CN116848148A

CN116848148A - Oxidized polysaccharide derivatives

Info

Publication number: CN116848148A
Application number: CN202280015162.5A
Authority: CN
Inventors: 黄峥峥; A·霍克斯特拉; S·B·克鲁特; Y·布伦; L·A·豪威
Original assignee: Nutrition and Biosciences USA 4 Inc
Current assignee: Nutrition and Biosciences USA 4 Inc
Priority date: 2021-02-19
Filing date: 2022-02-17
Publication date: 2023-10-03
Also published as: CN116897167A

Abstract

Disclosed herein are compositions comprising at least one oxidized polysaccharide derivative. Such oxidized polysaccharide derivatives may be produced by contacting the polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative. Polysaccharide derivatives for oxidation have a degree of substitution (DoS) with at least one organic group of up to about 3.0. Further disclosed are methods of producing oxidized polysaccharide derivatives and their use in various applications and products.

Description

Oxidized polysaccharide derivatives

The application claims the benefits of U.S. provisional application No. 63/151,237 (filed on day 19 of 2 months of 2021), 63/151,223 (filed on day 19 of 2 months of 2021), and 63/283,638 (filed on day 29 of 11 months of 2021), which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure is in the field of polysaccharide derivatives. For example, the present disclosure relates to polysaccharide derivatives and polysaccharide derivatives that have been oxidized, and the use of the materials in various applications.

Background

Multifunctional detergent compositions have been produced that provide cleaning, water softening and rinsing benefits. For example, detergent formulations for automatic dish washing machines and other appliances are designed to function under hard water conditions. Hard water cations such as Ca ²⁺ And Mg (magnesium) ²⁺ May crystallize with carbonates and form insoluble salts that form deposits (also known as scale) on surfaces such as tableware or appliance interior components (e.g., pipes, sprayers). Hard water cations also play a role in soap scum formation. Biobased ingredients such as sodium citrate, methyl glycine disodium salt (MGDA) and L-glutamic acid-N, N-diacetic acid (GLDA) can help prevent these unwanted deposits by sequestering hard water cations and keeping them in solution. However, none of these ingredients are sufficient to prevent hard water surface deposits after repeated washing steps. By incorporating synthetic polymers (typically petroleum-based) such as polyacrylates (e.g., sulfonated polyacrylates) or bisphosphonates (e.g., ethane-1-hydroxy-1, 1-bisphosphonates [ EHDP)]) Inhibition of hard water deposit formation is more successfully addressed. These components are non-renewable and non-biodegradable; due toSuch environmental problems, these and related components are the subject of increasingly intensive governmental regulations.

Several detergent products have been developed that contain one or more environmentally friendly components, but these products often do not provide acceptable cleaning performance to the consumer (e.g., the above-described bio-based agents). Thus, there remains a need for cleaning composition ingredients that are renewable and/or biodegradable and provide cleaning properties equal to or better than those of products having synthetic components. For example, polysaccharide derivatives, oxidized forms thereof, and detergent compositions that address this need are disclosed herein.

Disclosure of Invention

In one embodiment, the present disclosure relates to a composition comprising an oxidized polysaccharide derivative, wherein the oxidized polysaccharide derivative is produced by contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative, and wherein the polysaccharide derivative has a degree of substitution (DoS) with at least one organic group of up to about 3.0.

In another embodiment, the present disclosure relates to a method of producing an oxidized polysaccharide derivative of the present disclosure. The method comprises the following steps:

(a) Contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing said polysaccharide derivative, thereby producing an oxidized polysaccharide derivative, wherein said polysaccharide derivative has a degree of substitution (DoS) with at least one organic group of up to about 3.0; and

(b) Optionally isolating the oxidized polysaccharide derivative.

In another embodiment, the present disclosure relates to a detergent composition comprising:

(i) A dextran derivative substituted with at least one organic group comprising a carboxylic acid group or a sulfonate group, wherein the degree of substitution (DoS) of the dextran derivative with the organic group is about 0.1 to about 3.0, and wherein the dextran from which the dextran derivative is derived has a weight average degree of polymerization (DPw) of at least about 50; and/or

(ii) An oxidized polysaccharide derivative, wherein the oxidized polysaccharide derivative is produced by contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative;

wherein the hard surface washed or treated in a wash/treat composition comprising the detergent composition has reduced filming (filming), spotting (spotting), clouding, or other deposition.

In another embodiment, the present disclosure relates to a method of washing or treating a hard surface. The method comprises the following steps:

(a) Contacting the hard surface with a wash/treat composition comprising a detergent composition of the present disclosure, and

(b) Removing all or a portion of the wash/treat composition from the hard surface;

thereby washing or treating the hard surface, wherein the washed/treated hard surface has reduced filming, spotting, cloudiness, and/or other deposits.

Drawings

Fig. 1: such as calcium carbonate flocculation stage mediated by oxidized alpha-1, 3-glucan. Reference example 11.

Detailed Description

The disclosures of all cited patent and non-patent documents are incorporated herein by reference in their entirety.

The term "a/an" as used herein is intended to encompass the feature(s) recited, unless otherwise disclosed.

All ranges, if present, are inclusive and combinable unless otherwise specified. For example, when a range of "1 to 5" (i.e., 1-5) is recited, the recited range should be interpreted to include the ranges "1 to 4", "1 to 3", "1-2 and 4-5", "1-3 and 5", and the like. Unless expressly indicated otherwise, the numerical values of the various ranges in this disclosure are stated as approximations as if the minimum and maximum values within the stated ranges were both preceded by the word "about". In this way, slight variations above and below the ranges can typically be used to achieve substantially the same results as values within these ranges. Moreover, the disclosure of these ranges is intended as a continuous range including each value between the minimum and maximum values.

Every maximum numerical limitation given throughout this specification is intended to include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations 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.

It is to be appreciated that certain features of the disclosure, which are, for clarity, described above and below in the context of aspects/embodiments, 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.

The term "polysaccharide" means a polymeric carbohydrate molecule composed of long chains of monosaccharide units joined together by glycosidic bonds and which upon hydrolysis yields the constituent monosaccharides and/or oligosaccharides of the polysaccharide. The polysaccharides herein may be linear or branched, and/or may be homopolysaccharides (consisting of only one type of constituent monosaccharides) or heteropolysaccharides (consisting of two or more different constituent monosaccharides). Examples of polysaccharides herein include dextran (polydextrose), levan (polyfructose), galactan (polygalactose), mannan (polymannan), arabinan (polyarabinose), xylan (polyxylose) and soybean polysaccharide.

"dextran" herein is a class of polysaccharides that are polymers of glucose (polydextrose). The glucan can include, for example, about or at least about 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, or 100 wt% glucose monomer units. Examples of glucans herein are alpha-glucan and beta-glucan.

The terms "alpha-glucan", "alpha-glucan polymer", and the like are used interchangeably herein. Alpha-glucan is a polymer comprising glucose monomer units linked together by alpha-glycosidic linkages. In typical aspects, the glycosidic linkages of the α -glucan 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% of the α -glycosidic linkages. Examples of α -glucan polymers herein include α -1, 3-glucan, α -1, 4-glucan, and α -1, 6-glucan.

The terms "beta-glucan", "beta-glucan polymer", and the like are used interchangeably herein. Beta-glucan is a polymer comprising glucose monomer units linked together by beta-glycosidic linkages. In typical aspects, the glycosidic linkages of the β -glucan 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% β -glycosidic linkages. Examples of beta-glucan polymers herein include beta-1, 3-glucan, beta-1, 4-glucan, and beta-1, 6-glucan.

Unless otherwise indicated, the term "saccharide" and other like terms refer herein to mono-and/or di-saccharides/oligosaccharides. Herein, "disaccharide" refers to a carbohydrate having two monosaccharides linked by glycosidic linkages. "oligosaccharide" herein may refer to a carbohydrate having, for example, 3 to 15 monosaccharides linked by glycosidic linkages. Oligosaccharides may also be referred to as "oligomers". Monosaccharides (e.g., glucose and/or fructose) contained within a disaccharide/oligosaccharide may be referred to as "monomeric units," "monosaccharide units," or other like terms.

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

The terms "alpha-1, 6-glucan", "poly alpha-1, 6-glucan", "alpha-1, 6-glucan polymer", "dextran" and the like herein refer to water-soluble alpha-glucans comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are alpha-1, 6. In some aspects, the α -1, 6-glucan comprises about, or at least about 90%, 95%, or 100% of α -1,6 glycosidic linkages. Other linkages that may be present in alpha-1, 6-glucan include alpha-1, 2, alpha-1, 3, and/or alpha-1, 4 linkages. "substantially linear" ("mostly linear" and like terms) dextran herein has 5% or less branching, while "linear" dextran has no branching. Dextran branches may be short, one to three glucose monomers (side chains) in length. However, in some aspects, the dextran may be "dendritic" in that it is a branched structure emanating from the nucleus in which there are chains (containing most or all of the a-1, 6-linkages) that iterate each other (e.g., a chain may be a branch from another chain, which in turn is a branch from another chain, etc.). However, in still other aspects, the dextran is not dendritic, but has a branched structure of branches that do not emanate from the nucleus.

The terms "alpha-1, 4-glucan", "poly alpha-1, 4-glucan", "alpha-1, 4-glucan polymer" and the like are used interchangeably herein. The alpha-1, 4-glucan is an alpha-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are alpha-1, 4. In some aspects, the α -1, 4-glucan comprises about, or at least about 90%, 95%, or 100% of α -1,4 glycosidic linkages. Most or all of the other linkages in the α -1, 4-glucan herein, if present, are typically α -1,6 (typically forming branches), but may also be α -1,2 and/or α -1,3. Examples of α -1, 4-glucan herein include amylose, amylopectin, and starch.

The terms "beta-1, 4-glucan", "poly beta-1, 4-glucan", "beta-1, 4-glucan polymer", "cellulose", and the like are used interchangeably herein. Beta-1, 4-glucan is a water-insoluble beta-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein about 100% of the glycosidic linkages are beta-1, 4. Beta-1, 4-glucan may be as disclosed, for example, in U.S. patent application publication No. 2018/0334696

The terms "beta-1, 3-glucan", "poly beta-1, 3-glucan", "beta 0-1, 3-glucan polymer" and the like are used interchangeably herein. Beta 1-1, 3-glucan is a beta-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are beta-1, 3. In some aspects, the beta-1, 3-glucan comprises about, or at least about 90%, 95%, or 100% beta-1, 3 glycosidic linkages. Most or all of the other linkages in beta-1, 3-glucan herein (if present) are typically beta-1, 6 (often forming constituent chains). Beta-1, 3-glucan can be prepared as disclosed, for example, in U.S. patent application publication No. 2014/0287919 and Stone, b.a. (2009,Chemistry of Beta-Glucans [ beta-glucan chemistry ]Edited by Antonny Bacic et al,Chemistry,Biochemistry,and Biology of 1-3 Beta Glucans and related Polysaccharides [1-3 beta ] glucan and chemistry, biochemistry and biology of related polysaccharides]Academic Press [ Academic Press ]]Burlington, massachusetts (Burlington, MA)), which is incorporated herein by reference.

The terms "soy polysaccharide" and "soy fiber" are used interchangeably herein and refer to high molecular weight, water insoluble polysaccharide materials that can be obtained from soybeans. Typically, the soybean polysaccharide is obtained from the cell wall structural components of soybean. The soy polysaccharide herein may be as disclosed, for example, in U.S. patent application publication No. 2018/0079732, which is incorporated herein by reference.

"alpha-1, 2 branches" (and similar terms) as referred to herein typically comprise glucose alpha-1, 2-linked to a dextran backbone; thus, the α -1,2 branches herein may also be referred to as α -1,2,6 bonds. The alpha-1, 2 branch herein typically has one glucose group (which may optionally be referred to as side chain glucose).

"alpha-1, 3 branches" (and similar terms) as referred to herein typically comprise glucose alpha-1, 3-linked to a dextran backbone; thus, the alpha-1, 3 branches herein may also be referred to as alpha-1, 3,6 bonds. The alpha-1, 3 branch herein typically has one glucose group (which may optionally be referred to as side chain glucose).

"alpha-1, 4 branches" (and similar terms) as referred to herein typically comprise glucose alpha-1, 4 linked to a dextran backbone; thus, the α -1,4 branch herein may also be referred to as an α -1,4,6 bond. The α -1,4 branch herein typically has one glucose group (which may optionally be referred to as side chain glucose).

In some aspects, the term "copolymer" refers to a polymer comprising at least two different types of alpha-glucan, such as dextran and alpha-1, 3-glucan.

The terms "graft copolymer," "branched copolymer," and the like herein generally refer to a copolymer comprising a "backbone" (or "backbone") and one or more side chains branching from the backbone. The side chains are structurally different from the backbone.

Examples of graft copolymers herein are "dextran-alpha-1, 3-glucan graft copolymers" (and similar terms) that contain a dextran-containing backbone and one or more side chains of alpha-1, 3-glucan. In some aspects, the backbone may itself be branched dextran as disclosed herein; the addition of alpha-1, 3-glucan side chains to such backbones (thereby forming the graft copolymers herein) can be, for example, via enzymatic extension of the non-reducing ends presented by short branches (alpha-1, 2, alpha-1, 3, or alpha-1, 4 branches, each typically containing a single glucose monomer; i.e., side chain glucose). Short branches (which may be enzymatically extended to the alpha-1, 3-glucan side chains) may be present on additional linear or mostly linear dextran, or may be present on branched dextran. In some aspects, the α -1, 3-glucan can also be synthesized from the non-reducing end of the dextran backbone, as in embodiments where the dextran backbone is linear or largely linear, or in embodiments where the dextran backbone is branched (e.g., dendritic or non-dendritic [ branches do not emanate from the nucleus ] but have a branch-to-branch structure); technically, such alpha-1, 3-glucan is not a side chain of dextran, but rather an extension from one or more dextran backbones.

The branching percentage in polysaccharide herein refers to the percentage of bonds in all polysaccharides representing branching points. For example, the percent of alpha-1, 3 branches in an alpha-glucan herein refers to the percent of all bonds in the glucan that represent alpha-1, 3 branch points. Unless otherwise indicated, the percentages of bonds disclosed herein are based on the total bonds of the polysaccharide, or the portions specifically referred to for the disclosure in the polysaccharide.

The terms "bond", "glycosidic bond" and the like refer to a covalent bond linking sugar monomers within a sugar compound (oligosaccharide and/or polysaccharide). Examples of glycosidic linkages include 1,6- α -D-glycosidic linkages (also referred to herein as "α -1,6" linkages), 1,3- α -D-glycosidic linkages (also referred to herein as "α -1,3" linkages), 1,4- α -D-glycosidic linkages (also referred to herein as "α -1,4" linkages), and 1,2- α -D-glycosidic linkages (also referred to herein as "α -1,2" linkages).

The glycosidic bond profile (profile) of a polysaccharide or derivative thereof may be determined using any method known in the art. For example, a method of using Nuclear Magnetic Resonance (NMR) spectroscopy (e.g., ¹³ c NMR and/or ¹ H NMR) to determine a keygram. These and other methods that may be used are disclosed for example, Food Carbohydrates:Chemistry,Physical Properties,and Applications[Food carbohydrates: chemical, physical properties and applications](S.W.Cui, chapter 3, S.W.Cui, structural Analysis of Polysaccharides [ structural analysis of polysaccharide ]],Taylor&Francis Group LLC (Taylor Francis group Co., ltd.)]Bokapton, florida, 2005), which is incorporated herein by reference.

