be optionally derived with aromatic monoisocyanates, for example, phenyl, benzyl, diphenylmethyl, or diphenylethyl isocyanates, respectively. In some embodiments, the substituents of the alpha-glucan carbamate derivatives may be carbamate-linked ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or octadecyl groups; these groups may optionally be derivatized with an aliphatic monoisocyanate, such as ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or octadecyl isocyanate, respectively. In some embodiments, the substituents of the alpha-glucan carbamate derivatives may be carbamate-linked cyclohexyl, cycloheptyl, or cyclododecyl groups; these groups may optionally be derivatized with an alicyclic monoisocyanate, such as cyclohexyl, cycloheptyl, or cyclododecyl isocyanate, respectively.

[0107] The carbamate group of the alpha-glucan carbamate derivatives herein can be, for example, those disclosed in WO 2020 / 131711 or WO 2021 / 252569, or U.S. Patent Application Publication No. 2022 / 0033531, each of which is incorporated herein by reference.

[0108] In some embodiments, the alpha-glucan derivative may be an alpha-glucan sulfonyl derivative. The sulfonyl group of the alpha-glucan sulfonyl derivative herein may be, for example, one disclosed in WO 2021 / 252569 (which is incorporated herein by reference).

[0109] In some embodiments, the alpha-glucan derivative may have a carboxylate (carboxylic acid) group. The carboxylic acid group may be present, for example, alone (e.g., carbon 6 of glucose may be -COOH) or via (i) an ether, ester, carbamate, or sulfonyl bond to the alpha-glucan and (ii) an organic group that contains a carboxylic acid group (e.g., a carboxyalkyl group such as carboxymethyl). In some embodiments, the carboxylic acid group may be introduced by oxidizing the alpha-glucan or alpha-glucan derivative (e.g., to carbon 6 of glucose and / or to a substituent carbon); oxidation may be introduced, for example, to carbon 6 of glucose and / or to a substituent carbon, as described in Canadian Patent Publication No. 2028284 or Canadian Patent Publication No. 2038640, or U.S. Patent No. 4985553, U.S. Patent No. 2894945, U.S. Patent No. 5747658, or U.S. Patent No. 7595392, or U.S. Patent Application Publication No. 200200236644. This may be carried out via the processes disclosed in Publication No. 2015 / 0259439, Publication No. U.S. Patent Application No. 2018 / 0022834, or Publication No. U.S. Patent Application No. 2018 / 0079832, or Publication No. U.S. Patent Application No. 63 / 151,223 or Publication No. 63 / 151,237, or Publication No. WO 2022 / 178075 or Publication No. WO 2022 / 178073, each of which is incorporated herein by reference.

[0110] Thus, polysaccharides other than the alpha-1,3-glucans of the present disclosure may be derivatized and used herein. Such derivatization may be, for example, as disclosed above (e.g., DoS, types of derivatives, substituents). In some additional or alternative embodiments, non-derivatized polysaccharides may be used. In some embodiments, the polysaccharide can be a fructan, galactan, mannan, arabinan, xylan, soy polysaccharide, chitosan, chitin, glycosaminoglycan (e.g., heparan sulfate, dermatan sulfate, heparin), glucosamine, carrageenan, alginate, xanthan, guar, cyclodextrin, gellan, curdlan, beta-glucan (e.g., beta-1,4-glucan [cellulose], beta-1,3-glucan), or an alpha-glucan that is not an alpha-1,3-glucan herein (e.g., alpha-1,6-glucan, optionally with alpha-1,2 and / or alpha-1,3 branching, alpha-1,4-glucan, alternan, reuteran, pullulan). While polysaccharide derivatives and / or underivatized forms thereof may be used as additives in some embodiments (part c), in some embodiments polysaccharide derivatives and / or underivatized forms thereof (e.g., beta-1,4-glucan [cellulose]) are not used as additives.

[0111] The caustic solution herein can include one, two, three, or more different alpha-glucan derivatives herein (e.g., differing in DPw, percent alpha-1,3 bonds, substitutions, and / or DoS). In some embodiments, the caustic solution does not include an alpha-glucan derivative herein, such as an ether or ester.

[0112] Any of the aforementioned polysaccharide derivatives (e.g., alpha-glucan derivatives) can be used, for example, as an additive in the solid compositions of the present disclosure. In some embodiments where the additive is an alpha-glucan derivative, the alpha-glucan portion thereof (i.e., that remains present prior to derivatization) can have the same (or similar, e.g., ±1%, 2%, or 3%) linkage and molecular weight profile as the underivatized alpha-glucan component.

[0113] The caustic solvent of the present disclosure is typically capable of dissolving the water-insoluble alpha-glucan and / or derivatives thereof of the portion (b) of the caustic solution herein. The caustic solvent is, in some embodiments, aqueous. The aqueous caustic solvent may, for example, comprise an alkali hydroxide. The alkali hydroxide may comprise at least one metal hydroxide (e.g., NaOH, KOH, LiOH) or an organic hydroxide (e.g., tetraethylammonium hydroxide). The aqueous caustic solvent may, for example, be one disclosed in WO 2015 / 200612 or WO 2015 / 200590, or US 2017 / 0208823 or US 2017 / 0204203, each of which is incorporated herein by reference. Typically, the water-insoluble alpha-glucan and / or derivatives thereof of the portion (b) of the caustic solution herein is not dispersed in the caustic solvent or otherwise dissolved in the solvent. The causticizing agent of the solvent herein (e.g., NaOH) should not be considered an additive (part [c]) of the present disclosure.

[0114] In some embodiments, the aqueous caustic solvent comprises one or more alkali hydroxides dissolved in water. The concentration of the alkali hydroxide can be, for example, about or at least about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 3-15, 3-12, 3-10, 3-8, 3-7, 3-6, 3-5, 3-4.5, 4-15, 4-12, 4-10, 4-8, 4-7, 4-6, 4-5, or 4-4.5 wt %.

[0115] The pH of the caustic solution and / or caustic solvent thereof herein can be, for example, about, or at least about, 10.5, 10.75, 11.0, 11.5, 12.0, 12.5, 13.0, 10.5-13.0, 10.5-12.5, 10.75-13.0, 10.75-12.5, 11.0-13.0, 11.0-12.5, 11.5-13.0, 11.5-12.5, 12.0-13.0, 12.0-12.5, or 12.5-13.0. The temperature of the caustic solution herein can be, for example, about, or at least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 1-70, 1-60, 1-50, 1-45, 1-40, 1-35, 1-30, 1-25, 1-20, 15-70, 15-60, 15-50, 15-45, 15-40, 15-35, 15-30, 15-25, 15-20, 20-70, 20-60, 20-50, 20-45, 20-40, 20-35, 20-30, 20-25, 5-30, 10-30, 5-25, or 10-25°C.

[0116] The concentration of alpha-glucan and / or alpha-glucan derivative in the caustic solution herein can be, for example, about, or at least about 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, 5-20, 5-17.5, 5-15, 5-12.5, 5-10, 7.5-20, 7.5-17.5, 7.5-15, 7.5-12.5, 7.5-10, 10-20, 10-17.5, 10-15, 10-12.5, 12.5-20, 12.5-17.5, or 12.5-15 wt%.

[0117] The compositions of the present disclosure, such as the caustic solution or any other composition herein (e.g., fiber, fibrid, composite, or film / coating), may contain from about 0.1 to about 200 wt% of one or more additives, where the wt% is based on (relative to) the weight of the alpha-glucan and / or alpha-glucan derivative in the caustic solution (part b) or composition. In some embodiments, the compositions contain from about 0.05, 0.1, 0.5, 0.75, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 10000, 15000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 100000, 150000, 150000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 15 ... 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 1-200, 1-175, 1-150, 1-125, 25-200, 25-175, 25-150, 25-125, 50-200, 50-175, 50-150, 50-125 , 75~200, 75~175, 75~150, 75~125, 100~200, 100~175, 100~150, 100~125, 0.1~50, 1~30, 1~25, 1~20, 1~15, 1~10, 3~30, 3~25, 3~20, 3~15, 3~10, 10~30, 10~25, 10~20, 10~15, 3~7, 4~6, 8~12, 9~11, 22~28, 23~27, 0.05~1, 0.05~0.75, 0.05~0.5, 0.05~0.25, 0.1~1, 0.1~0.75, 0.1~0.5, 0.1~0.25, 0.25~1, 0.25~0.75, 0.25~0.5, 0.05~50, 0.05~25, 0.05~20, 0.05~15, 0.05~10, 0.1~50, 0.1~25, 0.1~20, 0.1~15, 0.1~10, 0. 5-50, 0.5-25, 0.5-20, 0.5-15, 0.5-10, 1-50, 1-25, 1-20, 1-15, 1-10, 2.5-50, 2.5-25, 2.5-20, 2.5-15, 2.5-10, 5-50, 5-25, 5-20, 5-15, or 5-10 wt% of one or more additives, where the wt% is based on the weight of the one or more insoluble alpha-glucans in the composition.

[0118] The amount of time (i.e., age) that the caustic solution may exist when all of its components (at least the caustic solvent, alpha-glucan and / or alpha-glucan derivative, and additives) are combined can be, for example, about, or at least about 0.25, 0.5, 0.75, 1, 1.25, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 75, 100, 150, 200, 0.5-3, 0.5-2.5, 0.5-2, 0.5-1.5, 0.5-1.25, 0.75-3, 0.75-2.5, 0.75-2, 0.75-1.5, or 0.75-1.25 days.

[0119] In some embodiments, the caustic solution can have an elastic modulus (G') of about, or at least about, 4, 5, 6, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 4-120, 4-110, 4-100, 4-90, 10-120, 10-110, 10-100, 10-90, 50-120, 50-110, 50-100, 50-90, 70-120, 70-110, 70-100, or 70-90 Pascals (Pa). The caustic solution in some embodiments can have a viscous modulus (G") of about, or at least about, 35, 40, 50, 75, 100, 125, 150, 175, 200, 35-200, 35-175, 35-150, 40-200, 40-175, 40-150, 100-200, 100-175, 100-150, 125-200, 125-175, or 125-150 Pascals (Pa). The elastic modulus (G') and / or viscous modulus (G") herein can be measured according to the following examples (e.g., where each condition / parameter is performed within 5%, 10%, or 15% of the relevant condition / parameter disclosed in the examples).

[0120] For example, part (c) of the caustic solution herein or any other composition (e.g., fiber, fibrid, composite, film / coating, or powder) herein additive may, in some embodiments, comprise or consist of one or more crosslinking agents. Examples of crosslinking agents herein include phosphoryl chloride (POCl3), polyphosphates, sodium trimetaphosphate (STMP), boron-containing compounds (e.g., boric acid, diborates, tetraborates, e.g., tetraboric acid decahydrate, pentaborates, polymeric compounds, e.g., Polybor®, alkali borates), polyvalent metals (e.g., titanium-containing compounds, e.g., titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, or polyhydroxy complexes of titanium; zirconium-containing compounds, e.g., zirconium lactate, zirconium carbonate, zirconium acetylacetonate, zirconium triethanolamine, zirconium lactate diisopropylamine, or polyhydroxy complexes of zirconium), glyoxal, glutaraldehyde, aldehydes, Examples of suitable glycidyl ethers include polyphenols, divinyl sulfones, epichlorohydrin, polyamide-epichlorohydrin (PAE), di- or polycarboxylic acids (e.g., citric acid, malic acid, tartaric acid, succinic acid, glutaric acid, adipic acid), dichloroacetic acid, polyamines, 1,2,7,8-diepoxyoctane, diethylene glycol dimethyl ether (diglyme), diglycidyl ethers (e.g., diglycidyl ether itself, ethylene glycol diglycidyl ether [EGDGE], 1,4-butanediol diglycidyl ether [BDGE], polyethylene glycol diglycidyl ether [PEGDE such as PEG2000DGE], bisphenol A diglycidyl ether [BADGE]), and triglycidyl ethers (e.g., trimethylolpropane triglycidyl ether). Further examples of suitable cross-linking agents are described in U.S. Pat. Nos. 4,462,917, 4,464,270, 4,477,360, or 4,799,550, or U.S. Patent Application Publication No. 2008 / 0112907, each of which is incorporated herein by reference.In some embodiments, the crosslinking agent is not a boron-containing compound (e.g., as described above). The crosslinking agent herein is typically soluble in the caustic solvent and can act to crosslink the alpha-glucan and / or alpha-glucan derivative molecules dissolved in the caustic solvent. Such crosslinking is typically covalent; that is, the alpha-glucan molecules and / or alpha-glucan derivative molecules are chemically crosslinked to each other (through intermolecular crosslinks). Thus, in some embodiments, the caustic solution may be characterized as comprising crosslinked alpha-glucan and / or crosslinked alpha-glucan derivatives, such crosslinked material optionally produced using any of the crosslinking agents of the present disclosure. In some embodiments, the alpha-glucan and / or alpha-glucan derivatives are crosslinked (optionally using a crosslinking agent of the present disclosure) before being placed in the caustic solvent to produce the caustic solution herein. Optionally, in embodiments herein that include a crosslinking agent or crosslinked alpha-glucan and / or alpha-glucan derivatives, there are no other additives or less than 0.1 wt% of other additives.