The "molecular weight" of a polysaccharide or polysaccharide derivative herein may be expressed as a weight average molecular weight (Mw) or a number average molecular weight (Mn), in daltons (Da) or grams/mole. Alternatively, the molecular weight may be expressed as DPw (weight average degree of polymerization) or DPn (number average degree of polymerization). The molecular weight of the smaller polysaccharide polymer (such as an oligosaccharide) may optionally be provided as "DP" (degree of polymerization), which refers only to the amount of monomer contained within the polysaccharide; "DP" may also characterize the molecular weight of a polymer based on a single molecule. Various means for calculating these different molecular weight measurements are known in the art, such as using High Pressure Liquid Chromatography (HPLC), size Exclusion Chromatography (SEC) or Gel Permeation Chromatography (GPC).

As used herein, mw=Σnimi may be ² Calculating Mw by Sigma NiMi; where Mi is the molecular weight of the individual chain i and Ni is the number of chains having that molecular weight. In addition to SEC, the Mw of the polymer may be determined by other techniques such as static light scattering, mass spectrometry, MALDI-TOF (matrix assisted laser desorption/ionization time of flight), small angle X-ray or neutron scattering, or ultracentrifugation. As used herein, mn can be calculated as mn=Σnimi/Σni, where Mi is the molecular weight of chain i and Ni is the number of chains having that molecular weight. In addition to SEC, mn of a polymer can be determined by various numerical methods such as vapor pressure osmosis, by spectroscopic methods such as proton NMR, proton FTIR, or end group determination by UV-Vis. As used herein, DPn and DPw can be determined from Mw and Mn, respectively, by dividing them by the molar mass M of one monomer unit ₁ And (5) calculating. In the case of unsubstituted dextran polymers, M ₁ =162. In the case of substituted (derivatized) dextran polymers, M ₁ ＝162+M _f x DoS, where M _f Is the molar mass of the substituent group and DoS is the degree of substitution (average number of substituent groups per one glucose unit of the dextran polymer).

"polysaccharide derivative" (and like terms) herein (e.g., dextran derivative such as an alpha-or beta-dextran derivative) typically refers to a polysaccharide that has been substituted with at least one type of organic group. The degree of substitution (DoS) of the polysaccharide derivatives herein can be up to about 3.0 (e.g., about 0.001 to about 3.0). For example, the organic group may be attached to the polysaccharide derivative herein via an ether, ester, carbamate/carbamoyl or sulfonyl linkage. The precursors of polysaccharide derivatives herein refer to the underivatized polysaccharide (which may also be referred to as the polysaccharide portion of the derivative) used to prepare the derivative. Unless otherwise disclosed, the polysaccharide derivative has not undergone the oxidation step herein, and thus may optionally be characterized as a precursor to the oxidized polysaccharide derivative of the present disclosure. The organic groups herein are typically uncharged (nonionic) or anionic; typically, such charge may be that which is present when an organic group is in the aqueous compositions herein, and also the pH of the aqueous composition (in some aspects, the pH may be 4-10 or 5-9, or any pH as disclosed herein) should be considered. If present as a substitution in the polysaccharide derivatives herein, the organic group comprising a carboxylic acid group may itself be a carboxylic acid group (e.g., carbon 6 of glucose may be-COOH), or may be (i) an organic group linked to a polysaccharide ether-, ester-, carbamate-, or sulfonyl-and (ii) comprising a carboxylic acid group (e.g., a carboxyalkyl group such as carboxymethyl).

The term "degree of substitution" (DoS, or DS) as used herein refers to the average number of hydroxyl groups substituted (e.g., via ether, ester, or other linkages herein) with an organic group in each monomer unit of the polysaccharide derivative. DoS of polysaccharide derivatives herein may be stated with reference to DoS of a particular substituent or to the overall DoS, which is the sum of DoS values of different substituent types (e.g., if mixed ethers or mixed esters). Unless otherwise disclosed, when DoS is not stated with reference to a particular substituent type, it is meant to be an overall DoS.

The term "molar substitution" (m.s.) as used herein refers to the number of moles of organic groups per monomer unit of the polysaccharide derivatives herein. It should be noted that the molar substitution value of the polysaccharide derivative may for example have a very high upper limit, for example of hundreds or even thousands. For example, if the organic group is a hydroxyl-containing alkyl group, via addition of ethylene oxide to one of these hydroxyl groups of the polysaccharide, the hydroxyl groups from the ethylene oxide so formed may then be further etherified to form a polyether.

The term used herein with respect to "ether" (e.g., polysaccharide ether derivative) may be as used, for example, in U.S. patent application No. 2014/17 9913. 2016/0304629, 2015/023995, 2018/023441, 2018/023786, or 2020/0002646, U.S. application Ser. No. 63/037,076, or International patent application publication No. WO 2021/252569, 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. Polysaccharide ether derivatives herein are polysaccharides that have been etherified with one or more organic groups (e.g., uncharged, anionic) such that the derivative has a DoS with one or more organic groups of up to about 3.0. Polysaccharide ether derivatives are herein described as comprising the substructure-C _G O-C-called "ether", wherein "-C _G - "means the carbon atom of the monomer unit (e.g., glucose) of the polysaccharide ether derivative (wherein such carbon atom is bonded to the hydroxyl [ -OH ] group of the ether's polysaccharide precursor]) And wherein "-C-" is a carbon atom of the organic group.

The term used herein with respect to an "ester" (e.g., polysaccharide ester derivative) may be as disclosed, for example, in U.S. patent application nos. 2014/0187767, 2018/0155455, or 2020/0308371, U.S. application No. 63/037,184, or international patent application publication No. WO 2021252575, 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. Polysaccharide ester derivatives herein are polysaccharides that have been esterified with one or more organic groups (i.e., acyl groups) such that the derivative has up to about 3.0 DoS with one or more organic groups. Polysaccharide ester derivatives are herein described as comprising the substructure-C _G O-CO-C-is called "ester", wherein "-C _G - "means the carbon atom of the monomer unit (e.g., glucose) of the polysaccharide ester derivative (wherein such carbon atom is bonded to the hydroxyl [ -OH ] group of the polysaccharide precursor of the ester]) And wherein "-CO-C-" is contained in the acyl group.

The terms "polysaccharide carbamate derivative", "polysaccharide carbamate", "carbamoyl polysaccharide" and the like are used interchangeably herein. Polysaccharide carbamate derivatives containing a bond moiety-OCONH-orAnd thus comprises the substructure-C _G -OCONH-C _R -or-C _G -OCON-C _R2 -, wherein "-C _G - "denotes the carbon of the monomer unit of the polysaccharide carbamate derivative (e.g. glucose), and" -C _R - "contained in an organic group. In some aspects, the nitrogen atom of the carbamate/carbamoyl moiety is attached to a hydrogen atom and an organic group. However, in some aspects, the nitrogen atom of the carbamate/carbamoyl moiety is attached to two organic groups (e.g., above "-C _R2 - "shown), the two organic groups may be the same (e.g., two methyl groups, two ethyl groups) or different (e.g., methyl and ethyl groups).

The terms "polysaccharide sulfonyl derivative", "sulfonyl polysaccharide" and the like are used interchangeably herein. Polysaccharide sulfonyl derivatives containing a bond moiety-OSO ₂ -, and thus comprises the substructure-C _G -O-SO ₂ -C _R -, wherein "-C _G - "represents a carbon of a monomer unit (e.g., glucose) of a polysaccharide sulfonyl derivative, and" -C _R - "contained in an organic group. The sulfonyl bond herein is non-ionizable. The sulfonyl groups of the polysaccharide sulfonyl derivatives herein may be as disclosed, for example, in U.S. application No. 63/037,076 or international patent application publication No. WO 2021/252569, each of which is incorporated herein by reference.

The "sulfonate" group herein may be as disclosed, for example, in international patent application publication No. WO 2019/246228, which is incorporated herein by reference.

"oxidized polysaccharide derivatives" (and like terms) herein refer to compounds resulting from the oxidation of polysaccharide derivatives (e.g., ethers, esters, carbamates, sulfonyl groups) such as those disclosed herein. Such oxidation may occur, for example, at one or more hydroxyl groups of the monomer units of the polysaccharide derivative, and/or at one or more hydroxyl groups of the substituted organic groups of the polysaccharide derivative. Oxidation can independently convert hydroxyl groups to aldehydes, ketones, or carboxyl groups. For example, polysaccharide derivatives herein may be oxidized by contacting them under aqueous conditions with one or more oxidizing (oxidizing) agents.

The term "aqueous conditions" in reference to an oxidation reaction herein refers to a solution or mixture in which the solvent is, for example, at least about 60wt% water. The oxidation reaction herein may be carried out under aqueous conditions. For example, the aqueous conditions may be acidic or basic.

The terms "aqueous liquid", "aqueous fluid", "aqueous conditions", "aqueous reaction conditions", "aqueous environment", "aqueous system", and the like as used herein may refer to water or an aqueous solution. An "aqueous solution" herein may comprise one or more dissolved salts, where the maximum total salt concentration may be about 3.5wt% in some aspects. Although the aqueous liquids herein typically comprise water as the sole solvent in the liquid, the aqueous liquid may optionally comprise one or more other solvents (e.g., polar organic solvents) miscible in water. Thus, the aqueous solution may comprise a solvent having at least about 10wt% water.

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

The oxidized polysaccharide derivatives herein "soluble", "aqueous soluble", "water soluble" (and like terms) are herein dissolved (or significantly dissolved) in water or other aqueous conditions, optionally wherein the aqueous conditions are further characterized as having a pH of 4-9 (e.g., pH 6-8) and/or a temperature of about 1 ℃ to 130 ℃ (e.g., 20 ℃ -25 ℃). In contrast, oxidized polysaccharide derivatives that are "insoluble", "water insoluble", and the like are insoluble under these conditions. In some aspects, less than 1.0 gram (e.g., an undetectable amount) of the aqueous insoluble oxidized polysaccharide derivative is dissolved in 1000 milliliters of such aqueous conditions (e.g., 23 ℃ water).

The terms "home care product," "home care product," and similar terms typically refer to products, goods, and services related to the treatment, cleaning, care, and/or conditioning of a home and its interior. The foregoing includes, for example, having a chemical, composition, product, or combination thereof applied to such care.

"fabric care composition", "laundry care composition" and like terms refer to any composition suitable for treating fabric, nonwoven, and/or any like material in some manner. Examples of such compositions include laundry detergents and fabric softeners.

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

The terms "heavy duty detergent", "general purpose detergent", and the like are used interchangeably herein to refer to detergents that can be used to routinely wash white and colored textiles at any temperature. The terms "light duty detergent", "fine fabric detergent" and the like are used interchangeably herein to refer to a detergent that can be used to care for fine fabrics such as viscose, wool, silk, ultra fine fibers or other fabrics that require special care. "Special care" may include, for example, conditions using excess water, low agitation, and/or no bleaching.

The terms "builder", "builder agent" and the like herein refer to compositions that are, for example, complexed with hard water cations such as calcium and magnesium cations. It is believed that the formation of such complexes prevents the formation of water insoluble salts and/or other complexes by one or more cations. In the context of detergent compositions for cleaning or maintenance applications, builders added thereto typically can enhance or maintain the cleaning efficiency of surfactants present in the detergent composition. The terms "builder capacity", "builder activity", and the like are used interchangeably herein and refer to the ability of an aqueous composition to exhibit characteristics imparted by one or more builders present in the aqueous composition. Polysaccharide/dextran materials in certain aspects herein may be used as builders.

The terms "flocculant", "flocculating agent", "flocculating composition", "agglomerating agent" and the like herein refer to such substances: insoluble particles suspended in water or other aqueous liquids may be promoted to agglomerate/aggregate/coalesce, thereby making such particles easier to remove by sedimentation/sedimentation, filtration, granulation, and/or other suitable means. Flocculation of the particles may typically be performed during removal/separation of the particles from the aqueous suspension. Polysaccharide/dextran materials in certain aspects herein may be used as flocculants.

The term "personal care product" and similar terms typically refer to products, goods, and services related to the treatment, cleaning, cleansing, care, or conditioning of a person. The foregoing includes, for example, having a chemical, composition, product, or combination thereof applied to such care.

The terms "ingestible product," "ingestible composition," and the like refer to any substance that may be orally administered (i.e., through the mouth) alone or with another substance, whether or not intended for consumption. Thus, ingestible products include food/beverage products. By "food product/beverage product" is meant any edible product intended for human or animal consumption (e.g., for nutritional purposes), including solid, semi-solid, or liquid. "food" herein may be optionally referred to as, for example, "foodstuff (food stuff)", "food product", or other similar terms. "non-edible product" ("non-edible composition") refers to any composition that can be ingested through the oral cavity, except for food or beverage consumption purposes. Examples of non-edible products herein include supplements, nutraceuticals, functional food products, pharmaceutical products, oral care products (e.g., dentifrices, mouthwashes) and cosmetics such as sweetened lipsticks. "pharmaceutical product (pharmaceutical product)", "drug", "medicament", "drug" or similar terms herein refer to a composition that is used to treat a disease or injury and that can be enterally or parenterally administered.

The term "industrial product" and similar terms typically refer to products, goods, and services used in an industrial or institutional environment, but are typically not used by individual consumers.

The term "viscosity" as used herein refers to a measure of the degree to which a fluid (aqueous or non-aqueous) resists forces that tend to cause it to flow. Various viscosity units that may be used herein include, for example, centipoise (cP, cps) and pascal seconds (pa·s). One centipoise is one hundredth of one poise; one poise is equal to 0.100 kg.m ^-1 ·s ^-1 . In some aspects, viscosity may be reported as "intrinsic viscosity" (IV, η in dL/g); the term refers to a measure of the viscosity contribution of a dextran polymer to a liquid (e.g., solution) comprising the dextran polymer. IV measurements herein may be obtained, for example, using any suitable method, such as those described in U.S. patent application publication nos. 2017/0002335, 2017/0002336, or 2018/0340199, or Weaver et al (j. Appl. Polym. Sci. [ journal of applied polymer science ]]35:1631-1637) or Chun and Park (macromol. Chem. Phys. [ Polymer chemistry and Physics ]]195:701-711), which are incorporated herein by reference in their entirety. For example, IV can be measured in part by dissolving dextran polymer (optionally at about 100 ℃ for at least 2, 4, or 8 hours) in DMSO with about 0.9 to 2.5wt% (e.g., 1, 2, 1-2 wt%) LiCl. IV herein may optionally be used as a relative measure of molecular weight.

The terms "volume percent (percent by volume)", "volume percent" (vol%), "v/v%", and the like are used interchangeably herein. The volume percent of solute in the solution can be determined using the formula: [ (solute volume)/(solution volume) ] x 100%.

The terms "weight percent (percent by weight)", "weight percent (weight percentage, wt%)," weight-weight percent (weight-weight percentage,% w/w) ", and the like are used interchangeably herein. Weight percent refers to the percentage of a material on a mass basis when the material is included in a composition, mixture, or solution.

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

The term "isolated" means a substance (or process) in a form that does not exist in nature or in an environment that does not exist in nature. Non-limiting examples of isolated materials include any polysaccharide derivative or oxidized polysaccharide derivative disclosed herein. It is believed that the embodiments disclosed herein are synthetic/artificial (impossible to manufacture or practice except for human intervention/participation), and/or have non-naturally occurring properties.