[0121] The concentration of one or more crosslinking agents in the caustic solution herein may be, for example, about 0.005, 0.01, 0.025, 0.05, 0.1, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 2.0, 3.0, 4.0, 5.0, 7.5, 10, 0.005-0.25, 0.005-0.20, 0.005-0.15, 0.005-0.10, 0.005-0.05, 0.005-0.01, 0.01-0.25, 0.01-0.20, 0.0 The concentration may be at least about, or less than about, 1-0.15, 0.01-0.10, 0.01-0.05, 0.1-3.0, 0.1-2.0, 0.1-1.5, 0.1-1.25, 0.1-1.0, 0.5-3.0, 0.5-2.0, 0.5-1.5, 0.5-1.25, or 0.5-1.0 wt%, where the wt% is based on (relative to) the weight of the alpha-glucan and / or alpha-glucan derivative in the caustic solution (part b). Such concentrations may typically be characterized as initial concentrations (e.g., concentrations calculated based on the amount of cross-linker added) since the concentration of free cross-linker typically decreases as the alpha-glucan and / or alpha-glucan derivative is cross-linked by the cross-linker.

[0122] The crosslinked alpha-glucans and / or crosslinked alpha-glucan derivatives of the present disclosure are typically soluble in the caustic solvents herein, while typically insoluble in non-caustic aqueous solvents (e.g., water alone). All or most (e.g., at least about 70%, 75%, 80%, 85%, 90%, or 95% complete) of the crosslinking herein (e.g., as measured by the maximum decrease in free crosslinker concentration) typically occurs in the caustic solution prior to setting the solution into a desired shape / product (e.g., fiber, fibrid, film / coating / layer, composite).

[0123] For example, additives herein for part (c) of the caustic solution herein or any other composition (e.g., fiber, fibrid, composite, film / coating, or powder), etc., may in some cases be referred to as, for example, an "ingredient / component" (when the first or other component is one or more alpha-glucan or alpha-glucan derivative compounds). Except for embodiments in which the additive is a crosslinker, the additive typically does not chemically react with the alpha-glucan or alpha-glucan derivative, and therefore does not chemically modify or derivatize the alpha-glucan or alpha-glucan derivative to result in a compound different from the alpha-glucan or alpha-glucan derivative as present prior to the addition of the additive (e.g., such additives do not function to replace any hydrogen of the glucose monomer unit hydroxyl groups of the alpha-glucan or alpha-glucan derivative; e.g., such additives do not change the molecular formula of the alpha-glucan or alpha-glucan derivative). In some embodiments, there may be one, two, three, four, or more additives. The additives may be soluble or insoluble in the caustic solution. The additive may be soluble or insoluble in a non-caustic aqueous solvent (eg, water alone).

[0124] The additives herein may be any compound of the present disclosure. The disclosure of additives herein typically relates to their existing state before being used to prepare the compositions herein (i.e., the state in which the additives are provided before being mixed with other components herein). In some embodiments, the additives comprise or consist of non-aqueous liquids and / or hydrophobic or non-polar liquids or compositions. Non-aqueous liquids may be, for example, polar or non-polar (non-polar). The additives in some embodiments may comprise or consist of solid materials, and such additives may be in aqueous or non-aqueous liquids, as the case may be. The additives may, for example, have a neutral, negative (anionic), or positive (cationic) charge; i.e., the additives may be electrically charged. Examples of charged additives include charged polysaccharides and charged polysaccharide derivatives (e.g., polysaccharide ethers) (e.g., soluble or insoluble forms thereof), such as any of those disclosed herein (e.g., with respect to alpha-glucans, where at least about 50% of the glycosidic linkages in the alpha-glucan are alpha-1,3 glycosidic linkages and the weight average degree of polymerization of the alpha-glucan is at least 15). The additive can be, for example, any ingredient typically used in personal care products, pharmaceuticals, household care products, industrial products, ingestible products, films / coatings, composites, latexes / dispersions / emulsions, encapsulants, detergent compositions (e.g., fabric care, dish care), oral care, or builder compositions. By way of example, additives herein include oils such as mineral oil, silicone oils (e.g., dimethicone / polydimethylsiloxane, hexamethyldisiloxane), paraffin oil, or vegetable / vegetable oils (e.g., linseed oil, soybean oil, palm oil, coconut oil, canola oil, corn oil, sunflower oil, grape seed oil, cocoa butter, olive oil, rice bran oil, rapeseed oil, peanut oil, sesame oil, cottonseed oil, palm kernel oil); shortenings (e.g., vegetable shortening); lipids; fats (e.g., lard, tallow, animal fats); glycerides (e.g., tri-, di-, and / or mono-glycerides; e.g., caprylic / capric triglyceride); glycerol (or other polyols, such as low molecular weight polyols); fatty acids; fatty aldehydes, fatty alcohols,The detergent may be a fatty acid ester (e.g., sorbitan oleate); a fatty acid amide (e.g., ethylene bis(stearamide)); a wax (e.g., paraffin wax, carnauba wax); a phospholipid; a sterol; an alkane; an alkene / olefin; a petrolatum (i.e., petrolatum jelly); a grease; a detergent; an anionic detergent (e.g., lauryl sulfate, alkylbenzene sulfonate); a cationic detergent; a nonionic or zwitterionic detergent (e.g., polyoxyethylene-based detergents such as Tween or Triton [ethoxylate], glycoside-based detergents such as octylthioglucoside maltoside, CHAPS); or any epoxidized version thereof; or any similar compound as disclosed in U.S. Patent Application Publication No. 2009 / 0093543 (e.g., Table 2 therein) or U.S. Patent Application Publication No. 2019 / 0144897 (which are incorporated herein by reference). By way of example, the additive herein may be a sugar alcohol (e.g., mannitol, sorbitol, xylitol, lactitol, isomalt, maltitol, hydrogenated starch hydrolysates), a polymer polyol (e.g., polyether polyol, polyester polyol, polyethylene glycol, polyvinyl alcohol), an aprotic solvent (e.g., a polar aprotic solvent such as acetone or propylene carbonate), a protic solvent (e.g., isopropanol, ethanol, methanol), a hardener (e.g., an active halogen compound, vinyl sulfone, epoxy), a resin (typically uncured) (e.g., a synthetic resin such as an epoxy or acetal resin; a natural resin such as a plant resin [e.g., rosin], an insect resin [e.g., shellac], or bitumin), or a propanediol. By way of example only, the additives herein may be fragrances / scents (e.g., hydrophobic aroma compounds or any of those disclosed in U.S. Pat. No. 7,196,049, which is incorporated herein by reference), ingestible products, foods, beverages, flavors (e.g., any of those disclosed in U.S. Pat. No. 7,022,352, which is incorporated herein by reference), hydrophobic flavorings or nutrients (e.g., vitamins such as vitamins A, D, E, or K), or dyes (e.g.,The dye may be an oil-soluble dye such as Sudan Red. By way of example, the additives herein may be any of the polysaccharide derivatives herein (water soluble or water insoluble), such as polyurethanes, polyvinyl acetates, polyacrylates, polylactic acids, polyvinylamines, polycarboxylates, polysaccharides herein other than the water insoluble alpha-glucans having at least 50% alpha-1,3 glycosidic bonds, derivatives of the water insoluble alpha-glucans having at least 50% alpha-1,3 glycosidic bonds of the present disclosure (in some embodiments, if the additive is an alpha-1,3-glucan derivative, the compositions herein may include a non-derivatized water insoluble alpha-1,3-glucan as a separate component, e.g., for portion [b] of the caustic solution or products made therefrom), or any other polysaccharide derivatives herein, gelatin, melamine, inorganic filler materials (e.g., carbon black, silicates such as sodium silicate, clays such as talk, chalk, bentonite clay, or calcium carbonate, calcium carbonate-magnesium carbonate, sodium percarbonate, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, barium carbonate, magnesium carbonate, potassium carbonate, etc. , or carbonates such as iron [II] carbonate), penetrating agents (e.g., 1,2-propanediol, triethylene glycol butyl ether, 2-pyrrolidone), biocides (e.g., metaborates, thiocyanates, sodium benzoate, benzisothiaolin-3-one), yellowing inhibitors (e.g., sodium hydroxymethylsulfonate, sodium p-toluenesulfonate), UV absorbers (e.g., benzotriazole compounds), antioxidants (e.g., sterically hindered phenolic compounds), water resistance agents (e.g., ketone resins, anionic latex, glyoxal), or binders (e.g., polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl acetate, silanol-modified polyvinyl alcohol, polyurethane, starch, corn dextrin, carboxymethyl cellulose, cellulose ether, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, alginate, sodium alginate, xanthan, carrageenan, casein, soy protein, guar gum,styrene butadiene latex, styrene acrylate latex). In some embodiments, the additive can be a bleaching agent (e.g., a chlorine bleaching agent such as sodium hypochlorite or chlorinated lime; a peroxide bleaching agent such as hydrogen peroxide, sodium percarbonate, peracetic acid, benzoyl peroxide, or potassium permanganate). In some embodiments, the additives can be characterized / classified as follows: amphiphilic materials (e.g., surfactants such as lauryl sulfate; polymeric surfactants such as polyethylene glycol or polyvinyl alcohol; particles such as silica), water-insoluble small molecules (e.g., mineral oil; silicone oil; natural oils such as linseed oil, soybean oil, palm oil, or coconut oil), water-insoluble polymer molecules (e.g., polyacrylates, polyvinyl acetates, polylactic acids), water-miscible small molecules (e.g., protic solvents such as isopropanol, ethanol, or methanol; polar aprotic solvents such as acetone or propylene carbonate; low molecular weight polyols such as glycerol; sugar alcohols), or water-miscible polymer molecules (e.g., polyols). In some embodiments, the additives can be alkyl ketene dimers (AKD), alkenyl succinic anhydrides (e.g., octenyl succinic anhydride), epoxy compounds (e.g., epoxidized linseed oil or diepoxy), phenethyl alcohol, undecyl alcohol, or tocopherol. The additive in some embodiments may be an elastomer. The additive in some embodiments may be a rubber or any other diene-based elastomer. Examples of rubbers herein include natural rubber (NR) (e.g., NR latex) and synthetic rubbers. Examples of synthetic rubbers herein include synthetic polyisoprene, polybutadiene, styrene-butadiene copolymers, styrene-isoprene copolymers, butadiene-isoprene copolymers, styrene-butadiene-isoprene terpolymers, ethylene propylene diene monomer rubbers, hydrogenated nitrile butadiene rubbers, silicone rubbers, and neoprenes, which are also examples of diene-based elastomers. Rubbers such as silicone rubbers are not diene-based in some embodiments. In some embodiments, the additive is not a rubber. In some embodiments, the additive is a hydrophobic material (e.g., hydrophobic fragrances, flavors, nutrients,The additives herein typically include the oils or any other hydrophobic solvents in which the additives (such as Na, NaCl ... + , Cl - The additives may be, for example, any of the salts (salt ions) or buffers such as NaCl, phosphate, Tris, etc., as well as any other salts / buffers as disclosed in US Patent Application Publication No. 2014 / 179913, US Patent Application Publication No. 2016 / 0304629, US Patent Application Publication No. 2016 / 0311935, US Patent Application Publication No. 2015 / 0239995, US Patent Application Publication No. 2018 / 0230241, or US Patent Application Publication No. 2018 / 0237816 (which are incorporated herein by reference). The additives may be, for example, any of the salts / buffers disclosed in US Patent Application Publication No. 2019 / 0153674 (which are incorporated herein by reference).

[0125] In some embodiments, the additive is a water-insoluble polysaccharide (e.g., any of those herein, such as cellulose) that remains undissolved (i.e., the insoluble polysaccharide does not dissolve in the selected caustic solution) throughout the processes herein that produce the solid composition. The solid composition in such embodiments contains the water-insoluble polysaccharide additive in a dispersed manner (i.e., the solid composition is a solid sol) rather than in the homogeneous manner that would occur if the water-insoluble polysaccharide were dissolved in the selected caustic solution.

[0126] The additives are hydrophobic in some embodiments (e.g., any of the above that are hydrophobic / non-polar / non-polar). Hydrophobic additives are, for example, liquid (e.g., at temperatures disclosed herein, e.g., 10-60, 15-60, 20-60, 25-60, 30-60, 10-55, 15-55, 20-55, 25-55, 30-55, 10-50, 15-50, 20-50, 25-50, 30-50, 10-45, 15-45, 20-45, 25-45, 30-45, 10-40, 15-40, 20-40, 25-40, or 30-40° C.) and are not miscible (i.e., water insoluble) in the aqueous composition (e.g., in the caustic or non-caustic aqueous conditions herein). The liquid hydrophobic additive can be, for example, an oil, such as the oils disclosed herein. In some embodiments, the hydrophobic additive is solid (e.g., at temperatures disclosed herein) and is not soluble in the aqueous composition (e.g., the caustic or non-caustic aqueous conditions herein). The solid hydrophobic additive can be, for example, a wax or grease. In some embodiments, the solid hydrophobic additive has a melting point of about, or at least about, 45, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 75, 80, 85, 90, 95, 100, 45-70, 45-65, 50-70, or 50-65°C.