The term "increased" as used herein may 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 that is increased as compared to the amount or activity that is increased. The terms "increased," "elevated," "enhanced," "greater than," "improved," and the like are used interchangeably herein.

Some aspects of the present disclosure relate to a composition comprising an oxidized polysaccharide derivative. Typically, oxidized polysaccharide derivatives of the present disclosure are produced by contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative, wherein the polysaccharide derivative (prior to oxidation) has a degree of substitution (DoS) with at least one organic group of up to about 3.0. Oxidized polysaccharide derivatives as disclosed herein have several advantageous features, such as the ability to prevent/reduce the formation of water-insoluble cations (e.g., ca ²⁺ 、Mg ²⁺ ) The formation of unwanted deposits caused by interactions with anionic compounds (e.g., carbonates, stearates).

The polysaccharide derivative used in some aspects to produce the oxidized polysaccharide derivatives herein may be a glucan derivative, a levan derivative, a galactan derivative, a mannan derivative, an arabinan derivative, a xylan derivative, or a soybean polysaccharide derivative. The glucan derivative herein may be, for example, an alpha-glucan derivative or a beta-glucan derivative. The glycosidic linkages of the α -glucan derivatives herein are typically about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% α -glycosidic linkages. Examples of suitable alpha-glucan derivatives include derivatives of alpha-1, 3-glucan, alpha-1, 6-glucan and alpha-1, 4-glucan.

For example, derivatives of alpha-1, 3-glucan may be used herein to provide oxidized polysaccharide derivatives (i.e., oxidized alpha-1, 3-glucan derivatives). In some aspects, such alpha-1, 3-glucan may comprise about or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% alpha-1, 3 glycosidic linkages. Thus, in some aspects, the α -1, 3-glucan has about, or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% glycosidic linkages that are not α -1, 3. Typically, glycosidic linkages other than alpha-1, 3 are mostly or entirely alpha-1, 6. It will be appreciated that the higher the percentage of alpha-1, 3 linkages present in the alpha-1, 3-glucan, the greater the likelihood that the glucan will be linear, as some linkages may occur less frequently as part of a branching point. In some aspects, the α -1, 3-glucan has no branching points or has less than about 5%, 4%, 3%, 2%, or 1% branching points as a percentage of glycosidic linkages in the α -1, 3-glucan.

In some aspects, the DPw, DPn, or DP of the α -1, 3-glucan portion of the α -1, 3-glucan derivative can be about, or at least about 10, 25, 50, 75, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, or 4000.DPw, DPn or DP may optionally be expressed as a range between any two of these values. By way of example only, the DPw, DPn, or DP of the alpha-1, 3-glucan may be about 50-1600, 100-1600, 200-1600, 300-1600, 400-1600, 500-1600, 600-1600, 700-1600, 50-1250, 100-1250, 200-1250, 300-1250, 400-1250, 500-1250, 600-1250, 700-1250, 50-1000, 100-1000, 200-1000, 300-1000, 400-1000, 500-1000, 600-1000, 700-1000, 50-900, 100-900, 200-900, 300-900, 400-900, 500-900, 600-900, 700-900, 600-800, or 600-750. Any of these DPw, DPn, or DP values may also be used with reference to polysaccharide derivatives herein, wherein such reference is used with respect to the polysaccharide portion of the derivative. In some aspects, the α -1, 3-glucan portion of the α -1, 3-glucan derivative can have a high molecular weight as 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 12-15dL/g. For comparison purposes, it is noted that an IV of α -glucan having at least 90% (e.g., about 99% or 100%) α -1,3 linkages and a DPw of about 800 has an IV of about 2-2.5 dL/g. IV herein can be measured as with, for example, an a-glucan polymer dissolved in DMSO having about 0.9 to 2.5wt% (e.g., 1, 2, 1-2 wt%) LiCl.

The α -1, 3-glucan moiety of the α -1, 3-glucan derivatives herein may be as disclosed (e.g., molecular weight, key map, production method) in, for example, U.S. patent nos. 7000000, 8871474, 10301604, and 10260053, and U.S. patent application publication nos. 2019/012456, 2019/00780562, 2019/0078063, 2018/0340199, 2018/0021238, 2018/0273731, 2017/0002335, 2015/023289, 2015/0064748, 2020/0165360, and 2019/0185893, each of which is incorporated herein by reference.

For example, derivatives of alpha-1, 6-glucan (dextran) may be used herein to provide oxidized polysaccharide derivatives (i.e., oxidized alpha-1, 6-glucan derivatives). Such alpha-1, 6-glucan may comprise, for example, about 100% of alpha-1, 6 glycosidic linkages (i.e., is a fully linear dextran), or about, or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 99.5% of alpha-1, 6 glycosidic linkages. In some aspects, the substantially linear alpha-1, 6-glucan may comprise 5%, 4%, 3%, 2%, 1%, 0.5% or less branching. Branches from alpha-1, 6-glucan, if present, are typically shorter, one, two or three glucose monomers (side chains) in length. In some aspects, the α -1, 6-glucan can comprise about, at least about, or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% α -1,4, α -1,3, and/or α -1,2 glycosidic linkages. Typically, such bonds exist entirely or almost entirely as branching points from the α -1, 6-glucan.

For example, the α -1, 6-glucan moiety of the α -1, 6-glucan derivatives herein can have α -1,2, α -1,3, and/or α -1,4 branches. In some aspects, about, at least about, or less than about 1%, 2%, 2.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 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% of all glycosidic linkages of the branched alpha-1, 6-glucan are alpha-1, 2, alpha-1, 3, and/or alpha-1, 4 glycosidic linkages. The length of such branches is typically mostly (> 90% or > 95%) or all (100%) of a single glucose monomer. Alpha-1, 6-glucan having an alpha-1, 3-branch can be prepared as disclosed in Vuillemin et al (2016, J.biol Chem. [ J. Biochem. 291:7687-7702), U.S. application Ser. No. 16/923,164, international patent application publication No. WO 2021/0078264, or U.S. patent application publication No. 2016/0136599, each of which is incorporated herein by reference. Alpha-1, 6-glucan having alpha-1, 2-branches can be prepared as disclosed in U.S. patent application publication No. 2018/0282385, which is incorporated herein by reference.

For example, the α -1, 6-glucan moiety of the α -1, 6-glucan derivative herein can have a molecular weight (Mw [ weight average molecular weight ]) of about, at least about, or less than about 1000, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 125000, 150000, 175000, 200000, 225000, 250000, 500000, 750000, 1000000, 50000-250000, 50000-200000, 100000-250000, 100000-225000, 100000-200000, 150000-250000, 150000-225000, 150000-200000, or 10000-20000 daltons. In some aspects, the Mw is about, at least about, or less than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 10-50, 10-70, 10-80, 10-100, 10-120, 10-130, 10-150, 10-200, 25-50, 25-70, 25-80, 25-100, 25-120, 25-130, 25-150, 25-200, 50-70, 50-80, 50-100, 50-120, 50-130, 50-150, 50-200, 70-80, 70-100, 70-120, 70-130, 70-150, 70-200, 80-100, 80-120, 80-150, 80-200, 100-130, 100-150, 100-120, 120-150, 120-120, 120-150, 130, 50-150, 130 or 130-130, or 130 daltons. Any of these Mw values may optionally be expressed as a weight average degree of polymerization (DPw), which is Mw divided by 162.14 (the calculated DPw may be rounded to the nearest integer).

The α -1, 6-glucan moiety of the α -1, 6-glucan derivatives herein can be as disclosed (e.g., molecular weight, bond/branching pattern, production method) for example in U.S. patent application publication nos. 2016/012445, 2017/0218093, 2018/0282385, 2020/0165360, and 2019/0185893, each of which is incorporated herein by reference. In some aspects, the α -1, 6-glucan may be glucan produced in a suitable reaction comprising Glucosyltransferase (GTF) 0768 (SEQ ID NO:1 or 2 of US 2016/012445), GTF 8117, GTF 6831, or GTF 5604 (these latter three GTF enzymes are SEQ ID NOs: 30, 32 and 33 of US2018/0282385, respectively) or a GTF comprising an amino acid sequence that is at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% identical to the amino acid sequence of GTF 0768, GTF 8117, GTF 6831, or GTF 5604.

For example, derivatives of alpha-glucan graft copolymers may be used herein to provide oxidized polysaccharide derivatives. The α -glucan graft copolymer portion of the graft copolymer derivatives herein may be as disclosed (e.g., molecular weight, bond/branching pattern, production method) for example in U.S. patent application publication nos. 2020/0165360 and 2019/0185893, U.S. application No. 63/034,437, or international patent application publication No. WO 2021247810, each of which is incorporated herein by reference. In some aspects, the α -glucan graft copolymer comprises a backbone of α -1, 6-glucan and one or more α -1, 3-glucan side chains. The α -1, 6-and α -1, 3-glucan components of such graft copolymers may be as disclosed herein. For example, the α -1, 6-glucan backbone may (i) have a molecular weight of about 5000 tens of thousands to 2 trillion daltons and/or have been synthesized using GTF 0768 (e.g., as above), and/or (ii) have been modified to have α -1, 2-and/or α -1,3 branches prior to grafting with α -1, 3-glucan side chains. For example, the α -glucan graft copolymer can comprise: (A) An alpha-1, 6-glucan backbone (100% of the alpha-1, 6-linkages prior to alpha-1, 2 and/or alpha-1, 3 branching) that has been branched (e.g., the backbone comprises a total of about 82% -86% or 84% of alpha-1, 6 linkages and about 14% -18% or 16% of alpha-1, 2 and/or alpha-1, 3 linkages) and (ii) has a Mw of about 15-25, 15-22.5, 17-25, 17-22.5, 18-22, or 20kDa, and (B) one or more (e.g., two, three, four, five, or six) glycans extending from the alpha-1, 2 and/or alpha-1, 3 of the alpha-1, 3 side chains of the alpha-1, 2 and/or alpha-1, 3; such graft copolymers are typically water insoluble.

For example, derivatives of alpha-1, 4-glucan may be used herein to provide oxidized polysaccharide derivatives (i.e., oxidized alpha-1, 4-glucan derivatives). In some aspects, such alpha-1, 4-glucan may comprise about or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% alpha-1, 4 glycosidic linkages. Thus, in some aspects, the α -1, 4-glucan has about, or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% glycosidic linkages that are not α -1, 4. Examples of α -1, 4-glucan herein include amylose, amylopectin, and starch. For example, alpha-1, 4-glucan such as starch may be derived from vegetable (e.g., potato, tapioca, pea, palm) or cereal (e.g., corn, wheat, rice, barley) sources.

In some aspects, the DPw, DPn, or DP of the α -1, 4-glucan portion of the α -1, 4-glucan derivative can be about, or at least about 10, 25, 50, 75, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, or 4000.DPw, DPn or DP may optionally be expressed as a range between any two of these values.

The polysaccharide derivative used in some aspects to produce the oxidized polysaccharide derivatives herein may be a β -glucan derivative. The glycosidic linkages of the beta-glucan derivatives herein are typically about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% beta-glycosidic linkages. Examples of suitable beta-glucan derivatives include beta-1, 3-glucan (e.g., laminarin, euglena, curdlan) and beta-1, 4-glucan (cellulose) derivatives.

For example, derivatives of beta-1, 4-glucan may be used herein to provide oxidized polysaccharide derivatives (i.e., oxidized beta-1, 4-glucan derivatives). Such beta-1, 4-glucans typically comprise about 100% beta-1, 4 glycosidic linkages. In some aspects, the DPw, DPn, or DP of the β -1, 4-glucan portion of the β -1, 4-glucan derivative can be about, or at least about 10, 25, 50, 75, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, or 4000.DPw, DPn, or DP may optionally be expressed as a range between any two of these values (e.g., 1000-2000, 1300-1700, 1400-1600).

The polysaccharide derivative used in some aspects to produce the oxidized polysaccharide derivatives herein may be a soy polysaccharide derivative. In some aspects, the soy polysaccharide portion of the soy polysaccharide derivative may be as disclosed in U.S. patent application publication No. 2018/0079732, which is incorporated herein by reference. In some aspects, the soy polysaccharide derivative used herein for oxidation may be an ether, such as disclosed in international patent application publication No. WO 2016/133734, which is incorporated herein by reference.

The polysaccharide derivatives used in some aspects to produce the oxidized polysaccharide derivatives herein may have a degree of substitution (DoS) with at least one organic group/substituent as disclosed herein up to about 3.0 (e.g., 0.001 to 3.0). DoS can be, for example, about, at least about, or up to about 0.001, 0.0025, 0.005, 0.01, 0.025, 0.05, 0.075, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0 (DoS can optionally be expressed as a range between any two of these values). Some examples of DoS ranges herein include 0.05-2.0, 0.05-1.6, 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, 0.1-2.0, 0.1-1.6, 0.1-1.5, 0.1-1.25, 0.1-1.0, 0.1-0.9, 0.1-0.8, 0.1-0.7, 0.1-0.6, 0.1-0.5, 0.15-2.0, 0.15-1.6, 0.15-1.5, 0.15-1.25, 0.15-0.9, 0.15-0.8, 0.15-0.7, 0.15-0.5, 0.15-0.0.5, 0.15-0.0.0, 0.15-2.5, 0.1-0.8, 0.1-0.5, 0.15-0.0.0.2.5, 0.1-2.8, 0.1-0.5, 0.15-2.0.0.0 0.2-1.25, 0.2-1.0, 0.2-0.9, 0.2-0.8, 0.2-0.7, 0.2-0.6, 0.2-0.5, 0.25-2.0, 0.25-1.6, 0.25-1.5, 0.25-1.25, 0.25-1.0, 0.25-0.9, 0.25-0.8, 0.25-0.7, 0.25-0.6, 0.25-0.5, 0.3-2.0, 0.3-1.6, 0.3-1.5, 0.3-1.25, 0.3-1.0, 0.9, 0.3-0.8, 0.3-0.7, 0.3-0.6, 0.3-0.5, 0.4-2.0, 0.4-1.6, 0.4-1.4.5, 0.4-0.4.0, 0.4-1.5, 0.4-0.4.0 and 4.4-0.5. In some aspects, oxidized polysaccharide derivatives herein may be characterized as having any of the aforementioned DoS values/ranges.

Regarding the polysaccharide derivative herein as a glucan derivative, for example, since at most three hydroxyl groups are present in a glucose monomer unit of glucan, the total DoS of the glucan derivative may be not higher than 3.0. It will be appreciated by those skilled in the art that since the dextran derivative as disclosed herein has a DoS with at least one type of organic group (e.g., between about 0.001 to about 3.0), all substituents of the dextran derivative cannot be hydroxyl only. Any polysaccharide derivative of the present disclosure (to be oxidized to produce an oxidized polysaccharide derivative) may be derived from the polysaccharides disclosed herein.

In some aspects the polysaccharide derivatives used to produce the oxidized polysaccharide derivatives herein are substituted with at least one organic group via an ether linkage, an ester linkage, a urethane linkage, or a sulfonyl linkage. Thus, the polysaccharide derivative herein may be, for example, a polysaccharide ether, ester, carbamate, or sulfonyl derivative. All of the various linking groups disclosed herein are examples of organic groups; for example, an organic group may be considered to contain at least one carbon atom and at least one hydrogen atom. The organic groups of the polysaccharide derivatives herein typically do not carry a cation/positive charge.

In some aspects, the polysaccharide derivative for oxidation herein may be a polysaccharide ether. The organic group in ether linkage with the polysaccharide herein may be, for example, an alkyl group. In some aspects, alkyl groups may be linear, branched, or cyclic ("cycloalkyl" or "alicyclic"). In some aspects, the alkyl is C ₁ To C ₁₈ Alkyl radicals, e.g. C ₄ To C ₁₈ Alkyl, or C ₁ To C ₁₀ Alkyl (in "C) _# "wherein, # refers to the number of carbon atoms in the alkyl group). Alkyl groups may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl; such alkyl groups are typically linear. In some aspects, one or more carbons of an alkyl group may be substituted with another alkyl group, such that the alkyl group is branched. Suitable examples of branched isomers of the linear alkyl groups include isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, neopentyl, isohexyl, neohexyl, 2-ethylhexyl, 2-Propylheptyl, and isooctyl. In some aspects, alkyl is cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl.

In some aspects, the organic group in ether linkage with the polysaccharides herein may be a substituted alkyl group having a substitution on one or more carbons of the alkyl group. The one or more substitutions may be one or more hydroxyl, aldehyde, ketone, and/or carboxyl groups. For example, the substituted alkyl group may be a hydroxyalkyl group, a dihydroxyalkyl group, or a carboxyalkyl group. Examples of suitable hydroxyalkyl groups are hydroxymethyl (-CH) ₂ OH), hydroxyethyl (e.g., -CH ₂ CH ₂ OH、-CH(OH)CH ₃ ) Hydroxypropyl (e.g., -CH) ₂ CH ₂ CH ₂ OH、-CH ₂ CH(OH)CH ₃ 、-CH(OH)CH ₂ CH ₃ ) Hydroxybutyl and hydroxypentyl. Other examples include dihydroxyalkyl (diols) such as dimethylol, dihydroxyethyl (e.g., -CH (OH) CH) ₂ OH), dihydroxypropyl (e.g., -CH ₂ CH(OH)CH ₂ OH、-CH(OH)CH(OH)CH ₃ ) Dihydroxybutyl and dihydroxypentyl. Examples of suitable carboxyalkyl groups are carboxymethyl (-CH) ₂ COOH), carboxyethyl (e.g., -CH ₂ CH ₂ COOH、-CH(COOH)CH ₃ ) Carboxypropyl (e.g., -CH) ₂ CH ₂ CH ₂ COOH、-CH ₂ CH(COOH)CH ₃ 、-CH(COOH)CH ₂ CH ₃ ) Carboxybutyl and carboxypentyl.

In some aspects, one or more carbons of an alkyl group in ether linkage with a polysaccharide herein can have one or more substitutions by another alkyl group. Examples of such substituted alkyl groups are methyl, ethyl and propyl. For example, the organic group may be, for example, -CH (CH) ₃ )CH ₂ CH ₃ or-CH ₂ CH(CH ₃ )CH ₃ Both of which are propyl groups having methyl substitution.

As should be apparent from the above examples of various substituted alkyl groups, in some aspects, the substitution on the alkyl group (e.g., hydroxy or carboxy) may be at a terminal carbon atom of the alkyl group, wherein the terminal carbon group is opposite to the alkyl side that is ether-linked to the polysaccharide ether in the monomer unit of the compound . An example of such a terminal substitution is hydroxypropyl-CH ₂ CH ₂ CH ₂ OH. Alternatively, the substitution may be on an internal carbon atom of the alkyl group. An example of an internal substitution is hydroxypropyl-CH ₂ CH(OH)CH ₃ . The alkyl group may have one or more substitutions, which may be the same (e.g., two hydroxy groups [ dihydroxy ]]) Or different (e.g., one hydroxyl group and one carboxyl group).

Optionally, etherified alkyl groups herein may contain one or more heteroatoms, such as oxygen, sulfur, and/or nitrogen, within the hydrocarbon chain. Examples include those containing an alkyl glycerol alkoxylate moiety (-alkylene-OCH) ₂ CH(OH)CH ₂ OH), moieties derived from the ring opening of 2-ethylhexyl glycidyl ether, and alkyl groups of tetrahydropyranyl (e.g., as derived from dihydropyran). Further examples include alkyl groups substituted at the terminal end thereof with cyano (-C.ident.N); such substituted alkyl groups may optionally be referred to as nitrile groups or cyanoalkyl groups. Examples of cyanoalkyl groups herein include cyanomethyl, cyanoethyl, cyanopropyl, and cyanobutyl.

In some aspects, the etherified organic group is C ₂ To C ₁₈ (e.g., C ₄ To C ₁₈ ) Alkenyl groups, and the alkenyl groups may be linear, branched, or cyclic. As used herein, the term "alkenyl" refers to a hydrocarbon group containing at least one carbon-carbon double bond. Examples of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexyl and allyl. In some aspects, one or more carbons of the alkenyl group can have one or more substitutions with an alkyl, hydroxyalkyl, or dihydroxyalkyl group, as disclosed herein. Examples of such substituted alkyl groups include methyl, ethyl and propyl. Optionally, alkenyl groups herein may contain one or more heteroatoms, such as oxygen, sulfur, and/or nitrogen, within the hydrocarbon chain; for example, alkenyl groups may contain moieties derived from the ring opening of allyl glycidyl ethers.

In some aspects, the etherified organic group is C ₂ To C ₁₈ Alkynyl groups. As used herein, the term "alkynyl" refers to straight and branched hydrocarbon groups containing at least one carbon-carbon triple bond. Alkynyl groups herein may beFor example, propynyl, butynyl, pentynyl, or hexynyl. Alkynyl groups may be optionally substituted with, for example, alkyl, hydroxyalkyl, and/or dihydroxyalkyl groups. Optionally, alkynyl groups may contain one or more heteroatoms such as oxygen, sulfur, and/or nitrogen within the hydrocarbon chain.

In some aspects, the etherified organic group is a compound comprising (-CH) ₂ CH ₂ O-)、(-CH ₂ CH(CH ₃ ) O-), or mixtures thereof, wherein the total number of repeating units is in the range of 2 to 100. In some aspects, the organic group is a compound comprising (-CH) ₂ CH ₂ O-) _3-100 Or (-CH) ₂ CH ₂ O-) _4-100 Polyether groups of (a). In some aspects, the organic group is a compound comprising (-CH) ₂ CH(CH ₃ )O-) _3-100 Or (-CH) ₂ CH(CH ₃ )O-) _4-100 Polyether groups of (a). As used herein for polyether groups, the subscripts to the indicated value ranges represent the potential number of repeating units; for example, (CH) ₂ CH ₂ O) _2-100 Meaning polyether groups containing from 2 to 100 repeating units. In some aspects, the polyether groups herein may be end-capped, such as with methoxy, ethoxy, or propoxy groups.

In some aspects, the etherified organic group includes an aryl group. As used herein, the term "aryl" means 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), optionally mono-, di-, or tri-substituted with an alkyl group (such as methyl, ethyl, or propyl). In some aspects, aryl is C ₆ To C ₂₀ Aryl groups. In some aspects, the aryl is a methyl-substituted aryl such as tolyl (-C) ₆ H ₄ CH ₃ ) Or xylyl [ -C ₆ H ₃ (CH ₃ ) ₂ ]A group. Tolyl can be, for example, p-tolyl. In some aspects, the aryl is benzyl (-CH) ₂ -phenyl). Benzyl herein may optionally be substituted with halo, cyano, ester, amide, ether, alkyl (e.g., C ₁ To C ₆ ) Aryl (e.g. benzene)Radical), alkenyl radical (e.g., C ₂ To C ₆ ) Or alkynyl (e.g. C ₂ To C ₆ ) One or more of the groups are substituted (typically on their benzene rings).

Polysaccharide ethers used for oxidation in some aspects may contain one type of etherified organic group. Examples of such compounds contain carboxyalkyl groups (e.g., carboxymethyl groups) as the sole etherified organic groups. Further examples include polysaccharide ethers containing alkyl groups (e.g., methyl, ethyl, propyl) as the sole etherified organic groups. Further examples include polysaccharide ethers containing dihydroxyalkyl groups (e.g., dihydroxypropyl groups) as the sole etherified organic groups.

Polysaccharide ethers used for oxidation in some aspects may contain two or more different types of etherified organic groups (i.e., mixed ethers of polysaccharides). Examples of such polysaccharide ethers contain (i) two different alkyl groups as etherified organic groups, (ii) an alkyl group and a hydroxyalkyl group as etherified organic groups (alkyl hydroxyalkyl polysaccharide), (iii) an alkyl group and a carboxyalkyl group as etherified organic groups (alkyl carboxyalkyl polysaccharide), (iv) a hydroxyalkyl group and a carboxyalkyl group as etherified organic groups (hydroxyalkyl carboxyalkyl polysaccharide), (v) two different hydroxyalkyl groups as etherified organic groups, (vi) two different carboxyalkyl groups as etherified organic groups, (vii) a carboxyalkyl group and an aryl group (e.g. benzyl). Non-limiting examples of some of these types of mixed ethers include ethyl hydroxyethyl polysaccharide, hydroxyalkyl methyl (e.g., hydroxypropyl methyl) polysaccharide, carboxymethyl hydroxyethyl polysaccharide, carboxymethyl hydroxypropyl polysaccharide, and carboxymethyl benzyl polysaccharide. In some cases, the mixed polysaccharide ether may be as disclosed in U.S. patent application publication 2020/0002646, which is incorporated herein by reference.

In some aspects, the polysaccharide derivative for oxidation herein may be a polysaccharide ester. The polysaccharide ester derivative may comprise, for example, at least one acyl group-CO-R ', wherein R' comprises a chain of 1 to 26 carbon atoms. R' may be, for example, linear, branched, or cyclic. Examples of the linear acyl group herein include acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, eicosanoyl, undecanoyl, docosanoyl, tricosanoyl, tetracosanoyl, pentacosanoyl, and hexacosanoyl. Some of the acyl groups listed above are commonly known as acetyl (acetyl or ethane yl group), propionyl (propionyl or propanyl group), butyryl (butyl or butyl group), pentanoyl (valyl or pentanyl group), hexanoyl (caproyl or hexanoyl group); heptanoyl (enantyl) or heptanoyl group, octanoyl (capryl or octanoyl group), nonanoyl (pelargonyl or nononoyl group), decanoyl (capryl or decanoyl group), lauroyl (dodecanoyl), myristyl (tetradecanoyl), palmitoyl (hexadecanoyl), stearyl (octadecanoyl), arachidyl (eicosanoyl), behenyl (behenyl), lignoceryl (tetracosanoyl), and ceryl (hexaceryl).

In some aspects, the acyl groups of the polysaccharide esters comprise aryl groups. For example, the aryl acyl group may include benzoyl (-CO-C) ₆ H ₅ ) It may also be referred to as a benzoate group. In some aspects, an aryl acyl group can comprise a benzoyl group substituted with at least one halogen ("X"; e.g., cl, F), alkyl, haloalkyl, ether, cyano, or aldehyde group, or a combination thereof, such as represented by structures III (a) through III (r) below:

in some aspects, the polysaccharide ester derivative may contain one type of esterified acyl group. Examples of such derivatives contain acetyl as the sole esterified acyl group. However, in some aspects, the polysaccharide ester derivative may contain two or more different types of esterified acyl groups (i.e., mixed esters of polysaccharides). Examples of such mixed esters include those having at least (i) acetyl and propionyl, (ii) acetyl and butyryl, and (iii) propionyl and butyryl.

The acyl groups of the polysaccharide ester derivatives herein may be as disclosed, for example, in U.S. patent application publication nos. 2014/0187767, 2018/0155455, or 2020/0308371, U.S. application No. 63/037,184, each of which is incorporated herein by reference.

In some aspects, the polysaccharide derivative for oxidation herein may be a polysaccharide carbamate. The polysaccharide carbamate derivative may comprise, for example, a carbamate group derived from an aliphatic, cycloaliphatic, or aromatic monoisocyanate. In some aspects, the substituents of the polysaccharide carbamate derivative may be carbamate linked phenyl, benzyl, diphenylmethyl, or diphenylethyl; these groups may optionally be derived using aromatic monoisocyanates such as phenyl, benzyl, diphenylmethyl, or diphenylethyl isocyanate, respectively. In some aspects, the substituents of the polysaccharide carbamate derivative may be carbamate-linked ethyl, propyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or octadecyl; these groups may optionally be derived using aliphatic monoisocyanates such as ethyl, propyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or octadecyl isocyanate, respectively. In some aspects, the substituents of the polysaccharide carbamate derivative may be carbamate-linked cyclohexyl, cycloheptyl, or cyclododecyl; these groups may optionally be derived using cycloaliphatic monoisocyanates such as cyclohexyl, cycloheptyl, or cyclododecyl isocyanate, respectively.

The carbamate groups of the polysaccharide carbamate derivatives herein may be as disclosed, for example, in international patent application publication nos. WO 2020/131711, U.S. application No. 63/037,076, each of which is incorporated herein by reference.

In some aspects, the polysaccharide derivative for oxidation herein may be a polysaccharide sulfonyl derivative. The sulfonyl groups of the polysaccharide sulfonyl derivatives herein may be as disclosed, for example, in U.S. application No. 63/037,076, each of which is incorporated herein by reference.

Oxidized polysaccharide derivatives of the present disclosure mayBy contacting a polysaccharide derivative (e.g., ether, ester, carbamate, sulfonyl) herein under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative. Examples of the reagent (oxidizing agent) for oxidizing polysaccharide derivatives herein include N-oxoammonium salts, periodate compounds, peroxide compounds, NO ₂ 、N ₂ O ₄ And/or ozone. Also for example, oxidized polysaccharide derivatives as disclosed herein may be prepared by applying the oxidation methods as disclosed in canadian patent publication nos. 2028284 or 2038640, or U.S. patent nos. 4985553, 2894945, 5747658, or 7595392, or U.S. patent application publication nos. 2015/0259439, 2018/0022834, or 2018/0079732, which are incorporated herein by reference in their entirety.

The oxidizing agent used in some aspects to oxidize the polysaccharide derivatives herein may include one or more N-oxoammonium salts, such as those disclosed in U.S. patent application publication nos. 2015/0259439, 2018/0022834, or 2018/0079803 (supra). The N-oxoammonium salts herein have the following structure:

wherein R is ¹ And R is ² Each represents the same or different organic groups (e.g. linear or branched carbon chains), and X ^- Is a counter ion. Alternatively, R ¹ And R is ² Each may be with N ⁺ Part of the same groups bound, in this case N ⁺ Is part of a ring structure (i.e., a cyclic N-oxoammonium salt). The cyclic N-oxoammonium salts useful herein have the following structure:

wherein each Me represents methyl, X ^- Is a counter ion, and R is hydrogen (H), acetamido, hydroxyl (-OH), amino (-NH) ₂ ) Carboxyl (-COOH), methoxy (-OCH) ₃ ) Cyano (-CN), oxo (= O), phosphonooxy [ -O-PO (OH) ₂ ]Acetoxy (-O-CO-CH) ₃ ) A benzoyloxy group, an acetamido group, a maleimide group, or an isothiocyanate group. It will be appreciated that in the case where R in structure II is H, the cyclic N-oxo ammonium salt is TEMPO salt. Examples of Structure II wherein R is a moiety other than H are represented at carbon position 4 (wherein N in Structure II ⁺ TEMPO salts substituted in position 1) in the ring. For example, where R is an acetamido group (-NH-CO-CH) ₃ ) In the present case, the cyclic N-oxoammonium salt of structure II is a 4-acetamido-TEMPO salt. Thus, for example, an N-oxoammonium salt herein may be a TEMPO salt having a substitution at carbon position 4. The polysaccharide derivatives as disclosed may be oxidized using TEMPO salts, 4-acetamido-TEMPO salts, and/or any other cyclic N-oxo ammonium salts herein (e.g., structure II).