[0127] In some embodiments, an emulsion aid (emulsion stabilizer) can be used to prepare an emulsion of the liquid additive in the caustic solvent. Examples of emulsion aids include surfactants (e.g., anionic surfactants such as sodium dodecyl sulfate) and polyelectrolytes (e.g., anionic polyelectrolytes). The emulsion stabilizer herein can be present, for example, in the caustic solvent herein at about 0.001-0.01, 0.004-0.006, or 0.005 wt %.

[0128] The caustic solution of the present disclosure may, in some embodiments, be in the form of a filament (dope filament), film / coating, or other three-dimensional material (e.g., fibrids, composites). Such forms may exist as the caustic solution, for example, immediately prior to removal of the caustic solvent to obtain a solid material (e.g., fiber, film / coating, fibrids, composites).

[0129] Some aspects of the present disclosure relate to methods of producing the caustic solution herein. Such methods may include, for example: mixing at least (i) the alpha-glucan and / or the alpha-glucan herein, and (ii) the additive herein with (in) a caustic solvent, where the alpha-glucan and / or derivatives thereof dissolve in the caustic solvent. The additive dissolves in the caustic solvent in some embodiments, while in other embodiments it remains undissolved (e.g., dispersed).

[0130] Some aspects of the present disclosure relate to methods of producing a solid composition. Such methods may include, for example: (a) providing a caustic solution herein; (b) putting (consolidating / putting / forming / extruding) the caustic solution into a desired form (e.g., fiber, film / coating, fibrid, or composite; e.g., extruded and / or drawn form, which may optionally be a fiber, film, or composite); and (c) removing the caustic solvent from the caustic solution of step (b) to produce a solid composition comprising alpha-glucan or a derivative thereof and additives. The solid composition produced from step (c) may be in the form / shape of, for example, a fiber (e.g., filament), fibrid, extrudate, composite, or film / coating (or any form produced by extruding and / or drawing the caustic solution prior to step [c], e.g., fiber or film). Such methods may, in some cases, be characterized herein as forming or solidifying methods. Some aspects herein relate to compositions / products comprising the solid composition produced by the methods / processes of the present disclosure.

[0131] In some embodiments, step (b) of forming the caustic solution into the desired form may include using an apparatus having one or more orifices (e.g., holes, nozzles, or perforations) through which the caustic solution is passed (ejected / ejected / forced). Such a process may in some cases be characterized as extrusion. One example of an apparatus suitable for carrying out step (b) in this manner is a spinneret. The shape of the caustic solution processed by extrusion in step (b) may be, for example, a fiber (e.g., filament), film, or composite; such shapes typically similarly characterize the product produced in step (c). In some embodiments, the fiber form (dope filaments / fibers) can be, for example, prepared using a spinneret, die, or similar device, in some cases at (i) an airflow pressure of about, or up to about, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 10-100, 10-90, 10-80, 10-70, 20-100, 20-90, 20-80, 20-70, 30-100, 30-90, 30-80, 30-70, 40-100, 40-90, 40-80, or 40-70 mbar; (ii) about , at least about, or at most about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 8-20, 8-15, 10-20, 10-15, 12-20, or 12-15 m / min; and / or (iii) a spinning speed of about, at least about, or at most about 10, 15, 20, 25, 30, 35, 40, 10-40, 10-35, 10-30, 15-40, 15-35, 15-30, 20-40, 20-35, or 20-30 m / min. The diameter (longest diameter) of one or more orifices in the device through which the caustic solution passes can be, for example, about, at least about, or up to about 30, 40, 50, 60, 70, 80, 90, 30-90, 30-80, 30-70, 40-90, 40-80, 40-70, 50-90, 50-80, 50-70, or 55-65 microns. The orifices herein can have, for example, a circular, elliptical, square, or rectangular cross section.In some embodiments, continuous dope filaments can be produced; such dope filaments do not undergo constant, repeated, or continuous breakage or other disruption after transition from the orifice. Step (b) of forming the caustic solution into the desired form can optionally further include stretching the caustic solution, such as after it is extruded; in some cases, stretching can be used to draw down the diameter of the extruded caustic solution, such as the dope filament. In some embodiments, the dope filament has a diameter (longest diameter) that is about, or at least about, 10%, 20%, 30%, 40%, 50%, 60%, 10-60%, 10-50%, 10-40%, 10-30%, 10-20%, 20-60%, 20-50%, 20-40%, or 20-30% smaller than the diameter of the orifice (e.g., herein) used to extrude the dope used to make the dope filament.

[0132] The amount of caustic solvent removed in step (c) of the forming process can be, for example, about, or at least about 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 100%, 80-100%, 90-100%, 95-100%, or 98-100% by weight of the caustic solvent present before performing step (c).

[0133] In some embodiments of the forming method, step (c) of removing the caustic solvent may include chemically or ionically modifying the caustic solvent (or caustic solution) so that the alpha-glucan or alpha-glucan derivative and additives (if soluble in the caustic solvent) are no longer soluble in the caustic solvent. This can be done, for example, by a coagulation process and / or a neutralization process. It is noted that when the caustic solution herein includes cross-linked alpha-glucan or alpha-glucan derivative, coagulation or neutralization is not required to retain the shape of the caustic solution form produced in step (b), although such processes can be used to cross-link material if desired (e.g., at least for neutralization purposes). In some embodiments, typically those in which no cross-linking agent is used, coagulation or neutralization is used to make the form / shape produced in step (b) self-supporting. To carry out step (c), for example, the form / shape produced in step (b) may be contacted with (e.g., immersed / soaked in, sprayed with, or otherwise exposed to) a coagulation / neutralization medium (e.g., liquid or aerosol form) for a suitable time and / or at a temperature less than about 60, 70, or 80° C. (e.g., about room temperature [about 20-25° C.] to about 80° C.). The coagulation / neutralization medium typically includes at least one non-solvent for the alpha-glucan or alpha-glucan derivative (and optionally additives), such as an alcohol (e.g., methanol, ethanol, propanol), water, an acid, or a mixture thereof. The acid for the coagulation / neutralization medium may be, for example, sulfuric acid, acetic acid, or citric acid. In some embodiments, the coagulation / neutralization medium may include water and about 4-25 wt % sulfuric acid and about 2-30 wt % sodium sulfate. In some embodiments, the coagulation / neutralization medium contains little (≦0.1 or 0.05 wt%) or no sulfates, such as zinc sulfate.

[0134] The solidified / neutralized form / shape after step (c) can be optionally washed; for example, water or alcohol can be used for washing. If necessary, washing can be done until a neutral pH (for washing) (e.g., pH 6-8 or about 7) is achieved. The washing or post-washing step can optionally further comprise immersing the form / shape in a 1-10 wt % (e.g., about 5 wt %) plasticizer (e.g., glycerol or ethylene glycol) solution (e.g., water-based or alcohol-based) for a suitable period of time (e.g., at least 2, 3, or 4 minutes). The form / shape herein can be dried, if desired, for example, by exposure to a temperature of about 70-85° C. for a suitable period of time (e.g., 10-20 minutes). In some embodiments, the solidified form / shape after step (c) is not neutralized and / or washed.

[0135] In some embodiments, coagulation and / or neutralization may be carried out as described in U.S. Patent Application Publication No. 2016 / 0177471, U.S. Patent Application Publication No. 2016 / 0333157, U.S. Patent Application Publication No. 2017 / 0283568, or U.S. Patent Application Publication No. 2015 / 0191550, or U.S. Patent No. 7,000,000 or U.S. Patent No. 1,098,334, which are incorporated herein by reference, or as disclosed in the Examples below (e.g., each condition / parameter is performed within 5%, 10%, or 15% of the relevant condition / parameter disclosed in the Examples).

[0136] In some embodiments, step (c) may include blowing air through the caustic solution such that the alpha-glucan or its alpha-glucan derivatives and additives (if soluble in the caustic solvent) are no longer soluble in the caustic solvent. Such a process may be carried out, for example, as described in US Patent Publication No. 2018 / 0282918, which is incorporated herein by reference. In some embodiments, step (c) may include air drying the caustic solution such that the alpha-glucan or its alpha-glucan derivatives and additives (if soluble in the caustic solvent) are no longer soluble in the caustic solvent. In some cases, the air-dried form / shape after step (c) is not neutralized and / or washed.

[0137] In some embodiments, the formed shape after step (c) herein is stretched and / or heated (eg, to about 100-110° C.), or is neither stretched nor heated.

[0138] In some embodiments of the forming method for the production of fibrids, steps (b) and (c) are generally performed simultaneously with each other in that the caustic solution herein is subjected to shear forces (step [b] of shape formation) and simultaneously subjected to precipitation conditions that precipitate alpha-glucan (e.g., as described above for step [c], e.g., with an acid or alcohol), resulting in the formation of fibrids that contain alpha-glucan (or alpha-glucan derivatives) and additives. Such fibrids may in some cases be characterized as "hybrid fibrids." Such processes may be performed, for example, as described in U.S. Pat. No. 1,118,312, which is incorporated herein by reference, or as disclosed in the Examples below (e.g., each condition / parameter is performed within 5%, 10%, or 15% of the relevant condition / parameter disclosed in the Examples). In some embodiments, it is believed that the additive is encapsulated within the hybrid fiber and / or embedded on the outer surface (and / or some other association mechanism) of the hybrid fiber such that the additive does not (or does not dissociate much) from the hybrid fiber under non-caustic aqueous conditions; in some embodiments, this may be true even if the additive is aqueous-soluble, water-soluble under non-caustic conditions. This additive retention behavior is believed to be applicable to other compositions herein, such as fibers (e.g., filaments), films / coatings, or composites as well. Some embodiments of producing hybrid fibers (or other hybrid compositions herein) relate to tuning, modulating / controlling the charge of the fiber / product. Such embodiments typically include using an appropriate amount of a charged additive herein (e.g., a charged polysaccharide or a charged polysaccharide derivative) as part (c) of the caustic solution with an alpha-glucan herein (uncharged / underivatized) as part (b) of the caustic solution to produce fibrids or other compositions.This approach has advantages over previous work in which the means of controlling the charge of the product was to select a specifically charged alpha-glucan derivative as the only fibrid / product component (i.e., no additives); such typically involved providing an alpha-glucan derivative with a particular degree of substitution with a charged moiety (e.g., a charged organic group). Now, the methodology of the present disclosure allows for the production of fibrids / products with a preselected charge, even when using water-soluble charged additives (e.g., washing and / or other processing of the product in non-caustic aqueous conditions does not remove any, or a significant amount of, the water-soluble charged additives).

[0139] Some embodiments herein relate to a method for producing a film / coating composition. Such a method may include, for example: (a) providing a preparation comprising at least (i) the caustic solvent herein, (ii) the water-insoluble alpha-glucan herein, and (iii) an additive herein (e.g., a hydrophobic additive), where the alpha-glucan dissolves in the caustic solvent; (b) contacting the preparation with a substrate; and (c) removing the caustic solvent from the preparation of step (b) to produce a film / coating composition comprising the alpha-glucan and the additive. This method may be characterized as a method for producing a film or coat, as the case may be. The step of removing the caustic solvent may be carried out as disclosed herein, as needed.

[0140] For example, when the additive is a hydrophobic additive, in some embodiments of the film / coating production method, the preparation is a dispersion. Such a dispersion can be an emulsion (i.e., the liquid is dispersed but not dissolved in the caustic solvent) in embodiments where a liquid hydrophobic additive is used; examples of suitable liquid hydrophobic additives are disclosed herein.

[0141] The substrate on which the film or coating can be produced can be, for example, any of those disclosed herein. In some embodiments, the substrate is or includes, for example, a cellulose substrate, glass, leather, metal, a non-cellulosic polymer or fibrous material, masonry, drywall, plaster, wood, a building surface, or a food product (e.g., a fruit or vegetable). Examples of non-cellulosic polymers herein include rubber (e.g., natural rubber) or other diene-based elastomers, polyamides, polyolefins, polylactic acid, polyethylene terephthalate (PET), poly(trimethylene terephthalate) (PTT), aramid, polyethylene sulfide (PES), polyphenylene sulfide (PPS), polyimide (PI), polyethyleneimine (PEI), polyethylene naphthalate (PEN), polysulfone (PS), polyether ether ketone (PEEK), polyethylene, polypropylene, poly(cyclic olefin), poly(cyclohexylene dimethylene terephthalate), and poly(trimethylene furan dicarboxylate) (PTF). In some embodiments, the cellulose substrate comprises about or at least about 80%, 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% by weight of cellulose (typically in the form of cellulose fibers). Other components of the cellulose substrate may optionally include hemicellulose and / or lignin. The cellulose substrate is typically porous. The substrate in some embodiments may be a woven or nonwoven material (e.g., a woven or nonwoven fabric).

[0142] In some embodiments, the film or coating can be a food casing, for example, for meat-based foods (e.g., meat products, such as ground meat products, sausages, or processed meat products) or plant-based foods (e.g., meat substitutes, tofu-containing foods, or bean-containing foods).