In some aspects, the N-oxoammonium salts herein (e.g., TEMPO salts, 4-acetamido-TEMPO salts) can be provided by oxidizing N-oxoammonium under aqueous conditions in which the N-oxoammonium salt is intended to contact (and oxidize) the polysaccharide ether. Examples of N-oxoammonium herein have the following structure:

wherein each Me represents methyl, and R is hydrogen (H) (i.e., structure IV is TEMPO), acetamido (-NH-CO-CH) ₃ ) (i.e., structure IV is 4-acetamido-TEMPO), hydroxy (-OH), amino (-NH) ₂ ) Carboxyl (-COOH), methoxy (-OCH) ₃ ) Cyano (-CN), oxo (= O), phosphonooxy [ -O-PO (OH) ₂ ]Acetoxy (-O-CO-CH) ₃ ) A benzoyloxy group, an acetamido group, a maleimide group, or an isothiocyanate group. Each of these agents can be converted to its corresponding oxoammonium salt by contacting it with one or more oxidizing agents (oxidizing agents) under aqueous conditions, as represented by structure II. Thus, structure IV can also be considered a precursor of the N-oxo ammonium salts herein. TEMPO and derivatives thereof For example, the above (e.g., 4-acetamido-TEMPO) is an example of a cyclic nitroxyl compound. Thus, for example, cyclic nitroxyl compounds can be used to provide the N-oxo ammonium salts herein.

The N-oxoammonium reagent may be oxidized to its corresponding N-oxoammonium salt under the aqueous conditions herein by contacting the reagent with one or more other oxidizing agents (oxidizing agents). The contacting may for example be performed under the same aqueous conditions wherein the polysaccharide derivative is intended to be contacted with the N-oxoammonium salt. In some aspects, the reactions used herein to oxidize polysaccharide derivatives may first be prepared to comprise at least one polysaccharide derivative, an N-oxoammonium reagent, and one or more oxidizing agents under aqueous conditions. The one or more oxidizing agents may convert the N-oxoammonium reagent to its corresponding N-oxoammonium salt, which in turn may oxidize the polysaccharide derivative.

Examples of oxidations that can be used to convert the N-oxoammonium reagents herein to their corresponding N-oxoammonium salts (such as TEMPO salts) include rock salts (e.g., chlorites such as sodium chlorite [ NaClO ] ₂ ]) Or hypohalites (e.g., hypochlorites such as sodium hypochlorite [ NaClO ]]) One or more of the following. Additional examples of oxidizing agents that may be used to convert an N-oxoammonium reagent to its corresponding N-oxoammonium salt include one or more of the following: a halide salt such as KCl, KBr, naCl, naBr, or NaI; hypohalites such as NaOBr; metals such as Fe (III), mn (II), mn (III), or Cu (II); KMnO ₄ ；Mn(OAc) ₃ ；Mn ₂ O ₃ ；MnO ₂ ；Mn(NO ₃ ) ₂ ；MgCl ₂ ；Mg(OAc) ₂ ；Cu(NO ₃ ) ₂ The method comprises the steps of carrying out a first treatment on the surface of the Iodobenzene diacetate [ PhI (OAc) ₂ ]；Ca(ClO) ₂ ；t-BuOCl；CuCl-O ₂ ；NaBrO ₂ ；Cl ₂ ；Br ₂ ；NO ₂ ；N ₂ O ₄ The method comprises the steps of carrying out a first treatment on the surface of the And trichloroisocyanuric acid. For example, hypochlorite such as NaClO and halogen salts such as NaBr can be used in combination with an N-oxoammonium reagent such as TEMPO in the oxidation reactants disclosed herein.

In some aspects for oxidation of polysaccharide derivatives hereinThe oxidizing agent of the compound may include one or more periodate compounds. The periodate compound may be, for example, a metal periodate (e.g., sodium periodate or potassium periodate). In some aspects, the periodate compound may be a metaperiodate (e.g., naIO ₄ ) Or a raw periodate. The conditions used herein for oxidizing polysaccharide derivatives with periodate compounds may be, for example, in accordance with those disclosed in U.S. patent nos. 3086969, 6800753, 5747658, or 6635755, or U.S. patent application publication nos. 2015/0259439, 2018/0022834, or 2018/0079732. Typically, the oxidation reaction with periodate involves providing the polysaccharide derivative in an aqueous periodate solution. The concentration of periodate in the reaction may be, for example, about 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%. The temperature of the periodate-containing reactants herein can be, for example, between about 18 ℃ and about 40 ℃ (e.g., room temperature). In some aspects, the reaction comprising periodate may be conducted for about 1-72 hours (e.g., about 5 hours or about 48 hours).

In some aspects, oxidizing the polysaccharide derivative may be produced by first contacting the polysaccharide derivative with a periodate compound, followed by contacting the periodate-oxidized polysaccharide derivative with an N-oxoammonium salt. Such sequential oxidation treatment may be, for example, in accordance with any of the methods disclosed in U.S. patent application publication nos. 2015/0259434, 2018/0022834, or 2018/0079732 (supra).

The oxidizing agent used in some aspects to oxidize the polysaccharide derivatives herein may include one or more peroxide compounds. For example, the peroxide compound may be hydrogen peroxide. In some aspects, the peroxide compound may be an inorganic peroxide compound or an organic peroxide compound. Suitable peroxide compounds herein also include, for example, perborate-monohydrate, perborate-tetrahydrate, percarbonate, basic persulfate, persilicate and percitrate (with sodium or calcium being the preferred cation), and hydrogen peroxide adducts of urea or amine oxide. In some aspects, the oxidized polysaccharide derivative is produced by first contacting the polysaccharide derivative with a peroxide compound, followed by contacting the peroxide oxidized polysaccharide derivative with an N-oxoammonium salt. For example, the amount of peroxide in the oxidation reactant may be about 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%. In some aspects, reactions employing the peroxide compounds herein can have a neutral pH (e.g., pH 6-8). The reaction temperature comprising periodate may be, for example, between about 110 ℃ and about 140 ℃ (e.g., about 121 ℃). It will be appreciated that achieving such elevated reaction temperatures may include applying pressure, such as may be provided with an autoclave or other high pressure device. In some embodiments, the oxidizing reactant comprising peroxide may be conducted for about 30 minutes to about 120 minutes (e.g., about 60 minutes).

The aqueous conditions are used in the reactions used herein to oxidize polysaccharide derivatives. Suitable aqueous conditions for the oxidation reactants herein include solutions or mixtures wherein the solvent is about or at least about 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, or 100wt% water. The aqueous conditions may comprise, for example, a buffer at a suitable concentration, such as an acidic, neutral, or basic buffer, and are selected based on the pH range provided by the buffer. Examples of buffers include citric acid, acetic acid, KH ₂ PO ₄ CHES and borates.

The aqueous conditions herein may be acidic, e.g., have a pH of about or at least about 5.5, 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, or 2.0. Acidic conditions may be prepared by a variety of means, such as by adding acetic acid and/or acetate to the solution or mixture. For example, sodium acetate buffer (acetate buffer) (pH 4-5) (e.g., 0.2-0.3M solution) may provide acidic conditions.

The aqueous conditions herein may be alkaline, e.g., have a pH of about or greater than about 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, or 12. The alkaline conditions can be prepared by a variety of means, such as by adding an alkaline hydroxide (e.g., sodium hydroxide) to the solution or mixture.

The polysaccharide derivatives herein may be included in the oxidation reactant, for example, at about or at least about 0.1wt%, 0.25wt%, 0.5wt%, 0.75wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 17.5wt%, 20wt%, 22.5wt%, 25wt%, 27.5wt%, 30wt%, 32.5wt%, 35wt%, 8wt% -17.5wt%, 8wt% -15wt%, 10wt% -17.5wt%, or 10wt% -15wt% of the reactant. The polysaccharide derivative may be added (e.g., mixed or dissolved) to the aqueous conditions before or after the one or more oxidizing agents are added to the aqueous conditions. Polysaccharide derivatives may be provided in some aspects of preparing the oxidation reactant in dry form (e.g., powder, flakes), wet form (e.g., aqueous solution, wet cake), or in any other suitable form for preparing the oxidation reactant. In some aspects, the polysaccharide derivative may be introduced into the oxidation reactant by utilizing some (e.g., > 90 wt-%), or all, of the derivatization reaction (e.g., etherification, esterification, urethanization, sulfonylation reaction) in which the polysaccharide derivative is produced; i.e. such polysaccharide derivatives are not purified or otherwise isolated before being subjected to an oxidation reaction.

N-oxoammonium reagents such as TEMPO or 4-acetamido-TEMPO can be included in the oxidation reactants herein, for example, at about or at least about 0.05wt%, 0.075wt%, 0.1wt%, 0.25wt%, 0.5wt%, 0.75wt%, 1wt%, or 2wt% of the reaction. In some aspects, an ammonium N-oxide reagent may be added to the oxidation reactant in which the polysaccharide derivative has been mixed or dissolved. Such addition may be performed before, after, or simultaneously with the addition of the oxidizing agent for oxidizing the N-oxoammonium reagent to the N-oxoammonium salt. The oxidizing agent (e.g., sodium bromide and/or sodium hypochlorite) herein can be included in the oxidizing reactant herein, for example, at about or at least about 0.1wt%, 0.25wt%, 0.5wt%, 0.75wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 2wt% -12wt%, 4wt% -12wt%, 2wt% -10wt%, or 4wt% -10wt% of the reactant.

For example, the period of time for which the polysaccharide derivative herein is contacted with at least one oxidizing agent herein under aqueous conditions may be about or at least about 0.5, 1, 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 72, or 96 hours (or any integer value between 1 and 96 hours). In some aspects, the reaction may be maintained for about 0.5-5 hours (e.g., about 1 hour) or 24-96 hours (e.g., about 48 hours). The period of time during which the polysaccharide derivative is contacted with the at least one oxidizing agent under aqueous conditions may be measured, for example, from a point in time after each of the reaction components has been dissolved and/or mixed under aqueous conditions.

In some aspects (e.g., when periodate and/or N-oxoammonium salts are employed), the temperature of the aqueous conditions of the oxidation reaction herein may be from about 18 ℃ to about 40 ℃ (or any integer value between 18 ℃ and 40 ℃). In some aspects, the aqueous conditions may be maintained at a temperature of about 20 ℃ to 25 ℃. The temperature of the aqueous conditions may be maintained from the time at which each of the reaction components is dissolved and/or mixed under the aqueous conditions until the reaction is completed.

After completion of the oxidation reaction in which acidic or basic aqueous conditions are used, the pH of the reaction may optionally be neutralized. Neutralization of the acidic reaction may be carried out using one or more bases, such as alkali metal hydroxides, e.g., sodium hydroxide. Neutralization of the alkaline reaction may be performed using one or more acids (e.g., mineral acids such as hydrochloric acid). The term "neutral pH" as used herein refers to a pH that is neither significantly acidic nor significantly basic (e.g., a pH of about 6-8, or about 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, or 8.0).

The present disclosure also relates to a method of producing oxidized polysaccharide derivatives. The method typically includes:

(a) Contacting the polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative, thereby producing an oxidized polysaccharide derivative, wherein the polysaccharide derivative has a degree of substitution (DoS) with at least one organic group of up to about 3.0; and

(b) Optionally isolating the oxidized polysaccharide derivative. Any of the features described above in relation to oxidizing polysaccharide derivatives can be applied accordingly in the oxidation process.

The oxidized polysaccharide derivatives produced in the oxidation reactions herein may optionally be isolated. In some aspects, such products may be first precipitated from the aqueous conditions of the reaction. Precipitation may be performed by adding an excess (e.g., at least 2-3 volumes of the reaction volume) of an alcohol (e.g., 100% or 95% concentration) such as methanol, ethanol, or isopropanol to the reaction. The precipitated product may then be separated using a filter funnel, centrifuge, filter press, or any other method or apparatus that allows for the removal of liquid from solids. The isolated product may be dried, such as by vacuum drying, air drying, or freeze drying.

In some aspects, oxidized polysaccharide derivative products may be isolated by steps that include filtering the completed reaction, or a water-diluted version thereof, by ultrafiltration (e.g., with a 5 or 10 molecular weight cutoff filter). Optionally, the completed reaction or diluted form thereof may first be periodically filtered (i.e., not ultrafiltered), and the filtrate may then be subjected to ultrafiltration. The concentrated liquid obtained by ultrafiltration may then be dried to its component solids, such as by freeze-drying, or the solids may be precipitated from the liquid and then dried (e.g., freeze-dried).

The oxidized polysaccharide derivative products herein may optionally be washed one or more times with a liquid that does not readily dissolve the compound after precipitation or drying. For example, the oxidation product may be washed with an alcohol, acetone, an aromatic compound, or any combination of these, depending on the solubility of the oxidation product therein (where lack of solubility is desirable for washing). In general, solvents comprising an organic solvent (e.g., 95% -100%) such as an alcohol are preferred for washing the oxidized polysaccharide derivative product. The washing may be performed one or more times with, for example, an aqueous solution containing an alcohol (e.g., methanol or ethanol).

Any of the above oxidation reactions can be repeated using the oxidized polysaccharide derivative products herein as starting materials for further modification. Such further modification may be with the same oxidant as used in the first reaction, or with a different oxidant. In some aspects, the polysaccharide derivative used for oxidation is water insoluble, and in some aspects, water soluble.

The polysaccharide derivatives or oxidized polysaccharide derivatives disclosed herein can be used, for example, in about, at least about, or less than about 0.01, 0.05, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 1.2, 1.25, 1.4, 1.5, 1.6, 1.75, 1.8, 2.0, 2.25, 2.5, 3.0, 3.5, 4.0, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51; 52, 53, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 0.01-0.1, 0.01-0.08, 0.01-0.06, 0.01-0.05, 0.03-0.1, 0.03-0.08, 0.03-0.06, 0.03-0.05, 4-12, 4-10, 4-8, 5-12, 5-10, 5-8, 6-12, 6-10, or 6-8wt% or w/v%, or ranges between any two of these values are present in the composition/system, such as an aqueous composition/system or a dry composition/system. The liquid component of the aqueous composition herein may be, for example, an aqueous fluid, such as water or an aqueous solution. The solvent of the aqueous solution is typically water, or may comprise, for example, about or at least about 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, 95wt%, 98wt%, or 99wt% water. The aqueous or dry compositions mentioned herein may also relate to aqueous or dry systems, respectively.

An aqueous composition comprising a polysaccharide derivative or oxidized polysaccharide derivative herein may have a viscosity of, for example, about or at least about 1, 5, 10, 100, 200, 300, 400, 500, 600, 700, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, or 15000 centipoise (cps). For example, the viscosity may be measured as with the aqueous composition at any temperature between about 3 ℃ and about 80 ℃ (e.g., 4 ℃ to 30 ℃, 15 ℃ to 25 ℃). Viscosity is typicallyMeasured at atmospheric pressure (about 760 torr) or at a pressure of + -10% thereof. The viscosity may be measured using, for example, a viscometer or rheometer, and may optionally be measured, for example, at 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 1.0-100s ^-1 (1/s) under shear rate (rotational shear rate).