[0143] The coating in some embodiments may be a seed coating or a fertilizer coating. Such coatings may have, for example, any of the film / coating characteristics (e.g., thickness, insoluble alpha-glucan content, additives) described herein. As with any solid composition / product of the present disclosure, the seed coating or fertilizer coating in some alternative embodiments does not include the additives described herein, such additives being present in the dope solution used to produce the seed coating or fertilizer coating. The seed coatings herein may be appropriately adapted for manufacture and / or use as disclosed in, for example, US Patent Application Publication No. 2018 / 0325104, US Patent Application Publication No. 2012 / 0220454, or US Patent Application Publication No. 2012 / 0065060, each of which is incorporated herein by reference. The fertilizer coatings herein may be accordingly adapted for manufacture and / or use as disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0229763, U.S. Patent Application Publication No. 2003 / 0033843, or U.S. Patent Application Publication No. 2009 / 0229330, each of which is incorporated herein by reference.

[0144] In some embodiments of the methods of producing a film or coat, or in embodiments of producing any other hybrid solid composition herein (e.g., fibers, extrudates, fibrids, powders, or composites), the film or coating (or other hybrid solid composition) can be heated to a temperature of at least about 45° C. (or a temperature that melts the additive). The additive in such embodiments can be, for example, hydrophobic and / or solid at 20-25° C. In some embodiments, heating can be to about, or at least about, 45, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 75, 80, 85, 90, 95, 100, 45-70, 45-65, 50-70, or 50-65° C., or to about, or at least about, the melting point temperature of a different solid hydrophobic additive herein. Typically, the heating temperature is maintained for a suitable time (e.g., ≧15, 30, 45, 60, 120, 240, or 360 seconds) to allow the additives to melt (i.e., melting occurs in situ in the composition) in the film / coating or other hybrid solid composition. Such heating and in situ melting of the additives may, in some embodiments, serve to heat seal the film / coating or other hybrid solid composition herein.

[0145] Some embodiments of producing a solid composition may further include providing a powder (or other particulate form, such as particles). For example, the solid composition may be comminuted or otherwise ground into a powder, typically after drying.

[0146] Some aspects of the present disclosure relate to compositions / products including solid compositions comprising at least alpha-glucan and / or derivatives thereof, where (i) the alpha-glucan and / or derivatives thereof are crosslinked, and / or (ii) the composition further comprises an additive (e.g., water-insoluble or water-soluble) that is not chemically bonded to the alpha-glucan or derivatives thereof, where at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, and the weight average degree of polymerization of the alpha-glucan is at least 15. Examples of solid compositions (hybrid solid compositions) herein include fibers (e.g., filaments), fibrids (hybrid fibrids), extrusions, composites, powders (dry powders), or films / coatings. The solid compositions may be produced, for example, as disclosed herein, and / or may have any of the features herein of one or more components used to produce the solid compositions. The solid compositions herein are typically not produced in a manner that does not involve the use of the caustic solutions herein; for example, the solid compositions herein are typically not produced by a method that involves dispersing an insoluble alpha-glucan or an insoluble derivative thereof in a non-caustic aqueous medium followed by shaping and water removal (drying) (without processing the alpha-glucan or derivative thereof in a caustic solution).

[0147] A solid composition / product of the present disclosure may, for example, comprise at least about 0.5 wt% of at least one additive herein and up to about 99.5 wt% of at least one water-insoluble alpha-glucan (or a water-insoluble derivative thereof, different from the additive, if present). In some embodiments, the solid composition / product comprises (i) about, or at least about 0.01, 0.025, 0.05, 0.1, 0.25, 0.5, 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, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 , 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89 , 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 0.01~50, 0.01~40, 0.01~30, 0.01~20, 0.01~10, 0.01~5, 0.1~50, 0.1~40, 0.1~30, 0.1~20, 0.1~10, 0.1~5, 0.5~50, 0.5~40, 0.5~30, 0.5~20, 0.5~10, 0.5-5, 1-50, 1-40, 1-30, 1-20, 1-10, 1-5, 2.5-50, 2.5-40, 02.5-30, 2.5-20, 2.5-10, 5-50, 5-40, 5-30, 5-20, or 5-10 wt % of at least one additive, and (ii) about, or up to about 99.99, 99.975, 99.95, 99.9, 99.75, 99.5, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 5 0, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 50~99. 99, 60~99.99, 70~99.99, 80~99.99, 90~99.99, 95~99.99, 50~99.9, 60~99.9, 70~99.9, 80~99.9, 90~99.9, 95~99.9, 50~99.5, 60~99.5, 70~99.5, 80~99.5, 90~99.5, 95~99.5, 50~99, 60-99, 70-99, 80-99, 90-99, 95-99, 50-97.5, 60-97.5, 70-97.5, 80-97.5, 90-97.5, 95-97.5, 50-95, 60-95, 70-95, 80-95, or 90-95 wt% of at least one water-insoluble alpha-glucan (or a water-insoluble derivative thereof).

[0148] The solid composition / product is, in some embodiments, biodegradable. Such biodegradability can be, for example, about, at least about, or up to about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 100%, 150%, 105%, 150%, 15 ... %, 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%.

[0149] The solid compositions / products herein are typically non-porous (e.g., pores cannot be detected at the micrometer or nanometer scale, either on the product surface or in cross-sectional analysis). However, in some embodiments, the solid compositions / products may be porous (e.g., contain discontinuous and / or continuous pores). The solid porous compositions / products may be, for example, foams, aerogels, or sponges, and / or may be nanoporous (e.g., mesoporous), microporous, or macroporous. Pores may be provided, for example, by introducing a gas (e.g., air, nitrogen, carbon dioxide) into the caustic solution during the forming step (b) and then performing step (c) by solidification / neutralization, etc. Furthermore, in some embodiments, pores may be provided, for example, by introducing a gas (e.g., carbon dioxide) into the caustic solution when performing step (c), including neutralization; in this sense, the forming step (b) may extend into step (c), insofar as pore formation may, in some cases, be considered as part of the shape forming process. Gas formation during neutralization in step (c) herein can be achieved by including an additive that reacts to form a product containing a gas (e.g., carbon dioxide) when the environment is neutralized with an acid or the like (e.g., during dope neutralization). An example of such an additive is a carbonate salt (e.g., calcium carbonate) herein; such an additive can be present, for example, in the dope solution at about 0.1-10 wt% (e.g., any wt% within this range as disclosed herein). Pores such as sponge pores can be provided in some embodiments by including one or more water-soluble salts in the caustic solution (provided in step [a]) and dissolving the salts from the solid composition with water or an aqueous solution after step (c).

[0150] A composition / product of the present disclosure comprising at least one solid composition herein can be, for example, an aqueous composition / product (e.g., a dispersion, such as a colloidal dispersion, a mixture) or a dry composition / product. In some embodiments, the compositions / products herein have a concentration of about 0.001, 0.0025, 0.005, 0.0075, 0.01, 0.025, 0.05, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 1.2, 1.25, 1.4, 1.5, 1.6, 1.75, 1.8, 2.0, 2.25, 2.5, 3.0, 3.5, 4.0, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32 , 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 wt% or w / v, or at least about or less than about the solid compositions herein. The composition / product may, for example, include a range between any two of these wt% or w / v% values. Any of these concentration values ​​may be expressed in terms of their respective parts per million (ppm) values, if necessary. The liquid component (liquid medium, aqueous medium) of the aqueous composition / product may, for example, be water or other non-caustic aqueous medium. The solvent of the non-caustic aqueous medium is typically water or may include, for example, about or at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 98, or 99 wt% water.

[0151] The temperature of the compositions herein, such as the aqueous medium in which the solid composition may be included, may be, for example, about, at least about, or up to about 0, 1, 5, 10, 15, 20, 25, 30, 35, 37, 40, 42, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 10-30, 10-25, 15-30, 15-25, 20-40, 20-35, 20-30, 25-40, 25-50, 25-60, 25-70, 25-80, 25-90, 25-100, 25-110, 25-120, 25-130, 25-140, 25-150, 25-160, 25-170, 25-180, 25-190, 25-260, 25-270, 25-30, 25-30, 25-40, 25-5 ... It may be 0 to 25, 25 to 30, 30 to 50, 30 to 45, 30 to 40, 30 to 35, 35 to 40, 35 to 50, 40 to 45, 50 to 60, 5 to 50, 40 to 130, 40 to 125, 40 to 120, 70 to 130, 70 to 125, 70 to 120, 80 to 130, 80 to 125, 80 to 120, 60 to 100, 60 to 90, 70 to 100, 70 to 90, 75 to 100, 75 to 90, 75 to 85, or 1 to 130°C.

[0152] The pH of an aqueous medium in which the solid compositions herein may be included can be, for example, 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.

[0153] The time period for which the solid compositions herein may reside in an aqueous medium may be, for example, about, or at least about 0.5, 1, 5, 10, 30, 60, 90, 120, 150, 180, 210, 240, 300, 360, 420, 480, 540, 600, 660, or 720 minutes, 0.5, 1, 2, 4, 6, 8, 10, 20, 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, or 360 days, or 1, 2, or 3 years.

[0154] The aqueous composition herein may, for example, have a viscosity of 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, 25-300, 50-300, 1-2 The viscosity may be at least about, or less than about, 50, 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 (cp). The viscosity may be measured by the aqueous composition herein at any temperature, for example, from about 3° C. to about 80° C. (e.g., 4-30° C., 15-30° C., 15-25° C.). The viscosity is typically measured at atmospheric pressure (about 760 Torr) or a pressure that is ±10% thereof. The viscosity may be measured, for example, using a viscometer or rheometer, and may be, for example, about 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 (1 / s) shear rate (rotational shear rate).

[0155] The solid compositions herein may have a positive or negative surface charge in some embodiments; in some embodiments, there is no surface charge (or very little, e.g., less than ±0.02 or ±0.015 mV) (i.e., neutral charge). In this specification, "±" refers to positive or negative. Typically, the cationic or anionic surface charge is due to the charge (or average charge) of one or more charged additives contained in the solid composition. The surface charge can be measured in terms of zeta potential, for example, by the solid composition in water (e.g., as a dispersion) and / or by the solid composition in particulate form (e.g., fibrids, powder). The zeta potential of the solid composition in some embodiments may be about ±5 mV, ±10 mV, ±15 mV, ±20 mV, ±25 mV, ±30 mV, ±35 mV, ±40 mV, ±45 mV, or ±50 mV, or about more than these. For simplicity, it should be understood that, for example, a zeta potential "greater than" ±5 mV excludes zeta potentials ranging from -5 mV to +5 mV. In some embodiments, the zeta potential is about +20 to +40 mV, +25 to +40 mV, +30 to +40 mV, +20 to +45 mV, +25 to +45 mV, +30 to +45 mV, +20 to +50 mV, +25 to +50 mV, or +30 to +50 mV. The foregoing zeta potential values ​​may, in some embodiments, be associated with aqueous compositions having a pH of about 6.5 to 7.5, 6 to 8, 5 to 9, or 4 to 9.

[0156] In some embodiments herein, the solid composition is contained in a non-caustic aqueous medium (e.g., water), and the additives of the solid composition are water-soluble under non-caustic conditions. About, or at least about, 80, 85, 90, 95, 96, 97, 98, 99, 100, 80-100, 80-99, 80-97, 90-100, 90-99, 90-97, 95-100, 95-99, or 95-97 wt% of the water-soluble additives can be contained in the solid composition, for example (remaining contained in the solid composition and not dissolved in the aqueous medium). This embodiment is notwithstanding the presence of water that would otherwise dissolve the soluble additives. Thus, in some embodiments, the aqueous medium may comprise about, or less than about, 20, 15, 10, 5, 4, 3, 2, 1, 0, 0-20, 1-20, 3-20, 0-10, 1-10, 3-10, 0-5, 1-5, or 3-5 wt % of the water-soluble additive that was initially / originally entirely contained in the solid composition (prior to placing the solid composition in the aqueous medium).

[0157] Thus, some aspects of the present disclosure relate to methods of handling the solid compositions herein (e.g., fibrids, fibers, extrudates, composites, powders, or hybrid solid compositions such as films / coatings herein). Such methods may include: (a) providing a solid composition herein; and (b) contacting (or subjecting / treating / washing under non-caustic aqueous conditions) the solid composition with a non-caustic aqueous liquid (wherein the contacting does not remove any additives from the solid composition or the contacting removes less than 20 wt% of the additives from the solid composition). The non-caustic aqueous liquid may be any of those disclosed herein (e.g., water), may have any of the relevant characteristics (e.g., temperature, non-caustic pH), and / or may be contacted for a suitable period of time (e.g., as disclosed herein). The volume of the liquid used in the handling methods herein may be, for example, about or at least about 0.25, 0.5, 1.0, 2, 3, 4, 5, 6, 7, 9, or 10 times the volume of the solid composition. The contacting may optionally be performed 2, 3, 4 or more times (e.g., repeatedly in washing, etc.) and / or may include some form of agitation (e.g., mixing, slurrying). The handling methods of the present disclosure may optionally further include separating (e.g., via filtration or decanting) all or a majority (e.g., at least about 50, 60, 70, 80, 90, 95, 96, 97, 98, 99, or 99.5 wt%) of the non-caustic aqueous liquid from the solid composition, where the non-caustic aqueous liquid (which remains present after separation) does not contain any of the additives (e.g., additives that are not dissolved in the liquid) or contains about 20, 15, 10, 5, 4, 3, 2, 1, 0, 0-20, 1-20, 3-20, 0-10, 1-10, 3-10, 0-5, 1-5, or 3-5 wt%, or less, of the additives that were in the solid composition prior to the contacting step. For example, a separation step may be performed after each contacting step. The aforementioned concentration values ​​may characterize the liquid used in any contacting step (e.g., the first contacting step and, if performed, the second or additional contacting steps). One or more additives in some embodiments of the handling method (e.g., any such additives disclosed herein, such as charging additives) may be water soluble under non-caustic conditions.The charged additive may be, for example, a charged polysaccharide or a charged polysaccharide derivative as described herein.

[0158] A solid composition herein may typically be considered non-aqueous (e.g., dry composition) if it is not contained in an aqueous medium. Examples of such embodiments include powders, granules, microcapsules, flakes, or any other form of particulate matter. Other examples include larger compositions such as pellets, bars, kernels, beads, tablets, sticks, or other aggregates. A non-aqueous or dry composition typically contains about 5, 4, 3, 2, 1.5, 1.0, 0.5, 0.25, 0.10, 0.05, or 0.01 wt% or less of water therein.

[0159] The solid composition may, in some embodiments, be a fiber (e.g., a filament). The product / composition containing the fiber may be a nonwoven product, a woven product (textile), or any other fiber-containing product. Textiles herein may be nonwoven or woven.

[0160] Materials / articles / products containing one or more textile fabrics herein include, for example, clothing (e.g., athletic / fitness / sports clothing), curtains, shower curtains, drapes, upholstery, carpets, bed linens, bath linens, towels, tablecloths, sleeping bags, tents, car interiors, laundry bins, and the like.

[0161] The nonwoven products (e.g., nonwoven fabrics, nonwoven webs) herein can be, for example, airlaid, drylaid, wetlaid, carded, electrospun, spunlaced, or spunbond (direct spun, direct spun). In some embodiments, the nonwoven products are abrasive or scouring sheets, agricultural coverings, agricultural seed strips, garment linings, automobile headliners or covers, aprons, cheese wraps, civil engineering textiles, coffee filters, makeup removers or applicators, detergent pouches / sachets, textile softener sheets, envelopes, face masks, filters, garment bags, thermally or electrically conductive textiles, household care wipes (e.g., for floor care, hard surface cleaning, pet care, etc.), house wraps, hygiene products (e.g., sanitary pads / napkins, etc.), and the like. , underpad), insulation, a label, a laundry aid, a medical or personal injury care product (e.g., a band-aid, cast padding or cover, a dressing, a pack, a sterile wrap, a sterile packaging, a surgical drape, a surgical gown, a cotton swab), a mop, a napkin or paper towel, paper, tissue paper, a personal or baby wipe, a reusable bag, a roofing undercover, a table linen, a tag, a tea or coffee bag, a cover, a vacuum cleaning bag, or wallpaper. Examples of nonwoven products and / or methods of making nonwoven products herein can be those disclosed in U.S. Patent Application Publication No. 2020 / 0370216, U.S. Patent Application Publication No. 2018 / 0282918, U.S. Patent Application Publication No. 2017 / 0167063, U.S. Patent Application Publication No. 2018 / 0320291, U.S. Patent Application Publication No. 2018 / 0340270, U.S. Patent Application Publication No. 2016 / 0053406, or U.S. Patent Application Publication No. 2010 / 0291213, each of which is incorporated herein by reference.

[0162] The fiber-containing product herein may be a paper / packaging composition or a cellulose fiber-containing composition. Examples of such compositions include paper (e.g., writing paper, office paper, copy paper, craft paper), cardboard, paperboard, corrugated cardboard, tissue paper, napkin / paper towel, wipe, or nonwoven fabric. The formulations and / or ingredients (in addition to those herein) of the paper / packaging composition or cellulose fiber-containing composition herein, as well as the form of these compositions, may be, for example, those described in US Patent Application Publication No. 2018 / 0119357, US Patent Application Publication No. 2019 / 0330802, US Patent Application Publication No. 2020 / 0062929, US Patent Application Publication No. 2020 / 0308371, or US Patent Application Publication No. 2020 / 0370216 (each of which is incorporated herein by reference).

[0163] In some embodiments, the nonwoven or woven products (fabrics) weigh about, or at most about, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, 70, 80, 90, 100, 25-50, 25-45, 25-40, 25-35, 25-33, 25-32, 28-50, 28-45, 28-40, 28-35, 28-33, 28-32, 28-31, 29-32, 29-31, 50-70, 50-65, 55-70, or 55-65 gsm (grams per square meter of fabric).

[0164] The solid composition may, in some embodiments, be an extruded product. Examples of extruded products include fibers (filaments), tubular products (e.g., tubes, pipes, straws, such as drinking straws), bags, sheets, films, gaskets, and rods.

[0165] In some embodiments, the compositions herein (e.g., films, coatings, fibers [e.g., filaments], fibrids, extrudates, composites) have a tensile strength (ultimate tensile strength) of about, or at least about, 35, 40, 45, 50, 55, 60, 65, 35-65, 40-65, 45-65, 35-60, 40-60, 45-60, 35-55, 40-55, or 45-55 MPa (megapascals). Tensile strength can be measured, for example, according to the Examples below (e.g., each condition / parameter performed within 5%, 10%, or 15% of the relevant condition / parameter disclosed in the Examples) or as disclosed in DIN EN ISO 527-3 (herein incorporated by reference). In some embodiments, the tensile strength of a composition herein that includes one or more additives is about, or at least about, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, or 150% greater than the tensile strength of an otherwise identical composition lacking one or more additives.

[0166] In some embodiments, the compositions herein (e.g., films, coatings, fibers [e.g., filaments], fibrids, extrudates, composites) have a percent elongation to break (% elongation) of about, or at least about, 40%, 45%, 50%, 55%, 60%, 65%, 40-65%, 45-65%, 50-65%, 40-60%, 45-60%, or 50-60%. Percent elongation can be measured, for example, according to the Examples below (e.g., each condition / parameter performed within 5%, 10%, or 15% of the relevant condition / parameter disclosed in the Examples) or as disclosed in DIN EN ISO 527-3 (herein incorporated by reference). In some embodiments, the percent elongation of the compositions herein that include one or more additives is about, or at least about, 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% higher than the percent elongation of an otherwise identical composition lacking one or more additives.

[0167] Films or coatings / layers of the compositions herein may, for example, have a thickness of about 1, 2.5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 85, 90, 95, 100, 105, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 10-30, 10-25, 10-20, 1 The thickness may be at least about, or less than 5-30, 15-25, 15-20, 30-70, 40-60, 70-130, 70-120, 70-110, 70-100, 80-130, 80-120, 80-110, 80-100, 90-130, 90-120, 90-110, or 90-100 microns (micrometers, μm). In some embodiments, such thickness is uniform, which may be characterized by having a continuous region that is (i) at least 20%, 30%, 40%, or 50% of the total coating area, and (ii) has a standard deviation in thickness that is less than about 0.5, 1, 1.5, or 2 microns.

[0168] In some embodiments, the substrate is coated with one layer (monolayer) of the coating composition herein. However, in some embodiments, there may be multiple (e.g., two, three, or more) coats of the coating composition, and such additional coats may be the same or different from the first coat. The coating herein may be, for example, one or more coatings contained in a laminate material.

[0169] The films / coatings herein may exhibit various degrees of transparency as desired. For example, the films / coatings may be highly transparent (e.g., high light transmission and / or low haze). Light transmission as used herein may refer to, for example, a film / coating that provides at least about 10-99% light transmission, or at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, or 99% light transmission, and / or less than 30%, 25%, 20%, 15%, 10%, 5%, 2.5%, 2%, or 1% haze. High light transmission may, in some cases, refer to a film / coating that provides at least about 90% light transmission and / or less than 10% haze. The light transmittance of the films / coatings herein can be measured, for example, according to the ASTM D1746 test (2009, Standard Test Method for Transparency of Plastic Sheeting, ASTM International, West Conshohocken, PA), which is incorporated herein by reference. The haze of the films / coatings herein can be measured, for example, according to the ASTM D1003-13 test (2013, Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics, ASTM International, West Conshohocken, PA), which is incorporated herein by reference.

[0170] The films / coatings herein may optionally further comprise a plasticizer, such as glycerol, propylene glycol, ethylene glycol, and / or polyethylene glycol. In some embodiments, other film / coating components (in addition to at least the insoluble alpha-glucan and additives) may be those disclosed in U.S. Patent Application Publication No. 2011 / 0151224, U.S. Patent Application Publication No. 2015 / 0191550, or U.S. Patent Application Publication No. 2017 / 0208823, or U.S. Patent No. 9,688,035, or U.S. Patent No. 3,345,200, all of which are incorporated herein by reference.

[0171] The film or other sheet-like product of the present disclosure can be, for example, in the form of a membrane. The membrane in some embodiments can be used in separation or purification processes, such as dialysis, biological component separation / purification, or reverse osmosis (e.g., dialysis membrane, protein separation membrane, reverse osmosis membrane). As with any solid composition / product of the present disclosure, the membrane in some alternative embodiments does not include additives therein, such additives being present in the dope solution used to produce the membrane.

[0172] The film, sheet, or sheet-like product of the present disclosure may be for application (e.g., placing on, pressing onto) skin (e.g., human skin). Examples of skin suitable for this purpose include facial skin (e.g., entire face, nose, lips, eyelids, eyebrows, cheeks, chin, forehead) (face masks are an example of such products), ear skin, and body skin (e.g., arms, legs, torso, hands, feet, cuticles, neck, scalp (typically when shaved)). Such products may have, for example, any of the film / coating characteristics (e.g., thickness, insoluble alpha-glucan content, water content, transparency) described herein. As with any solid composition / product of the present disclosure, the film product for application to skin in some alternative embodiments does not include the additives described herein, which were present in the dope solution used to make the film product. Regardless of whether the film product for application to the skin contains a doped additive, the film product may be treated / modified (e.g., impregnated) after its formation to contain one or more additives / agents, typically such one or more additives / agents providing a therapeutic, cosmetic, or any other benefit to the skin targeted by the film product. Examples of such one or more additives / agents (skin treatment agents) include enzymes, vitamins (e.g., vitamin C), minerals, drugs, keratolytic agents (e.g., salicylic acid, azelaic acid), anti-acne agents (e.g., salicylic acid, benzoyl peroxide), skin lightening agents, anti-wrinkle / wrinkle agents, antioxidants, moisturizers, oil-reducing (anti-sebum) agents, hyaluronic acid, glycolic acid, ceramides, charcoal, clay, activated charcoal, and curcumin (and / or any suitable additives disclosed herein). One or more of these or other skin treatment agents may optionally be doped additives (in addition to or instead of additives added to the film product after film formation). The film products for application to the skin herein may be suitably adapted for manufacture and / or use as disclosed, for example, in U.S. Pat. No. 8,425,477, U.S. Pat. No. 5,538,732, or U.S. Pat. No. 10,448,727, each of which is incorporated herein by reference.

[0173] In some embodiments, one side of the film / coating is hydrophilic and the other side of the film / coating is hydrophobic (e.g., a property of a film / coating having at least one additive herein that is an oil). Such films / coatings may in some cases be characterized as having a "surface polarity" with respect to the attraction / dis-attraction of water. The hydrophobicity or hydrophilicity of a film or coating surface can be determined, for example, by measuring the contact angle of water in direct contact with the surface. For example, a droplet of water in contact with a hydrophobic surface may exhibit a contact angle that is about, or at least about, 85°, 90°, 95°, 100°, 105°, 85°-105°, 90°-105°, 95°-105°, 85°-100°, 90°-100°, 95°-100°, 85°-95°, or 90°-95°, and / or a droplet of water in contact with a hydrophilic surface may exhibit a contact angle that is about, or less than, 80°, 75°, 70°, 65°, 60°, 55°, 50°, 45°, 45°-80°, 45°-75°, or 45°-70°. The film / coating may, for example, be more hydrophilic (or hydrophobic) on one side than the other side (e.g., >10%, 20%, 30%, or 40% more).

[0174] Some embodiments relate to coatings on substrates herein, where the side of the coating opposite the side of the coating that contacts the substrate is hydrophobic (i.e., the exterior or outer side of the coating is hydrophobic), while the side that contacts the substrate (i.e., the inner side of the coating) is hydrophilic. In such embodiments, the coating typically adheres better (e.g., at least 10%, 20%, 30%, 40%, or 50% better) to substrates having hydrophilic surfaces compared to neutral or hydrophobic surfaces and / or compared to coatings herein that do not have surface polarity. In such embodiments, the coating typically repels water better (e.g., at least 10%, 20%, 30%, 40%, or 50% better) compared to coatings herein that do not have surface polarity.

[0175] Substrates that may be coated with the compositions herein may include or be, for example, cellulosic substrates, glass, leather, metals, non-cellulosic polymers or fibrous materials, masonry, drywall, plaster, wood, architectural surfaces, or food products (e.g., fruits or vegetables). Examples of non-cellulosic polymers herein include rubber (e.g., natural rubber) or other diene-based elastomers, polyamides, polyolefins, polylactic acid, polyethylene terephthalate (PET), poly(trimethylene terephthalate) (PTT), aramids, polyethylene sulfide (PES), polyphenylene sulfide (PPS), polyimides (PI), polyethyleneimine (PEI), polyethylene naphthalate (PEN), polysulfone (PS), polyether ether ketone (PEEK), polyethylene, polypropylene, poly(cyclic olefins), poly(cyclohexylene dimethylene terephthalate), and poly(trimethylene furan dicarboxylate) (PTF). In some embodiments, the cellulose substrate comprises about or at least about 80%, 82.5%, 85%, 87.5%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% by weight of cellulose (typically in the form of cellulose fibers). Other components of the cellulose substrate may optionally include hemicellulose and / or lignin. The cellulose substrate is typically porous. The substrate in some embodiments may be a woven or nonwoven material (e.g., a woven or nonwoven fabric).