In some aspects, an aqueous composition comprising a polysaccharide derivative or an oxidized polysaccharide derivative may have one or more salts/buffers (e.g., na ⁺ 、Cl ^- NaCl, phosphate, tris, citrate) (e.g., 0.1wt%, 0.5wt%, 1.0wt%, 2.0wt%, or 3.0 wt%) and/or, e.g., about 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 4.0-10.0, 4.0-9.0, 4.0-8.0, 5.0-10.0, 5.0-9.0, 5.0-8.0, 6.0-10.0, 6.0-9.0, 6.0-8.0, 9.0-13.5, 10.0-13.5, 10.5-13.5, 11.0-13.5, 9.0-13.0, 10.0 or 13.0-13.0. For example, the polysaccharide derivative or oxidized polysaccharide derivative herein may be anionic or uncharged (nonionic). Typically, oxidized polysaccharide derivatives are anionic. For example, the charge of the polysaccharide derivative or oxidized polysaccharide derivative herein may be that which is present when the polysaccharide derivative or oxidized polysaccharide derivative is in an aqueous composition herein, also taking into account the pH of the aqueous composition (in some aspects, the pH may be 4-10 or 5-9, or any pH as disclosed above).

A composition herein comprising a polysaccharide derivative or an oxidized polysaccharide derivative (e.g., the aqueous composition) may be, for example, at a temperature of about, or up to about, or less than about 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 0-150 ℃, 0-140 ℃, 0-130 ℃, 0-120 ℃, 0-110 ℃, 0-100 ℃, 0-90 ℃, 0 ℃ -80 ℃, 0 ℃ -70 ℃, 0 ℃ -60 ℃, 10 ℃ -160 ℃, 10 ℃ -150 ℃, 10 ℃ -140 ℃, 10 ℃ -130 ℃, 10 ℃ -120 ℃, 10 ℃ -110 ℃, 10 ℃ -100 ℃, 10 ℃ -90 ℃, 10 ℃ -80 ℃, 10 ℃ -70 ℃, 10 ℃ -60 ℃, 50 ℃ -80 ℃, 50 ℃ -75 ℃, 50 ℃ -65 ℃, 55 ℃ -80 ℃, 55 ℃ -75 ℃, 55 ℃ -70 ℃, 55 ℃ -65 ℃, 60 ℃ -80 ℃, 60 ℃ -75 ℃, 60 ℃ -70 ℃, 60 ℃ -65 ℃, 5 ℃ -50 ℃, 15 ℃ -25 ℃, 20 ℃ -30 ℃, or 20 ℃ -40 ℃.

In some aspects, the compositions herein comprising polysaccharide derivatives or oxidized polysaccharide derivatives may be non-aqueous (e.g., dry compositions). Examples of such embodiments include powders, granules, microcapsules, flakes, or any other form of particulate matter. Other examples include larger compositions such as pellets, sticks, cores, beads, tablets, sticks, or other agglomerates. The non-aqueous or dry composition typically has about or no more than about 12, 10, 8, 6, 5, 4, 3, 2, 1.5, 1.0, 0.5, 0.25, 0.10, 0.05, or 0.01wt% water contained therein. In some aspects (e.g., those involving laundry or dishwashing detergents), the dry compositions herein may be provided in pouches or sachets.

In some aspects, the compositions herein comprising a polysaccharide derivative or an oxidized polysaccharide derivative may be a detergent composition. Examples of such compositions are disclosed herein as detergents for dishwashing and as detergents for fabric care.

In some aspects, the compositions herein comprising polysaccharide derivatives or oxidized polysaccharide derivatives may comprise one or more salts, such as sodium salts (e.g., naCl, na ₂ SO ₄ ). Other examples of salts include those having (I) aluminum, ammonium, barium, calcium, chromium (II or III), copper (I or II), iron (II or III), hydrogen, lead (II), lithium, magnesium, manganese (II or III), mercury (I or II), potassium, silver, sodium, strontium, tin (II or IV), or zinc cations, and (II) acetate, borate, bromate, bromide, carbonate, chlorate, chloride, chlorite, chromate, cyanamide, cyanide, dichromate, dihydrogen phosphate, ferricyanide, ferrocyanide, fluoride, bicarbonate, hydrogen phosphate, hydrogen sulfateSalts, hydrogen sulfide, bisulfites, hydrides, hydroxides, hypochlorites, iodates, iodides, nitrates, nitrides, nitrites, oxalates, oxides, perchlorates, permanganates, peroxides, phosphates, phosphides, phosphites, silicates, stannates, stannous salts, sulfates, sulfides, sulfites, tartrates, or those of thiocyanate anions. Thus, for example, any salt having a cation from (i) above and an anion from (ii) above may be in the composition. The salt may be present in the aqueous compositions herein in wt%, for example, or at least about.01,.025,.05,.075,.1,.25,.5,.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.5, 3.0, 3.5,.01-3.5,.5-2.5, or.5-1.5 wt% (such wt% values typically refer to the total concentration of one or more salts).

The compositions herein comprising polysaccharide derivatives or oxidized polysaccharide derivatives may optionally contain one or more enzymes (active enzymes). Examples of suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g. metallolipolytic enzymes), xylanases, lipases, phospholipases, esterases (e.g. aryl esterases, polyester enzymes), perhydrolases, cutinases, pectinases, pectin lyases, mannanases, keratinases, reductases, oxidases (e.g. choline oxidase), phenol oxidases, lipoxygenases, ligninases, pullulanases, tannase, pentosanases, malates (malanases), beta-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, metalloproteases, amadoriases (amadoriases), glucoamylases, arabinofurannases, phytases, isomerases, transferases, nucleases, and amylases. If one or more enzymes are included, they may be included in the compositions herein, for example, in about 0.0001wt% to 0.1wt% (e.g., 0.01wt% to 0.03 wt%) of the active enzyme (e.g., calculated as pure enzyme protein). In fabric care or automatic dishwashing applications, the enzyme (e.g., any of the above, such as cellulase, protease, amylase, and/or lipase) may be present in the aqueous composition (e.g., wash liquor, grey water) in which the fabric or dish is treated, for example, at a concentration of from a minimum of about 0.01 to 0.1ppm total enzyme protein, or from about 0.1 to 10ppb total enzyme protein (e.g., less than 1 ppm) to a maximum of about 100, 200, 500, 1000, 2000, 3000, 4000, or 5000ppm total enzyme protein.

In some aspects, the polysaccharide derivative or oxidized polysaccharide derivative is biodegradable. After 15, 30, 45, 60, 75, or 90 days of testing, for example, such a biodegradation rate may be determined as 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%, 5% -60%, 5% -80%, 5% -90%, 40% -70%, 50% -70%, 60% -70%, 40% -75%, 50% -75%, 60% -75%, 70% -75%, 40% -80%, 50% -80%, 70% -80%, 40% -85%, 50% -85%, 60% -85%, 70% -85%, 40% -90%, 50% -90%, 60% -90%, or any value between 5% -90%, or 5% -and 90% by the carbon dioxide release test method (OECD guideline 301B, incorporated herein by reference). In some aspects, the biodegradability may be in relation to an existing material (e.g., an existing dispersant), such as a polyacrylate. It is contemplated that the biodegradability of the polysaccharide derivative or oxidized polysaccharide derivative herein may be about, at least about, or up to about 10%, 25%, 50%, 75%, 100%, 150%, 200%, 250%, 500%, 750%, or 1000% higher than the biodegradability of the material in use; such a biodegradability may for example be determined as above.

The composition may comprise one, two, three, four or more different polysaccharide derivatives and/or oxidized polysaccharide derivatives herein. For example, the composition may comprise at least one type of oxidized polysaccharide derivative and at least one type of polysaccharide derivative; in some aspects, the latter may be a precursor compound of the former (e.g., carboxymethyl polysaccharide is used with oxidized carboxymethyl polysaccharide).

In some aspects, the polysaccharide derivatives (e.g., dextran substituted with at least one organic group comprising a carboxylic acid group or a sulfonate group) are included hereinSugar) or oxidized polysaccharide derivative further comprises at least one cation, and the polysaccharide derivative or oxidized polysaccharide derivative is bound to the cation. Such binding is typically via ionic binding. Examples of cations include one or more hard water cations such as Ca ²⁺ And/or Mg ²⁺ . The combination of the polysaccharide derivative or oxidized polysaccharide derivative herein with cations in the aqueous composition/system may be used to soften the water of the aqueous composition/system (acting as a builder).

The aqueous composition/system in which the polysaccharide derivative or oxidized polysaccharide derivative herein may be combined with at least one cation may be, for example, a wash liquor/grey water for washing tableware herein (e.g., in an automatic dishwashing machine) or fabric-containing articles herein (e.g., clothing, such as in a laundry machine), or any other aqueous composition/system to which a detergent for washing and/or providing maintenance has been added; such aqueous compositions/systems typically may benefit from the ability of the polysaccharide derivative or oxidized polysaccharide derivative to prevent/reduce negative effects (e.g., scale deposition and/or scale formation) caused by the presence of one or more cations. In some aspects, the aqueous composition/system in which the polysaccharide derivative or oxidized polysaccharide derivative may be combined with at least one cation may be any system disclosed herein in which water or aqueous solution is circulated, transported, and/or stored (the presence of a detergent is not necessarily required); such systems may also typically benefit from the same reasons as disclosed above. Typically, the polysaccharide derivative or oxidized polysaccharide derivative herein may be used as a builder/softener by chelating (sequencing/precipitating) and/or precipitating cations. In some aspects, the aqueous soluble polysaccharide derivative or oxidized polysaccharide derivative herein can bind cations and remain aqueous soluble. The binding (or other interactions, as the case may be) between polysaccharide derivatives or oxidized polysaccharide derivatives and cations herein may prevent/reduce undesirable insoluble salts (e.g., carbonates such as CaCO ₃ Or MgCO ₃ Hydroxides such as Mg (OH) ₂ Or Ca (OH) ₂ Sulfates such as CaSO ₄ ) And/or other insoluble compounds (e.g., calcium and/or magnesium salts of fatty acids such as stearates), and/or their formation of deposits (e.g., scale, scum such as soap scum) that may form in aqueous systems with hard water cations (e.g., prevent/reduce formation by about or at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% compared to the absence of the polysaccharide derivative or oxidized polysaccharide derivative). In some aspects, the scale may comprise CaCO ₃ 、MgCO ₃ 、CaSO ₄ 、Fe ₂ O ₃ FeS, and/or FeS ₂ 。

Some examples of aqueous systems that may be treated herein with the polysaccharide derivatives or oxidized polysaccharide derivatives herein include those of industrial environments, in addition to those mentioned above. Examples of industrial environments herein include those of: energy (e.g., fossil fuels such as petroleum or natural gas), water (e.g., water treatment and/or purification, industrial water, wastewater treatment), agriculture (e.g., grain, fruit/vegetable, fishery, aquaculture, dairy, livestock, wood, plants), chemistry (e.g., pharmaceutical processing, chemical processing), food processing/manufacturing, mining, or transportation (e.g., fresh water and/or sea, train or truck container) industries. Additional examples of aqueous systems that may be treated herein with the polysaccharide derivatives or oxidized polysaccharide derivatives herein include those used for: water treatment, water storage, and/or other aqueous systems (e.g., pipes/conduits, heat exchangers, condensers, filters/filtration systems, storage tanks, water cooling towers, water cooling systems/devices, pasteurizers, boilers, atomizers, nozzles, ship hulls, ballast water). Additional examples of aqueous systems that may be treated herein with the polysaccharide derivatives or oxidized polysaccharide derivatives herein include those of: medical/dental/healthcare environments (e.g., hospitals, clinics, examination rooms, nursing homes), food service environments (e.g., restaurants, employee restaurant kitchens, cafeterias), retail environments (e.g., grocery stores, soft drink machines/vending machines), hospitality/travel environments (e.g., hotel/motel), sports/recreational environments (e.g., swimming pools/bathtubs, hydrotherapy), or office/home environments (e.g., bathrooms, bathtubs/shower rooms, kitchens, appliances [ e.g., washing machines, automatic dish washers, refrigerators, freezers ], water spray systems, household/building plumbing, water storage tanks, water heaters). Additional examples of aqueous systems that may be treated herein with the polysaccharide derivatives or oxidized polysaccharide derivatives herein include those as disclosed in any one of the following: U.S. patent application publication nos. 2013/0029884, 2005/023829, 2010/0298275, 2016/0152495, 2013/0052250, 2015/009891, 2016/0152495, 2017/0044468, 2012/0207699, or 2020/0308592, or U.S. patent nos. 4552591, 4925582, 6478972, 6514458, 6395189, 7927496, or 8784659, all of which are incorporated herein by reference. In some aspects, aqueous systems that may be treated herein comprise (i) brine, such as seawater, or (ii) an aqueous solution having about 2.0wt%, 2.25wt%, 2.5wt%, 2.75wt%, 3.0wt%, 3.25wt%, 3.5wt%, 3.75wt%, 4.0wt%, 2.5wt% to 4.0wt%, 2.75wt% to 4.0wt%, 3.0wt% to 4.0wt%, 2.5wt% to 3.5wt%, 2.75wt% to 3.5wt%, 3.0wt% to 4.0wt%, or 3.0wt% to 3.5wt% of a salt or combination of salts (e.g., including at least NaCl).

In some aspects, oxidized polysaccharide (e.g., oxidized alpha-1, 3-glucan) may be used in place of oxidized polysaccharide derivatives (i.e., oxidized polysaccharide is not a derivative prior to being oxidized). For example, oxidized polysaccharides may be based on any of the polysaccharides as disclosed herein. In some aspects, oxidized polysaccharides (e.g., oxidized alpha-1, 3-glucan) can be combined with hard water salts (e.g., carbonates such as CaCO) ₃ ) Forming a complex; such complexes may comprise a hard water salt encapsulated/covered (e.g., 100%, or at least 80%, 85%, 90%, 95%, 98%, 99% encapsulated/covered) by an oxidized polysaccharide. Such complexes are typically water insoluble; because of this feature, such complexes can be easily removed from the aqueous composition. Thus, further disclosed herein is a method comprising treating a polysaccharide having at least one hard water salt (e.g., a carbonate such as CaCO) ₃ Or MgCO ₃ Hydroxides such as Ca (O)H) ₂ Or Mg (OH) ₂ Sulfates such as CaSO ₄ ) Wherein the treatment results in the formation of a water insoluble complex comprising a hard water salt and an oxidized polysaccharide. The method may optionally further comprise removing all or a substantial portion of the water insoluble complex (complex formed during the treating step) from the aqueous composition. To the extent that the process removes water insoluble hard water salts, the process may optionally be considered a flocculation process. The water insoluble complexes herein comprising at least one oxidized polysaccharide and at least one hard water salt can be used as ingredients in a variety of products, such as paper products. Thus, disclosed herein are products such as paper comprising a complex comprising oxidized polysaccharide and a hard water salt. In some aspects, dextran derivatives or oxidized polysaccharide derivatives as disclosed herein may be used in place of oxidized polysaccharides for methods and compositions related to the removal of hard water salts from aqueous compositions.

A composition, such as an aqueous composition or a non-aqueous composition (above), comprising a polysaccharide derivative or an oxidized polysaccharide derivative herein may be in the form of, for example, a home care product, a personal care product, an industrial product, an ingestible product (e.g., a food product), or a pharmaceutical product, such as described in any of the following: U.S. patent application publication nos. 2018/0022834, 2018/023716, 2018/02023411, 20180079832, 2016/0311935, 2016/0304629, 2015/0232785, 2015/0368594, 2015/0368595, 2016/012445, 2019/0202942, or 2019/0309096, or international patent application publication No. WO 2016/133734, all of which are incorporated herein by reference. In some aspects, a composition comprising a polysaccharide derivative or an oxidized polysaccharide derivative may comprise at least one component/ingredient of a household care product, personal care product, industrial product, pharmaceutical product, or ingestible product (e.g., a food product) as disclosed in any of the foregoing publications and/or as disclosed herein.

It is believed that the polysaccharide derivatives or oxidized polysaccharide derivatives disclosed herein may be used to provide one or more of the following physical properties to personal care products, pharmaceutical products, household products, industrial products, or ingestible products (e.g., food products): for example thickening, freeze/thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, adhesion, suspension, dispersion, gelation, reduced mineral hardness. Examples of the concentration or amount of polysaccharide derivative or oxidized polysaccharide derivative in the product may be, for example, any weight percent provided herein.

The personal care products herein are not particularly limited and include, for example, skin care compositions, cosmetic compositions, antifungal compositions, and antibacterial compositions. The personal care products herein may be in the form of, for example, lotions, creams, pastes, balms, ointments, pomades, gels, liquids, combinations of these, and the like. The personal care products disclosed herein may include at least one active ingredient, if desired. Active ingredients are generally considered to be ingredients that cause the desired pharmacological effect.

In some aspects, a skin care product may be applied to the skin to address skin damage associated with lack of moisture. Skin care products may also be used to address the visual appearance of skin (e.g., reduce the appearance of flaky, cracked, and/or red skin) and/or the feel of skin (e.g., reduce the roughness and/or dryness of skin, while improving the softness and microtexture of skin). Typically, the skin care product may include at least one active ingredient for treating or preventing skin disorders, providing a cosmetic effect, or providing a moisturizing benefit to the skin, such as zinc oxide, petrolatum, white petrolatum, mineral oil, cod liver oil, lanolin, dimethicone, stearin, vitamin a, allantoin, calamine, kaolin, glycerin or colloidal oatmeal, and combinations of these. The skin care product may include one or more natural moisturizing factors such as ceramide, hyaluronic acid, glycerol, squalane, amino acids, cholesterol, fatty acids, triglycerides, phospholipids, glycosphingolipids, urea, linoleic acid, glucosaminodextran, mucopolysaccharide, sodium lactate, or sodium pyrrolidone carboxylate. Other ingredients that may be included in the skin care product include, but are not limited to, glycerides, almond oil, canola oil, squalane, squalene, coconut oil, corn oil, jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter, soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter, palm oil, cholesterol esters, wax esters, fatty acids, and orange peel oil. In some aspects, the skin care product may be an ointment, lotion, or disinfectant (e.g., hand disinfectant).

The personal care products herein may also be in the form of, for example, cosmetics, lipsticks, mascaras, rouges, foundations, cheeks, eyeliners, lip pencils, lip colors, other cosmetics, sunscreens, sunblocks, nail conditioners, body washes (back gels), shower gels (body washes), facial washes, lip balms, skin creams, cold creams, body lotions, body sprays, soaps, body scrubs, exfoliants (exfollives), astringents, neck rinses (hair removal), hair waving solutions (permanent waving solution), anti-dandruff formulations, antiperspirant compositions, deodorants, shaving products, pre-shave products, post-shave products, cleaners, skin gels, hair dyes, dentifrice compositions, toothpastes, or mouthwashes. Examples of personal care products (e.g., cleansers, soaps, scrubs, cosmetics) include carriers or exfoliants (e.g., jojoba beads [ jojoba ester beads ]) (e.g., about 1-10, 3-7, 4-6, or 5 wt%; such agents may optionally be dispersed within the product.

In some aspects, the personal care product may be a hair care product. Examples of hair care products herein include shampoos, conditioners (leave-on or rinse-off), nutritional hair lotions, hair dyes, hair coloring products, hair lightening products, hair care essences, hair anti-frizziness products, hair bifurcation repair products, mousses, hair sprays, and hair styling gels. In some embodiments, the hair care product may be in the form of a liquid, paste, gel, solid, or powder. The hair care products disclosed herein typically comprise one or more of the following ingredients commonly used in formulating hair care products: anionic surfactants such as sodium polyoxyethylene lauryl ether sulfate; cationic surfactants such as stearyl trimethyl ammonium chloride and/or distearyl dimethyl ammonium chloride; nonionic surfactants such as glyceryl monostearate, sorbitan monopalmitate and/or polyoxyethylene cetyl ether; wetting agents, such as propylene glycol, 1, 3-butanediol, glycerol, sorbitol, pyroglutamate, amino acids and/or trimethylglycine; hydrocarbons such as liquid paraffin, vaseline, paraffin wax, squalane and/or olefin oligomers; higher alcohols such as stearyl alcohol and/or cetyl alcohol; a lipid-rich agent; an anti-dandruff agent; a disinfectant; an anti-inflammatory agent; crude drug; water-soluble polymers such as methylcellulose, hydroxycellulose, and/or partially deacetylated chitin; preservatives, such as parabens; an ultraviolet light absorber; a pearlizing agent; a pH regulator; a perfume; and (3) pigment.

The pharmaceutical products herein may be in the form of, for example, emulsions, liquids, elixirs, gels, suspensions, solutions, creams or ointments. Furthermore, the pharmaceutical products herein may be in the form of any of the personal care products disclosed herein, such as antibacterial or antifungal compositions. The pharmaceutical product may further comprise one or more pharmaceutically acceptable carriers, diluents and/or pharmaceutically acceptable salts. The polysaccharide derivatives or oxidized polysaccharide derivatives herein may also be used in capsules, encapsulants, tablets, tablet coatings, and as excipients for medicaments and pharmaceuticals.

The household and/or industrial products herein may take the form, for example, of: dry wall tape bonding compounds; mortar; grouting; cement gypsum; spraying gypsum; cement plaster; an adhesive; a paste; wall/ceiling modifiers; adhesives and processing aids for tape casting, extrusion, injection molding and ceramics; spray adhesives and suspension/dispersion aids for pesticides, herbicides and fertilizers; fabric care products such as fabric softeners and laundry detergents; a hard surface cleaner; an air freshener; a polymer emulsion; a latex; gels, such as water-based gels; a surfactant solution; coatings, such as water-based coatings; a protective coating; an adhesive; sealant and caulking; inks, such as water-based inks; a metal working fluid; a film or coating; or emulsion-based metal cleaning solutions for electroplating, phosphating, galvanization and/or general metal cleaning operations. In some aspects, the polysaccharide derivative or oxidized polysaccharide derivative herein is included in a fluid as a viscosity modifier and/or drag reducer; such uses include downhole operations/fluids (e.g., hydraulic fracturing and enhanced oil recovery).

In some aspects, the compositions comprising the polysaccharide derivatives or oxidized polysaccharide derivatives herein may be in the form of a fabric care composition. For example, the fabric care composition may be used for hand washing, machine washing, and/or other purposes, such as soaking and/or pretreatment of fabrics. The fabric care composition may take the form: for example, laundry detergents; a fabric conditioner; any product added during washing, rinsing or drying; unit dose or spray. The fabric care composition in liquid form may be in the form of an aqueous composition. In other embodiments, the fabric care composition may be in a dry form, such as a granular detergent or dryer added fabric softener sheet. Other non-limiting examples of fabric care compositions may include: general purpose or heavy duty detergents in particulate or powder form; general purpose or heavy duty detergents in liquid, gel or paste form; liquid or dry fine fabric (e.g., delicate laundry) detergents; cleaning aids such as bleach additives, "detergent bars" or pretreatments; substrate-containing products such as dry and wet wipes, pads or sponges; sprays and fine mists; a water-soluble unit dose article. As further examples, the compositions herein may be in the form of a liquid, gel, powder, hydrocolloid, aqueous solution, granule, tablet, capsule, bead or lozenge, single-compartment pouch, multi-compartment pouch, single-compartment pouch, or multi-compartment pouch.

The detergent compositions herein may be in any useful form, such as powders, granules, pastes, bars, unit doses, or liquids. The liquid detergent may be aqueous, typically comprising up to about 70wt% water and 0wt% to about 30wt% organic solvent. The liquid detergent may also be in the form of a compact gel type containing only about 30wt% water.

The detergent composition (e.g., a composition of a fabric care product or any other product herein) typically comprises one or more surfactants, wherein the surfactants are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, semi-polar nonionic surfactants, and mixtures thereof. In some embodiments, the surfactant is present at a level of from about 0.1% to about 60%, and in alternative embodiments, from about 1% to about 50%, and in still further embodiments, from about 5% to about 40%, by weight of the detergent composition. Typically, the detergent will contain from 0wt% to about 50wt% of an anionic surfactant such AS Linear Alkylbenzene Sulfonate (LAS), alpha Olefin Sulfonate (AOS), alkyl sulfate (fatty Alcohol Sulfate) (AS), alcohol ethoxy sulfate (AEOS or AES), secondary Alkane Sulfonate (SAS), alpha-sulfo fatty acid methyl ester, alkyl-or alkenyl succinic acid or soap. Additionally, the detergent composition may optionally contain from 0wt% to about 40wt% of a nonionic surfactant, such as an alcohol ethoxylate (AEO or AE), carboxylated alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, or polyhydroxy alkyl fatty acid amide (as described, for example, in WO 92/06154, which is incorporated herein by reference). However, in some aspects, the detergent composition does not comprise a surfactant, or has less than 5wt%, 4wt%, 3wt%, 2wt%, 1wt%, 0.5wt%, 0.25wt%, 0.1wt%, 0.05wt%, or 0.025wt% surfactant (e.g., such "detergent composition" may optionally be referred to as a "composition", "wash composition", or "treatment composition"; in some aspects, any disclosure of detergent composition herein does not necessarily require the inclusion of a surfactant).

In addition to the polysaccharide derivatives and/or oxidized polysaccharide derivatives disclosed herein that may be used as builders, the detergent compositions herein may optionally further comprise one or more detergent builders or builder systems. In some aspects, oxidized alpha-1, 3-glucan may be included as a co-builder; the compounds useful for oxidizing alpha-1, 3-glucan are disclosed herein in U.S. patent application publication No. 2015/0259439. In some aspects incorporating at least one builder, the cleaning composition comprises at least about 1%, from about 3% to about 60%, or even from about 5% to about 40% builder by weight of the composition. Examples of builders include alkali metal, ammonium and alkanolammonium salts of polyphosphates; alkali metal silicates, alkaline earth metals and alkali metal carbonates; an aluminosilicate; a polycarboxylic acid compound; ether hydroxy polycarboxylic esters; copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid, and carboxymethyl oxy succinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acid, such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; along with polycarboxylic acids (polycarboxylates) such as mellitic acid, succinic acid, citric acid, oxo disuccinic acid (oxydisuccinic acid), polymaleic acid, benzene 1,3, 5-tricarboxylic acid, carboxymethyl oxysuccinic acid and soluble salts thereof. Additional examples of detergent builders or complexing agents include zeolites, bisphosphates, triphosphates, phosphonates, citrates, nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTMPA), alkyl or alkenyl succinic acids, soluble silicates or layered cinnamates (e.g., SKS-6 from Helrst company (Hoechst)).

In some embodiments, the builder forms water-soluble hard ion complexes (e.g., chelating builders), such as citrates and polyphosphates (e.g., sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate, and mixed sodium tripolyphosphate and potassium tripolyphosphate, etc.). It is contemplated that any suitable builder will be useful in the present disclosure, including those known in the art (see, e.g., EP 2100949).

In some embodiments, suitable builders may include phosphate builders and non-phosphate builders. In some embodiments, the builder is a phosphate builder. In some embodiments, the builder is a non-phosphate builder. The builder may be used at a level of from 0.1% to 80%, or from 5% to 60%, or from 10% to 50% by weight of the composition. In some embodiments, the product comprises a mixture of phosphate and non-phosphate builder. Suitable phosphate builders include the mono-, di-, tri-or oligomeric polyphosphates, including alkali metal salts, including sodium salts, of these compounds. In some embodiments, the builder may be Sodium Tripolyphosphate (STPP). In addition, the composition may comprise carbonates and/or citrates, preferably citrates, which help to achieve neutral pH compositions. Other suitable non-phosphate builders include homopolymers and copolymers of polycarboxylic acids and partially or fully neutralized salts thereof, monomeric polycarboxylic acids and hydroxycarboxylic acids and salts thereof. In some embodiments, salts of the above compounds include ammonium and/or alkali metal salts, i.e., lithium, sodium and potassium salts, including sodium salts. Suitable polycarboxylic acids include acyclic, cycloaliphatic, heterocyclic and aromatic carboxylic acids, wherein in some embodiments they may contain at least two carboxyl groups, which are in each case separated from one another, in some cases by no more than two carbon atoms.

The detergent compositions herein may comprise at least one chelating agent. Suitable chelating agents include, but are not limited to, copper, iron, and/or manganese chelating agents and mixtures thereof. In embodiments where at least one chelating agent is used, the composition comprises from about 0.1% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the composition.

The detergent compositions herein may comprise at least one deposition aid. Suitable deposition aids include, but are not limited to, polyethylene glycol, polypropylene glycol, polycarboxylates, soil release polymers (such as polyethylene terephthalate), clays such as kaolin, montmorillonite, attapulgite, illite, bentonite, halloysite, and mixtures thereof.

The detergent compositions herein may comprise one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones, polyvinylimidazoles, or mixtures thereof. Additional dye transfer inhibitors include manganese phthalocyanine, peroxidase, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles, and/or mixtures thereof; chelating agents, examples of which include ethylenediamine tetraacetic acid (EDTA); diethylenetriamine pentamethylenephosphonic acid (DTPMP); hydroxyethane diphosphonic acid (HEDP); ethylenediamine N, N' -disuccinic acid (EDDS); methylglycine diacetic acid (MGDA); diethylenetriamine pentaacetic acid (DTPA); propylene diamine tetraacetic acid (PDT a); 2-hydroxypyridine-N-oxide (HPNO); or methylglycine diacetic acid (MGDA); in embodiments where at least one dye transfer inhibitor is used, the compositions herein may comprise from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3% of the at least one dye transfer inhibitor by weight of the composition, of glutamic acid N, N-diacetic acid (N, N-dicarboxymethyl glutamic acid tetrasodium salt (GLDA), nitrilotriacetic acid (NTA), 4, 5-dihydroxyisophthalic acid, citric acid and any salts thereof, N-hydroxyethyl ethylenediamine triacetic acid (HEDTA), triethylenetetramine hexaacetic acid (TTHA), N-hydroxyethyl iminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediamine tetrapropionic acid (EDTP), and derivatives thereof.

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

The detergent compositions herein may comprise a dispersant. Suitable water-soluble organic materials include, but are not limited to, homo-or co-polymeric acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms.