[0176] The cellulose substrate in some embodiments may be a paper product, a woven product, or a nonwoven product. Examples of paper products include paper, cardboard, paperboard, corrugated board, box board, and molded or compressed paper fibers. Another example of a paper product is a paper straw (drinking straw). The above are also examples of compositions or products herein that include a cellulose substrate. The compositions or products herein that include a cellulose substrate may be packaging or containers in some embodiments, typically including one or more of the paper products described above. Examples of packaging and / or containers herein include boxes (e.g., cardboard boxes, cardboard boxes, corrugated boxes, rigid boxes), chipboards, cartons (e.g., beverage cartons, folding cartons), bags, cups, plates, wraps / wrappers, tubes / tube systems, cones, fries holders or similar holders, trays, tissue paper, parchment paper, and kraft paper. Paper products may have one side covered (e.g., foil sealed) with a foil such as aluminum foil or plastic, but the paper products herein typically do not include such a covering. The package or container may be closed (eg blocked) or open (eg unsealed).

[0177] The coating compositions applied to the substrates herein can, for example, cover all of, or at least about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 99.5% of the area of ​​one or both sides of the substrate. For compositions or products having an interior and exterior surface (e.g., boxes, cartons, fryer holders), the coating can be on the interior surface, the exterior surface, or both surfaces.

[0178] In some embodiments, the compositions herein, such as packaging or containers, hold a product, and in some cases, the coating (typically on the interior / inner surface of the packaging / container) is in contact with the product. Such products can be, for example, ingestible products (e.g., food), pharmaceuticals, personal care products, home care products, or industrial products. Examples of these types of products are described in US Patent Application Publication No. 2018 / 0022834, US Patent Application Publication No. 2018 / 0237816, US Patent Application Publication No. 2018 / 0230241, US Patent Application Publication No. 2018 / 0079832, US Patent Application Publication No. 2016 / 0311935, US Patent Application Publication No. 2016 / 0304629, US Patent Application Publication No. 2015 / 0232785. No. 2015 / 0368594, U.S. Patent Application Publication No. 2015 / 0368595, U.S. Patent Application Publication No. 2016 / 0122445, U.S. Patent Application Publication No. 2019 / 0202942, or U.S. Patent Application Publication No. 2019 / 0309096, or WO 2016 / 133734, all of which are incorporated herein by reference. In some embodiments, the packaging or container holds, and the coating is optionally in contact with, at least one component of an ingestible product (e.g., a food product), pharmaceutical product, personal care product, home care product, or industrial product disclosed in any of the aforementioned publications and / or of the present disclosure.

[0179] In some embodiments, the product to be held in the package / container contains oil, grease, and / or water on its surface, and the product is in contact with the inner surface of the package / container (in some cases, the product is in contact with the layer of the coating composition if the layer of the coating composition happens to be located on the inner surface of the package / container).Typically, at least a part (e.g., at least about 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 wt%) or all of the oil, grease, and / or water of the product is contained inside the package or container.In other words, most or all of the oil, grease, and / or water cannot pass through the package or container and be on the outer / external surface of the package or container.

[0180] The compositions herein can be at and / or in an environment / system at a temperature of, for example, about 1-50, 1-45, 1-40, 1-35, 1-30, 1-25, 1-20, 5-30, 10-30, 15-30, 20-30, 5-25, 10-25, 15-25, or 20-25° C. (or any other temperature disclosed herein). The compositions herein may be in an environment, for example, where the relative humidity level is about or at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 20%-100%, 30%-100%, 40%-100%, 50%-100%, 60%-100%, 70%-100%, 80%-100%, 20%-90%, 30%-90%, 40%-90%, 50%-90%, 60%-90%, 70%-90%, or 80%-90%. An illustrative example of a composition that may be in any of the foregoing temperature and / or relative humidity conditions is a package or container herein that holds a product.

[0181] Typically, a product herein (e.g., a pharmaceutical product, a personal care product, a home care product, an industrial product, or an ingestible product such as a food product) can be protected from exposure to water, water vapor, and / or oxygen originating from outside the package / container if it is stored in a closed or sealed package / container herein (e.g., for 1, 2, 3, 6, 9, 12, 18, 24, 30, or 36 months). Such storage, for example, prevents the product from losing freshness and / or spoilage, or any other form of spoilage or loss of freshness or functionality.

[0182] Compositions of the present disclosure, e.g., fibers [e.g., filaments], fibrids, extrudates, composites, powders, or hybrid solid compositions such as films / coatings herein, can be prepared by, for example, any of the methods described in U.S. Patent Application Publication No. 2018 / 0022834, U.S. Patent Application Publication No. 2018 / 0237816, U.S. Patent Application Publication No. 2018 / 0230241, U.S. Patent Application Publication No. 2018 / 0079832, U.S. Patent Application Publication No. 2016 / 0311935, U.S. Patent Application Publication No. 2016 / 0304629, U.S. Patent Application Publication No. 2015 / 0232785, U.S. Patent Application Publication No. 2015 / 0232786, U.S. Patent Application Publication No. 2015 / 0232787, U.S. Patent Application Publication No. 2015 / 0232789, U.S. Patent Application Publication No. 2015 / 0232790, U.S. Patent Application Publication No. 2015 / 0232792, U.S. Patent Application Publication No. 2015 / 0232794, U.S. Patent Application Publication No. 2015 / 0232796, U.S. Patent Application Publication No. 2015 / 0232798 ... The composition may be in the form of or may be included in a household care product, personal care product, industrial product, ingestible product (e.g., food), medical product, or pharmaceutical product as described in any of US Patent Publications 0368594, 2015 / 0368595, 2016 / 0122445, 2019 / 0202942, 2019 / 0309096, or 2021 / 0130504, or WO 2016 / 133734 (all of which are incorporated herein by reference). In some embodiments, the composition may comprise at least one component of a household care product, personal care product, industrial product, pharmaceutical product, medical product, or ingestible product (e.g., food) disclosed in any of the aforementioned publications and / or of the present disclosure.

[0183] In some embodiments, the compositions are believed to be useful for providing one or more of the following physical properties to personal care products, pharmaceutical products, household products, industrial products, or ingestible products (e.g., foods): thickening, freeze-thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsifying properties, binding, suspending, dispersing, gelling properties, reduced mineral hardness.

[0184] In some alternative embodiments, the solid composition / product may be any of those disclosed herein further comprising no additives, such additives being present in the dope solution used to generate the solid composition / product (i.e., such solid composition / product is not a "hybrid" as disclosed elsewhere herein).

[0185] Non-limiting examples of the compositions and methods disclosed herein include: 1. A solution (e.g., a caustic solution / dope solution) comprising at least (a) a caustic solvent, (b) an alpha-glucan and / or a derivative thereof (or an alpha-glucan that has been cross-linked prior to entering the caustic solvent) (typically, the alpha-glucan or a derivative thereof [or a pre-cross-linked alpha-glucan] is water-insoluble under non-caustic conditions), and (c) an additive, wherein the additive is (i) a cross-linking agent, and / or (ii) optionally an additive that does not chemically react with the alpha-glucan or a derivative thereof (optionally, no additive if an alpha-glucan that has been cross-linked prior to entering the caustic solvent is used), wherein at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, the weight average degree of polymerization of the alpha-glucan is at least 15, the alpha-glucan or a derivative thereof is dissolved in the caustic solvent, and the additive is either dissolved or not dissolved in the caustic solvent. 2. The solution of embodiment 1, wherein at least about 90% of the glycosidic bonds in the alpha-glucan are alpha-1,3 glycosidic bonds. 3. The solution of embodiment 1 or 2 comprising alpha-glucan (i.e., underivatized alpha-glucan). 4. The solution of embodiment 1, 2, or 3, comprising about 5 wt% to about 20 wt% (e.g., 7.5 wt% to 15 wt%) of alpha-glucan and / or derivatives thereof. 5. The solution of embodiment 1, 2, 3, or 4, wherein the additive is a crosslinking agent. 6. The solution of embodiment 1, 2, 3 or 4, wherein the additive is an additive that does not react with the alpha-glucan or its derivatives. 7. The solution of embodiment 1, 2, 3, 4, 5, or 6, wherein the additive is water soluble under non-caustic conditions. 8. The solution of embodiment 1, 2, 3, 4, 5, 6, or 7, wherein the additive is a polysaccharide derivative. 9. The solution of embodiment 1, 2, 3, 4, 5, 6, 7, or 8, wherein the caustic solvent is an aqueous alkali metal hydroxide solution. 10. The solution of embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the solution is in the form of a doped filament. 11. A method for producing a solution according to any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, comprising: mixing at least alpha-glucan and / or derivatives thereof, and an additive with a caustic solvent, wherein the alpha-glucan and / or derivatives thereof dissolves in the caustic solvent. 12. A method of producing a solid composition comprising: (a) providing a solution according to any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or a solution produced by the method of embodiment 11; (b) forming the solution into a desired form / shape; and (c) removing the caustic solvent from the solution of step (b) to produce a solid composition comprising alpha-glucan or a derivative thereof, and an additive. 13. The method of embodiment 12, wherein the step of removing the solvent comprises: (i) chemically or ionically modifying the caustic solvent (chemically or ionically modifying the solution) so that the alpha-glucan or derivative thereof, and additives, if dissolved in the solvent, are no longer soluble in the caustic solvent; or (ii) blowing air through the solution so that the alpha-glucan or derivative thereof, and additives, if dissolved in the solvent, are no longer soluble in the caustic solvent. 14. The method of embodiment 12 or 13, wherein the solid composition of step (c) is a fiber (e.g., a filament), an extrudate, a fibrid, a composite, a powder, or a film / coating. 15. The method of embodiment 12 or 13, wherein step (b) comprises using an apparatus (e.g., a spinneret) having one or more orifices (e.g., holes, nozzles, or perforations) through which the solution is passed / emitted / ejected / forced, and optionally fibers (e.g., filaments) are produced in step (c). 16. A composition comprising a solid composition produced by the method of embodiment 12, 13, 14, or 15, and optionally the solid composition is a fiber (e.g., a filament), an extrudate, a fibrid, a composite, a powder, or a film / coating. 17. A composition comprising a solid composition comprising at least a water-insoluble alpha-glucan and / or a water-insoluble derivative thereof, wherein (i) the alpha-glucan and / or its derivative is crosslinked, and / or (ii) the composition further comprises an additive that is not chemically bonded to the alpha-glucan or its derivative, wherein at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, and the weight average degree of polymerization of the alpha-glucan is at least 15. 18. The composition of embodiment 17, wherein the solid composition is a fiber (e.g., a filament), a fibrid, an extrudate, a composite, a powder, or a film / coating. 19. The composition of embodiment 17, wherein the solid composition is a fiber (e.g., a filament), and the fiber is included in a nonwoven product or other fiber-containing product herein.

[0186] Non-limiting examples of the compositions and methods disclosed herein include: 1b. A composition comprising a fibrid (hybrid fibrid) (or other hybrid solid composition herein, e.g., a fiber [e.g., filament], extrudate, composite, powder, or film / coating) comprising a water-insoluble alpha-glucan and an additive, wherein (i) at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds and the weight average degree of polymerization of the alpha-glucan is at least 15, and (ii) the additive is not chemically bonded to the alpha-glucan. 2b. The composition of embodiment 1b, wherein at least about 90% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds. 3b. The composition of embodiment 1b or 2b, wherein the weight average degree of polymerization of the alpha-glucan is at least 400. 4b. The composition of embodiment 1b, 2b, or 3b, wherein the additive is water soluble under non-caustic conditions. 5b. The composition of embodiment 1b, 2b, or 3b, wherein the additive is water-insoluble under non-caustic conditions. 6b. The composition of embodiment 1b, 2b, 3b, 4b, or 5b, wherein the fibrids (or other solid composition) comprise at least about 0.5 wt.% of the additive and up to about 99.5 wt.% of the water-insoluble alpha-glucan. 7b. The composition of embodiment 1b, 2b, 3b, 4b, 5b, or 6b, wherein the additive comprises an electrostatic additive. 8b. The composition of embodiment 7b, wherein the electrostatic additive is a cationic additive (or an anionic additive). 9b. The composition of embodiment 8b, wherein the cationic excipient is a cationic polysaccharide derivative (e.g., an ether) (or a cationic underivatized polysaccharide). 10b. The composition of embodiment 9b, wherein the polysaccharide of the cationic polysaccharide derivative is an alpha-glucan, at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, and the weight average degree of polymerization of the alpha-glucan is at least 15. 11b. The composition of embodiment 9b or 10b, wherein the cationic polysaccharide derivative (or the cationic underivatized polysaccharide) is water-soluble (or water-insoluble) under non-caustic conditions. 12b. The composition of embodiment 9b, 10b, or 11b, wherein the cationic polysaccharide derivative comprises ether-linked cationic organic groups. 13b. The composition of embodiment 12b, wherein the ether-linked cationic organic group is a substituted ammonium group. 14b. The composition of embodiment 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, or 13b, wherein the fibrids (or other solid composition) are contained in an aqueous medium (e.g., water or other non-caustic aqueous medium). 15b. The composition of embodiment 14b, wherein the additive is water soluble under non-caustic conditions. 16b. The composition of embodiment 14b or 15b, wherein at least about 80 wt.% of the additive is contained in the fibrids (or other solid composition) (i.e., less than 20 wt.% of the additive is dissolved in the aqueous medium). 17b. A method of treating fibrids (hybrid fibrids) (or other solid compositions herein, e.g., fibers [e.g., filaments], extrudates, composites, powders, or films / coatings) comprising: (a) providing a fiber (or other solid composition herein, e.g., fibers [e.g., filaments], extrudates, composites, powders, or films / coatings) according to embodiment 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, or 13b; and (b) contacting the fiber (or other solid composition) with a non-caustic aqueous liquid (or subjecting / treating under non-caustic aqueous conditions), which does not remove any additive from the fiber (or other solid composition), or which removes less than 20 wt. % of the additive from the fiber (or other solid composition). 18b. The method of embodiment 17b, further comprising separating the non-caustic aqueous liquid from the fibrids (or other solid composition), wherein the non-caustic aqueous liquid does not contain any additives (e.g., additives that do not dissolve in the liquid) or the non-caustic aqueous liquid contains less than 20 wt.% of the additives that were in the fibrids (or other solid composition) prior to contacting step (b). 19b. The method of embodiment 17b or 18b, wherein the additive is water soluble under non-caustic conditions. 20b. The method of embodiment 17b, 18b, or 19b, wherein the additive comprises an electrostatic additive.

[0187] Non-limiting examples of the compositions and methods disclosed herein include: 1c. A film / coating composition (or other hybrid solid composition herein, e.g., fiber [e.g., filament], fibrid, extrudate, composite, or powder) comprising a water-insoluble alpha-glucan and a hydrophobic additive, wherein (i) at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds and the weight average degree of polymerization of the alpha-glucan is at least 15, and (ii) the hydrophobic additive is not chemically bonded to the alpha-glucan. 2c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, wherein at least about 90% of the glycosidic bonds in the alpha-glucan are alpha-1,3 glycosidic bonds. 3c. The film / coating composition (or other hybrid solid composition) of embodiment 1c or 2c, wherein the weight average degree of polymerization of the alpha-glucan is at least 400. 4c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, or 3c, wherein the hydrophobic additive is water-insoluble under caustic and non-caustic conditions. 5c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, or 4c, wherein the hydrophobic additive is capable of forming emulsions in caustic and non-caustic aqueous conditions. 6c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, 4c, or 5c, wherein the hydrophobic additive comprises an oil (e.g., rapeseed oil, canola oil) (or other hydrophobic additive that is a liquid that can be dispersed in caustic aqueous conditions). 7c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, 4c, or 5c, wherein the hydrophobic additive comprises a wax. 8c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, 4c, 5c, 6c, or 7c, comprising about 0.05 wt% to about 50 wt% of a hydrophobic additive, the wt% being based on the weight of the alpha-glucan in the film / coating composition. 9c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, 4c, 5c, 6c, 7c, or 8c, wherein one side of the film / coating is hydrophilic and the other side of the film / coating is hydrophobic (i.e., the film / coating exhibits surface polarity with respect to the attraction / repulsion of water). 10c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, 4c, 5c, 6c, 7c, 8c, or 9c, wherein the film / coating composition is a coating on a substrate and the side of the coating opposite the side that contacts (adjacent) the substrate (the outer coating side) is hydrophobic (and the side that contacts the substrate is hydrophilic). 11c. The film / coating composition (or other hybrid solid composition) of embodiment 1c, 2c, 3c, 4c, 5c, 6c, 7c, 8c, 9c, or 10c, wherein the film / coating composition has: (i) a tensile strength (ultimate tensile strength) of at least about 35 MPa; and / or (ii) a percent elongation (percent elongation at break) of at least about 40%. 12c. A method of producing a film / coating composition (or other hybrid solid composition) according to embodiment 1c, 2c, 3c, 4c, 5c, 6c, 7c, 8c, 9c, 10c, or 11c, comprising: (a) providing a preparation comprising at least (i) a caustic solvent, (ii) the water-insoluble alpha-glucan, and (iii) the hydrophobic additive, wherein the alpha-glucan is soluble in the caustic solvent; (b) contacting the preparation with a substrate (to form the preparation into a film or coating) (or forming the preparation into a desired form / shape, e.g., fibers [e.g., filaments], fibrids, or extrudates); and (c) removing the caustic solvent from the preparation of step (b) to produce a film / coating composition (or other hybrid solid composition, e.g., fibers [e.g., filaments], fibrids, or extrudates) comprising the alpha-glucan and the additive. 13c. The method of embodiment 12c, wherein the preparation is a dispersion and the hydrophobic additive is dispersed in the caustic solvent. 14c. The method of embodiment 12c or 13c, wherein the dispersion is an emulsion (or the preparation is an emulsion) and the hydrophobic additive is dispersed in the caustic solvent as an emulsion (i.e., the hydrophobic additive is a liquid that is immiscible with the caustic solvent). 15c. The method of embodiment 12c, 13c, or 14c, wherein the step of removing the caustic solvent comprises: (i) chemically or ionically modifying the caustic solvent (chemically or ionically modifying the preparation) so that the alpha-glucan is no longer soluble in the caustic solvent, or (ii) blowing air through the preparation so that the alpha-glucan is no longer soluble in the caustic solvent. 16c. The method of embodiment 12c, 13c, 14c, or 15c, wherein the substrate comprises glass. 17c. The method of embodiment 12c, 13c, 14c, or 15c, wherein the substrate is a cellulosic substrate (eg, paper, cardboard, paperboard, corrugated board, or box board). 18c. The method of embodiment 12c, 13c, 14c, 15c, 16c, or 17c, further comprising the step of heating the film / coating composition (or other hybrid solid composition, e.g., fiber [e.g., filament], extrudate, fibrid, powder, or composite) to a temperature of at least about 45° C. (or optionally to a temperature that melts the hydrophobic additive if the hydrophobic additive is a solid at 20-25° C.). 19c. The method of embodiment 12c, 13c, 14c, 15c, 16c, 17c, or 18c, wherein the hydrophobic additive has a melting point of at least about 45° C. 20c. A film / coating (or other hybrid solid composition, e.g., fiber [e.g., filament], extrudate, fibrid, or composite) produced by the method of embodiment 12c, 13c, 14c, 15c, 16c, 17c, 18c, or 19c. EXAMPLES

[0188] The present disclosure will be further illustrated in the following examples. Although these examples show certain aspects of the present specification, it should be understood that they are presented for illustrative purposes only. From the above discussion and these examples, those skilled in the art can confirm the essential features of the disclosed embodiments, and can make various changes and modifications to adapt the disclosed embodiments to various uses and conditions without departing from the spirit and scope of the present invention.

[0189] Materials / methods Representative method for preparation of insoluble alpha-glucan solution (dope) Unless otherwise disclosed, an alpha-glucan dope solution was prepared containing about 7.5-15 wt% alpha-1,3-glucan (DPw about 800, about 100% alpha-1,3 linkages, water insoluble under non-caustic conditions) in water and about 4.2-4.5 wt% NaOH. Generally, the dope solution was prepared by charging the reactor with water and then adding the alpha-1,3-glucan dry powder under stirring. After the glucan powder was visibly uniformly dispersed, the NaOH solution was added and then the reactor contents were stirred for about an additional 30 minutes. The final alpha-1,3-glucan dope solution was clear and colorless. One or more additives can be added before, during, or after the addition of NaOH.

[0190] Example 1 Cross-linked alpha-glucan in the dope solution In this example, various levels of ethylene glycol diglycidyl ether (EGDGE) crosslinker were added to alpha-1,3-glucan doped solutions and their rheological properties were monitored.

[0191] A dope solution with 10 wt% water-insoluble alpha-1,3-glucan, 4.5 wt% NaOH, and 85.5 wt% water was prepared and divided into aliquots. Immediately after preparing the dope solution, 0 wt%, 0.1 wt%, or 1 wt% EGDGE (PolySource, Independence, MO) (based on the weight of alpha-1,3-glucan in the dope) was added to the aliquot of the dope solution and mixed for 30 minutes using an overhead mixer equipped with a propeller impeller (50 rpm). The rheological properties of each aliquot were then measured using a cone-and-plate oscillatory shear rheometer (Malvern, Kinexus). The elastic modulus (G') and viscous modulus (G") were measured by varying the strain from 0.1% to 100% using a vibration frequency of 1 Hz. These measurements were taken immediately (day 0) or after 1 day. Table 1 below provides the G' and G" values ​​measured at 1% strain.

[0192] [Table 1]

[0193] Without the addition of EGDGE (0 wt%) to the alpha-1,3-glucan doped solution, negligible differences in G' and G" from day 0 to day 1 were observed (Table 1). However, with the addition of 0.1 wt% and 1 wt% of EGDGE, there was a notable increase in G' and G" values ​​from day 0 to day 1, respectively, suggesting that EGDGE cross-linking took some time between days 0 and 1 for complete occurrence. For the addition of 1 wt% of EGDGE, an increase in G' and G" was observed even at day 0, respectively, compared to the 0 wt% and 0.1 wt% EGDGE samples, suggesting that cross-linking may occur rapidly at relatively high EGDGE concentrations.

[0194] Example 2 Formation of continuous doped filaments from cross-linked alpha-glucan dope solutions A dope solution was prepared having 7.5 wt% water insoluble alpha-1,3-glucan (based on the weight of alpha-1,3-glucan in the dope) and 4.5 wt% NaOH, and 1 wt% EGDGE. After one day, this dope solution and the corresponding dope solution without the EGDGE crosslinker were separately used in a fiber blower equipped with a meltblown die (Exxon type Meltblown Die, 58 500 micron holes).

[0195] Air drawing of the crosslinked (EGDGE treated) alpha-1,3-glucan dope solution was possible with air flow pressures up to about 100 mbar without breakage of the dope filaments (a continuous dope filament was produced); see FIG. 1A. In contrast, when attempting to air draw an alpha-1,3-dope solution that did not contain a crosslinker, the process was not possible (no uniform dope filaments could be produced) as each attempt resulted in deformation and / or breakage of the air drawn dope; see FIG. 1B. These results were unexpected as the inclusion of a crosslinker would have been expected to make the rheological conditions unsuitable for drawing a continuous dope filament.

[0196] Example 3 Fibers produced using cross-linked alpha-glucan dope solutions Fibers were produced using dope solutions having 7.5 wt% water-insoluble alpha-1,3-glucan and 4.5 wt% NaOH (based on the weight of alpha-1,3-glucan in the dope), and 0.1, 0.5, or 1.0 wt% EGDGE. Each dope solution was prepared and held for 1 day before entering fiber production. For fiber production, a fiber spinning nozzle with 120 60 micron diameter holes was used. An extrusion speed of 13.3 m / min and a spinning speed of 25 m / min were used. An increase in nozzle pressure proportional to the EGDGE content of each dope solution was observed when producing the dope filaments (see Table 2 below). For coagulation of the dope filaments into fibers, a solution containing 80 g / L H2SO4, 220 g / L Na2SO4, and 30 g / L ZnSO4 at 42°C was used. After coagulation, the fibers were washed with water and dried at 70°C.

[0197] Each fiber was tested for tenacity, modulus (E modulus), and elongation. Yarns (120 fiber bundles) of each prepared fiber were used for these tests. Table 2 below shows the results of these analyses.

[0198] [Table 2]

[0199] Example 4 Films produced using cross-linked alpha-glucan dope solutions Alpha-1,3-glucan films were produced using dope solutions containing either 1,4-butanediol diglycidyl ether (BDGE) or polyethylene glycol 2000 diglycidyl ether (PEG2000DGE) as the crosslinker.

[0200] An alpha-1,3-glucan dope solution was prepared containing 15 wt% water-insoluble alpha-1,3-glucan (based on the weight of alpha-1,3-glucan in the dope), 4.9 wt% NaOH, and 80.1 wt% water, followed by the addition of 0 wt%, 0.01 wt%, or 0.05 wt% BDGE, or 0.01 wt% PEG2000DGE. Films were then cast onto glass surfaces using a 100 micron doctor blade. The cast films were coagulated using a 5% H2SO4 / 2.5% Na2SO4 aqueous bath and washed with DI water until neutral. The films were then treated in a 5% glycerol aqueous bath and dried.

[0201] Each of the films produced above was tested for tensile strength and elongation. The alpha-1,3-glucan films produced using the dope solution containing the crosslinker exhibited higher tensile strength and elongation properties, as shown in Table 3 below. These characteristics were increased compared to the films produced using the alpha-1,3-glucan dope solution lacking the crosslinker (Table 3).

[0202] [Table 3]

[0203] Example 5 Films produced using alpha-glucan dope solutions containing additives The alpha-1,3-glucan films were produced using a dope solution containing at least one additive.

[0204] An alpha-1,3-glucan dope solution was prepared containing 15 wt% water-insoluble alpha-1,3-glucan, 4.9 wt% NaOH, and 80.1 wt% water, followed by the addition of 10 wt% carbon black or bentonite clay (based on the weight of alpha-1,3-glucan in the dope). A film was then cast onto a glass surface using a 100 micron doctor blade. The cast film was coagulated using a 5% H2SO4 / 2.5% Na2SO4 aqueous bath and washed with DI water until neutral. The film was then treated in a 5% glycerol aqueous bath and dried.

[0205] The films containing carbon black were black and totally opaque, whereas the films containing bentonite were hazy white / translucent. The alpha-1,3-glucan films produced using the dope solution without any additives were transparent.

[0206] Example 6 Hybrid fibrids produced using alpha-glucan dope solutions containing additives Alpha-1,3-glucan fibrids were produced using a dope solution containing at least one additive. In particular, fibrids were produced having water-insoluble alpha-1,3-glucan with a water-soluble cationic ether alpha-1,3-glucan derivative as an additive.

[0207] Dope solutions were prepared containing underivatized water-insoluble alpha-1,3-glucan (DPw approx. 800, approx. 100% alpha-1,3 linkages) and its cationic ether derivative (hydroxypropyltrimethylamine ether derivative, DoS 0.3, water-soluble under non-caustic conditions; i.e., insoluble in water). Each dope solution contained a total glucan content (alpha-1,3-glucan and its ether derivative) of 13 wt% and 4.5 wt% NaOH in water. The ratio of alpha-1,3-glucan to its ether derivative in the prepared dope samples was 100:0 (i.e., no derivatives), 95:5, or 80:20 (w / w ratio). The dopes were prepared at room temperature (20-25°C); after blending the glucan, water, and NaOH, each dope solution was mixed and held for 1 hour.

[0208] For fibrid production, each dope solution was simultaneously fed and mixed with 1.5% H2SO4 in a shear mixer (room temperature, tip speed 38 m / s, mixing time <1 sec). The shear mixer precipitated alpha-1,3-glucan (now in the form of fibrids) by homogenizing the dope and acid solutions and lowering the overall pH. Besides glucan fibers, Na2SO4 salt (from acid-base reaction) and residual acid were present after mixing. The pH of the final mixture was about 2-3.

[0209] The fibrids were washed in water and analyzed for degree of substitution (DoS) and aspect ratio by NMR (Table 4).

[0210] [Table 4]

[0211] The high aspect ratio of the measured samples (Table 4) confirms that the product was in the form of fibrids. NMR confirmed that fibrids produced using a dope solution having both alpha-1,3-glucan and its cationic derivative had DoS measurements, and the fibrids were confirmed to have a positive charge by zeta potential analysis in deionized water (Table 4). Thus, the fibrids were able to trap charge on and / or within the fibrid structure. This is a noteworthy finding. The cationic alpha-1,3-glucan derivatives used here are water soluble and therefore could have remained in solution and been washed away during the fibrid production process. However, even after washing, charge was found to be retained on / within the fibrid particles. It is believed that other water soluble materials may be retained in the solid alpha-1,3-glucan products herein as well.

[0212] The process described in this example facilitates the adjustment of charge when producing fibrids, and possibly other solid products. By varying the amount of charged glucan derivative additive in the dope solution with underivatized glucan, the charge on the fibrids, and possibly other solids produced with the dope solution, can be adjusted. Now, instead of needing to prepare a specifically charged glucan derivative to produce a specifically charged solid material, the charged glucan derivative additive from its stock source can simply be blended with the underivatized glucan to achieve the desired charge in the solid product. This blending approach also allows for the production of solid products with unique / tunable charge distributions (depending on how the blending is performed) compared to using a charged glucan derivative as the only glucan component in the product, resulting in a fixed charge distribution across all products produced with the charged glucan derivative.

[0213] Example 7 Films produced using alpha-glucan dope solutions containing additives The alpha-1,3-glucan films were produced using a dope solution containing at least one additive.

[0214] This example discloses the use of additives to improve the mechanical properties (e.g., ultimate tensile strength, elongation) of alpha-1,3-glucan-based materials, such as free-standing films. Addition of small amounts of additive (in some cases less than 0.1 wt% additive relative to the alpha-1,3-glucan content) improved the ultimate tensile strength of free-standing films containing alpha-1,3-glucan to about 140% and the elongation to 77%. In addition, it was shown that alpha-1,3-glucan films with dual hydrophilic and hydrophobic behavior can be produced using oil as an additive.

[0215] In this example, the following chemicals / compounds were used: alpha-1,3-glucan (IFF, ca. 100% alpha-1,3 bonds, DPw ca. 800), NaOH (99.5%, ChemSolute), sulfuric acid (95%, ChemSolute), sodium lauryl sulfate (Carlo Erda), BDGE (1,4-butanediol diglycidyl ether, >95%, Sigma Aldrich), polyvinyl alcohol (Kuraray Exceval™ AQ-4140, ethylene modified PVA, degree of hydrolysis 98-99 mol%), paraffin wax (Fluka Chemika, ref. no. 76233), rapeseed oil (Bellasan®), glycerol (99.5%, Th. Geyer), sodium sulfate (99%, ChemSolute).

[0216] The caustic dope used in this study was prepared by dissolving alpha-1,3-glucan in aqueous NaOH (4.2 wt%) at room temperature; the final concentration of alpha-1,3-glucan in the dope was 15 wt%. Additives were added to this formulation. The amount of additive listed in this example is relative to the amount of alpha-1,3-glucan in the formulation (and therefore relative to the amount of alpha-1,3-glucan in the dry film produced by the caustic dope).

[0217] A film was produced using a caustic dope containing alpha-1,3-glucan and additives as follows: All operations were carried out at room temperature unless otherwise stated. The dope was poured onto a glass plate and a film was cast using a blade coater (ELCOMETER model 3530 / 4) with a gap of about 420 mm. The glass and cast film were introduced for 5 minutes into a coagulation bath filled with an aqueous solution of sulfuric acid (5 wt%) and sodium sulfate (2.5 wt%). In the middle of coagulation, the film was peeled off from the glass plate. The film was then immersed in a water bath for 40 minutes. The film was then introduced into a bath filled with water and glycerol (5 wt%) for 60 minutes. Once this process was complete, the film was dried at room temperature for about 20 hours, with weights applied at the corners to prevent shrinkage. Finally, the film was introduced into a 68°C oven for 2 hours to obtain a completely dried film. The film had a thickness of about 50 mm.

[0218] The ultimate tensile strength (in megapascals [MPa]) and elongation (percent elongation at break) of the films were measured using the standard procedure of DIN EN ISO 527-3, which is incorporated herein by reference. Samples were tested on an AllroundLine Z005 material testing machine with a preload of 0.1 MPa, a test speed of 200 mm / min, and a starting length of 30.00 mm.

[0219] Example 7A To determine whether the mechanical properties of the alpha-1,3-glucan film product can be improved, the crosslinker BDGE was used as an additive in the production of alpha-1,3-glucan films. Various amounts of BDGE were added to the alpha-1,3-glucan dope solution at room temperature with stirring, thereby preparing films (according to the methodology described above). The ultimate tensile strength and percent elongation of each film were measured (Table 5).

[0220] [Table 5]

[0221] An increase in ultimate tensile strength of up to about 68% and percent elongation of about 77% was observed in the alpha-1,3-glucan films with the BDGE additive.

[0222] Example 7B PVA was dissolved in water (1 wt%) and a certain amount of this solution was added to a water mixture of alpha-1,3-glucan (15 wt%). NaOH was then added to dissolve the alpha-1,3-glucan with stirring for 2 hours. Films were prepared from these dope solutions (following the methodology above). The ultimate tensile strength and percent elongation of each film were measured (Table 6).

[0223] [Table 6]

[0224] An increase in ultimate tensile strength of up to about 142% and percent elongation of about 17% was observed in the alpha-1,3-glucan films with PVA additive.

[0225] Example 7C Paraffin wax was added to a mixture of alpha-1,3-glucan (15 wt%) and about 0.005 wt% sodium lauryl sulfate in water. NaOH was then added to dissolve the alpha-1,3-glucan with stirring for 2 hours; the paraffin wax was dispersed in the resulting dope. Films were prepared from these dope emulsions (following the methodology above). The ultimate tensile strength and percent elongation of each film were measured (Table 7).

[0226] [Table 7]

[0227] An increase in ultimate tensile strength of up to about 123% and percent elongation of about 36% was observed in the alpha-1,3-glucan films with paraffin wax additive.

[0228] Additionally, light transmission activity was retained in alpha-1,3-glucan films with paraffin wax additive (Figure 2).

[0229] Example 7D Rapeseed oil was added to a mixture of alpha-1,3-glucan (15 wt%) and about 0.005 wt% sodium lauryl sulfate in water. The amount of rapeseed oil was used to have 10, 15, or 20 wt% rapeseed oil, where the wt% is relative to the alpha-1,3-glucan content. NaOH was then added to dissolve the alpha 1,3-glucan with stirring for 2 hours; the rapeseed oil was dispersed in the resulting dope. Films were prepared from these dope emulsions (following the methodology described above).

[0230] In particular, the films containing alpha-1,3-glucan and rapeseed oil exhibited a polarity where one side was hydrophilic and the other side was hydrophobic. In particular, the side of the film formed in direct contact with the glass ("inside") was hydrophilic and the opposite side ("outside") was hydrophobic. This hydrophilicity / hydrophobicity was identified, for example, by observing that water placed on the inside (hydrophilic) side of the film had a low contact angle with the film, whereas water placed on the outside (hydrophobic) side of the film readily beaded up into droplets with a high contact angle with the film (Figure 3). This polarity in water film association was not observed in alpha-1,3-glucan films lacking rapeseed oil; water generally beaded up equally on both the inside and outside of the film (data not shown). This hydrophilicity / hydrophobicity of the film surface was not observed in the alpha-1,3-glucan film with paraffin wax of Example 7C (data not shown).

Claims

1. A solution comprising at least (a) a caustic solvent, (b) an alpha-glucan or a derivative thereof, and (c) an additive, the additive is (i) a cross-linking agent, and / or (ii) an additive that does not chemically react with the alpha-glucan or derivative thereof; at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds, and the weight average degree of polymerization of the alpha-glucan is at least 15; The alpha-glucan or derivative thereof is dissolved in the caustic solvent, and the additive is either dissolved or not dissolved in the caustic solvent.

2. 2. The solution of claim 1, wherein at least about 90% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds.

3. The solution of claim 1 comprising said alpha-glucan.

4. 10. The solution of claim 1 comprising about 5 wt% to about 20 wt% of the alpha-glucan or derivative thereof.

5. The solution of claim 1 , wherein the additive is the crosslinking agent.

6. The solution of claim 1 , wherein the additive is an additive that does not react with the alpha-glucan or a derivative thereof.

7. 7. The solution of claim 6, wherein the additive is water soluble under non-caustic conditions.

8. The solution of claim 1 , wherein the additive is a polysaccharide derivative.

9. 2. The solution of claim 1, wherein the caustic solvent is an aqueous alkali metal hydroxide solution.

10. 10. The solution of claim 1 in the form of a doped filament.

11. 10. A method of producing the solution of claim 1, comprising: The method includes mixing at least the alpha-glucan or derivative thereof and the additive with a caustic solvent, wherein the alpha-glucan or derivative thereof dissolves in the caustic solvent.

12. 1. A method of producing a solid composition comprising the steps of: (a) providing a solution according to claim 1; (b) forming the solution into a desired form; and (c) removing the caustic solvent from the solution of step (b) to produce a solid composition comprising the alpha-glucan or derivative thereof and the additive; A method comprising:

13. Removing the solvent (i) chemically or ionically modifying the caustic solvent such that the alpha-glucan or derivative thereof, and the additive, if dissolved in the solvent, are no longer soluble in the caustic solvent; or (ii) blowing air through the solution; The method of claim 12, comprising:

14. 13. The method of claim 12, wherein the solid composition of step (c) is a fiber / filament, a fibrid, an extrudate, a composite, or a film / coating.

15. 13. The method of claim 12, wherein step (b) comprises using a device having one or more orifices through which the solution is passed / ejected / injected / forced, and optionally fibers / filaments are produced in step (c).

16. 13. A composition comprising a solid composition produced by the method of claim 12, wherein in some cases the solid composition is a fiber / filament, an extrudate, a fibrid, a composite, or a film / coating.

17. 1. A composition comprising a solid composition comprising at least a water insoluble alpha-glucan or a water insoluble derivative thereof, (i) the alpha-glucan or derivative thereof is cross-linked; and / or (ii) the composition further comprises an additive that is not chemically bound to the alpha-glucan or derivative thereof; The composition, wherein at least about 50% of the glycosidic bonds of the alpha-glucan are alpha-1,3 glycosidic bonds and the weight average degree of polymerization of the alpha-glucan is at least 15.

18. 20. The composition of claim 17, wherein the solid composition is a fiber / filament, a fibrid, an extrudate, a composite, a powder, or a film / coating.

19. 20. The composition of claim 17, wherein the solid composition is a fiber / filament, and the fiber / filament is included in a nonwoven product.

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