The detergent compositions herein may additionally comprise, for example, one or more enzymes as disclosed hereinabove. In some aspects, the detergent composition may comprise one or more enzymes, each at a level of from about 0.00001% to about 10% by weight of the composition, and the balance of cleaning adjunct materials by weight of the composition. In some other aspects, the detergent composition may further comprise each enzyme at a level of from about 0.0001% to about 10%, from about 0.001% to about 5%, from about 0.001% to about 2%, or from about 0.005% to about 0.5% by weight of the composition. Enzymes contained in the detergent compositions herein may be stabilized using conventional stabilizers such as, for example: polyols such as propylene glycol or glycerol; sugar or sugar alcohol; lactic acid; boric acid or a boric acid derivative (e.g., an aromatic borate).

In some aspects, the detergent composition may comprise one or more other types of polymers in addition to the polysaccharide derivative or oxidized polysaccharide derivative as disclosed herein. Examples of other types of polymers useful herein include carboxymethyl cellulose (CMC), dextran, poly (vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly (vinyl alcohol) (PVA), polycarboxylic acid esters such as polyacrylates, maleic/acrylic acid copolymers, and lauryl methacrylate/acrylic acid copolymers.

The detergent compositions herein may contain a bleach system. For example, the bleaching system may comprise H ₂ O ₂ Sources such as perboric acid or percarbonic acid, which may be combined with a peracid-forming bleach activator such as tetraacetylethylene diamine (TAED) or nonanoyloxybenzene sulfonate (NOBS). Alternatively, the bleaching system may comprise a peroxyacid (e.g., an amide, imide, or sulfone type peroxyacid). Still alternatively, the bleaching system may be an enzymatic bleaching system comprising a perhydrolase enzyme, such as for example the system described in WO 2005/056783.

The detergent compositions herein may also contain conventional detergent ingredients such as fabric conditioning agents, clays, suds boosters, suds suppressors, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, bactericides, color-changing inhibitors, optical brighteners or perfumes. The pH of the detergent compositions herein (measured in use of a concentrated aqueous solution) is generally neutral or alkaline (e.g., pH from about 7.0 to about 11.0).

Examples of suitable anti-redeposition agents and/or clay soil removal agents for use in fabric care products herein include polyethoxy zwitterionic surfactants, water-soluble copolymers of acrylic or methacrylic acid and acrylic or methacrylic acid-ethylene oxide condensates (e.g., U.S. patent No. 3719647), cellulose derivatives such as carboxymethyl cellulose and hydroxypropyl cellulose (e.g., U.S. patent nos. 3597416 and 3523088), and mixtures comprising nonionic alkyl polyethoxy surfactants, polyethoxy alkyl quaternary cationic surfactants, and fatty amide surfactants (e.g., U.S. patent No. 4228044). Non-limiting examples of other suitable anti-redeposition and clay soil removal agents are disclosed in U.S. patent nos. 4597898 and 4891160 and international patent application publication No. WO 95/32272, which are incorporated herein by reference in their entirety.

Particular forms of detergent compositions that may be suitable for the purposes disclosed herein are disclosed in, for example, US20090209445 A1, US20100081598 A1, US 7001878 B2, EP 1504994 B1, WO 2001085888 A2, WO 2003089562 A1, WO 20090998659 A1, WO 20090998660 A1, WO 200912992 A1, WO 200924160 A1, WO 200952031 A1, WO 2010059483 A1, WO 2010088112 A1, WO 2010090915 A1, WO 20101335238 A1, WO 201201102686887 A1, WO 201201101127102 A1, WO 201110678 A1, WO 2012011106767 A1, WO 2006007911 A1, WO 2012027404 A1, EP 1740690 B1, WO 2012059336 A1, US 67306846 B1, WO 201016139 A1, and WO 2012104613A1, all of which are incorporated herein by reference.

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

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

The detergents herein, such as heavy duty laundry detergent compositions, may optionally include additional polymers, such as soil release polymers (including anionically end capped polyesters (e.g., SRP 1), polymers in random or block configuration comprising at least one monomer unit selected from the group consisting of sugars, dicarboxylic acids, polyols, and combinations thereof, ethylene glycol terephthalate-based polymers in random or block configuration, and copolymers thereof, such as REPEL-O-TEX SF, SF-2, and SRP6, TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN300, and SRN325, MARRoQUEST SL); the one or more anti-redeposition agents herein (0.1 wt% to 10 wt%) include carboxylate polymers, such as polymers comprising at least one monomer selected from the group consisting of acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and any mixtures thereof; a vinylpyrrolidone homopolymer; and/or polyethylene glycols, molecular weights ranging from 500 to 100,000 da); and polymeric carboxylic esters (such as maleate/acrylate random copolymers or polyacrylate homopolymers).

The detergents herein, such as heavy duty laundry detergent compositions, may optionally further comprise saturated or unsaturated fatty acids, preferably saturated or unsaturated C12-C24 fatty acids (0 wt% to 10 wt%); deposition aids (examples of which include polysaccharides, cellulosic polymers, polydipropylene dimethyl ammonium halide (DADMAC), and copolymers of DAD MAC with vinyl pyrrolidone, acrylamide, imidazole, imidazoline halides, and mixtures thereof (in random or block configurations), cationic guar gum, cationic starch, cationic polyacrylamide, and mixtures thereof.

The detergents herein, e.g., heavy duty laundry detergent compositions, may optionally further comprise dye transfer inhibitors, examples of which include manganese phthalocyanine, peroxidases, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles, and/or mixtures thereof; chelating agents, examples of which include ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentamethylenephosphonic acid (DTPMP), hydroxyethanediphosphonic acid (HEDP), ethylenediamine N, N' -disuccinic acid (EDDS), methylglycine diacetic acid (MGDA), diethylenetriamine pentaacetic acid (DTPA), propylenediamine tetraacetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO), or methylglycine diacetic acid (MGDA), glutamic acid N, N-diacetic acid (N, N-dicarboxymethylglutamic acid tetrasodium salt (GLDA), nitrilotriacetic acid (NTA), 4, 5-dihydroxyisophthalic acid, citric acid and any salts thereof, N-hydroxyethylethylenediamine triacetic acid (HEDTA), triethylenetetramine hexaacetic acid (TTHA), N-hydroxyethylethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediamine tetrapropionic acid (EDTP), and derivatives thereof.

The detergents herein, such as heavy duty laundry detergent compositions, may optionally include a silicone or fatty acid based suds suppressor; hueing dye, calcium and magnesium cations, visual signaling component, antifoam agent (0.001 wt% to about 4.0 wt%), and/or structuring/thickening agent (0.01 wt% to 5 wt%), selected from the group consisting of: diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, superfine cellulose, biopolymers, xanthan gum, gellan gum, and mixtures thereof). The structurant may also be referred to as a structurant (structurant).

For example, the detergents herein may be in the form of heavy duty dry/solid laundry detergent compositions. Such detergents may include: (i) Cleaning surfactants such as any of the anionic cleaning surfactants disclosed herein, any of the nonionic cleaning surfactants disclosed herein, any of the cationic cleaning surfactants disclosed herein, any of the zwitterionic and/or amphoteric cleaning surfactants disclosed herein, any of the amphoteric surfactants, any of the semi-polar nonionic surfactants, and mixtures thereof; (ii) Builders such as any phosphate-free builder (e.g., zeolite builder in the range of 0wt% to less than 10 wt%), any phosphate builder (e.g., sodium tripolyphosphate in the range of 0wt% to less than 10 wt%), citric acid, citrate and nitrilotriacetic acid, any silicate (e.g., sodium or potassium silicate or sodium metasilicate in the range of 0wt% to less than 10 wt%); any carbonate (e.g., sodium carbonate and/or sodium bicarbonate in the range of 0wt% to less than 80 wt%) and mixtures thereof; (iii) Bleaching agents such as any photobleach (e.g., sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, xanthene dye, and mixtures thereof); any hydrophobic or hydrophilic bleach activator (e.g., dodecanoyloxy benzene sulfonate, decanoyloxy benzoic acid or salts thereof, 3, 5-trimethylhexanoyloxy benzene sulfonate, tetraacetylethylene diamine-TAED, nonanyloxy benzene sulfonate-NOBS, nitrile quaternary ammonium salts, and mixtures thereof); any hydrogen peroxide source (e.g., inorganic peroxyhydrate salts, examples of which include mono-or tetrahydrated sodium salts of perborate, percarbonate, persulfate, perphosphate, or persilicate salts); any preformed hydrophilic and/or hydrophobic peracids (e.g., percarboxylic acids and salts, percarbonic acids and salts, periodic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof); and/or (iv) any other component such as bleach catalysts (e.g., imine bleach boosters, examples of which include ammonium sulfite cations and polyanions, imine zwitterionic, modified amines, modified amine oxides, N-sulfonylimines, N-phosphonoimines, N-acyl imines, thiadiazole dioxides, perfluorinated imines, cyclic sugar ketones, and mixtures thereof) and metal-containing bleach catalysts (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, as well as auxiliary metal cations (such as zinc or aluminum) and chelants (such as EDTA, ethylenediamine tetra (methylene phosphonic acid)).

The detergents herein, such as those used for fabric care (e.g., laundry), may be contained in, for example, a unit dose (e.g., a pouch or sachet). The unit dosage form may comprise a water-soluble outer film that completely encapsulates the liquid or solid detergent composition. A unit dose may comprise a single compartment, or at least two, three, or more (multiple) compartments. The plurality of compartments may be arranged in a stacked orientation or in a side-by-side orientation. The unit dose herein is typically a closed structure of any form/shape suitable for containing and protecting its contents without allowing the contents to be released prior to contact with water.

The compositions disclosed herein comprising polysaccharide derivatives or oxidized polysaccharide derivatives may, for example, be in the form of a dishwashing detergent composition. Examples of dish detergents include automatic dish detergents (typically used in dish washing machines) and hand dish detergents. The dishwashing detergent composition can, for example, be in any dry or liquid/aqueous form as disclosed herein. Components that may be included in some aspects of the dishwashing detergent composition include, for example, one or more of the following: phosphate; bleaching agents based on oxygen or chlorine; a nonionic surfactant; alkaline salts (e.g., metasilicate, alkali metal hydroxide, sodium carbonate); any of the active enzymes disclosed herein; corrosion inhibitors (e.g., sodium silicate); a defoaming agent; additives to slow down the removal of glaze and pattern from the ceramic; a perfume; anti-caking agents (in granular detergents); starch (in tablet-based detergents); gelling agents (in liquid/gel-based detergents); and/or sand (powdered detergents).

A dishwashing detergent such as an automatic dishwasher detergent or a liquid dishwashing detergent may comprise (i) a nonionic surfactant comprising any ethoxylated nonionic surfactant, alcohol alkoxylate surfactant, epoxy-capped poly (oxyalkylated) alcohol, or amine oxide surfactant present in an amount from 0 to 10 wt%; (ii) About 5-60wt% builder including any phosphate builder (e.g., mono-phosphate, di-phosphate, tri-phosphate, other oligomeric polyphosphates, sodium tripolyphosphate-STPP), any phosphate-free builder (e.g., amino acid based compounds including methyl-glycine-diacetic acid [ MGDA ] and salts or derivatives thereof, glutamic acid-N, N-diacetic acid [ GLDA ] and salts or derivatives thereof, iminodisuccinic acid (IDS) and salts or derivatives thereof, carboxymethyl inulin and salts or derivatives thereof, nitrilotriacetic acid [ NTA ], diethylenetriamine pentaacetic acid [ DTPA ], B-alanine diacetic acid [ B-ADA ] and salts thereof), homopolymers and copolymers of polycarboxylic acids and partially or fully neutralized salts thereof, monomeric polycarboxylic and hydroxycarboxylic acids and salts thereof in the range of 0.5wt% to 50wt%, or sulfonated/carboxylated polymers in the range of about 0.1wt% to about 50 wt%; (iii) Drying aids (e.g., polyesters, particularly anionic polyesters (optionally together with additional monomers having 3 to 6 functional groups, typically acid, alcohol or ester functional groups, which facilitate polycondensation), polycarbonate-, polyurethane-, and/or polyurea-polyorganosiloxane compounds or precursor compounds thereof, particularly reactive cyclic carbonates and urea types) in the range of about 0.1wt% to about 10 wt%; (iv) Silicate (e.g., sodium silicate or potassium silicate such as sodium disilicate, sodium metasilicate, and crystalline phyllosilicate) in the range of from about 1wt% to about 20 wt%; (v) Inorganic bleaching agents (e.g., peroxyhydrate salts such as perborates, percarbonates, perphosphates, persulfates, and persilicates) and/or organic bleaching agents (e.g., organic peroxy acids such as diacyl-and tetraacyl peroxides, particularly diperoxydodecanedioic acid, diperoxydetradecyldiacid, and diperoxydischiadic acid); (vi) Bleach activators (e.g., organic peracid precursors in the range of from about 0.1wt% to about 10 wt%) and/or bleach catalysts (e.g., manganese triazacyclononane and related complexes; co, cu, mn and Fe bipyridyl amines and related complexes; and cobalt (III) pentaamine acetate and related complexes); (vii) Metal care agents (e.g., benzotriazoles, metal salts and complexes, and/or silicates) in the range of from about 0.1wt% to 5 wt%; (viii) Glass corrosion inhibitors (e.g., salts and/or complexes of magnesium, zinc, or bismuth) in the range of about 0.1wt% to 5 wt%; and/or (ix) any of the active enzymes disclosed herein (ranging from about 0.01 to 5.0mg active enzyme per gram of automatic dishwashing detergent composition) and enzyme stabilizer components (e.g., oligosaccharides, polysaccharides, and inorganic divalent metal salts). In some aspects, the dishwashing detergent ingredients or the entire composition (but adjusted accordingly to include the polysaccharide derivative or oxidized polysaccharide derivative herein) may be as disclosed in U.S. patent No. 8575083 or 9796951, or U.S. patent application publication No. 2017/0044468, each of which is incorporated herein by reference.

The detergents herein, such as those used for dishwashing, may be contained, for example, in unit doses (e.g., pouches or sachets) (e.g., water-soluble unit dose articles), and may be as described above for fabric care detergents, but comprise suitable dishwashing detergent compositions.

It is believed that many commercially available detergent formulations can be tailored to contain polysaccharide derivatives or oxidized polysaccharide derivatives as disclosed herein. Examples of commercially available detergent formulations includeULTRAPACKS (Hangao Co., ltd. (Henkel)) @>QUANTUM (Reckitt Benckiser) CLOROX) ^TM 2PACKS (Clorox), OXICLEAN MAX FORCE POWER PAKS (Church, duwei cut&Dwight))、/>STAIN RELEASE、/>ACTIONPACS, and->PODS ^TM (Procter Co., ltd&Gamble))。

Some aspects herein relate to a detergent composition comprising:

(i) A dextran derivative substituted with at least one organic group comprising a carboxylic acid group (carboxyl) or a sulfonate group, wherein the degree of substitution with organic groups (DoS) of the dextran derivative is about 0.1 to about 3.0, wherein the dextran from which the dextran derivative is derived has a weight average degree of polymerization (DPw) of at least about 50, and optionally wherein at least 50% of the glycosidic linkages of the dextran derivative are alpha-1, 3, alpha-1, 4, or alpha-1, 6 linkages; and/or

(ii) Oxidized polysaccharide derivatives, wherein the oxidized polysaccharide derivatives are produced by contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative (such derivative may be, for example, any oxidized polysaccharide derivative as disclosed herein);

wherein the hard surface washed or treated in a wash/treat composition comprising a detergent composition has reduced filming, spotting, turbidity, or other deposition. Such detergent compositions may optionally be characterized as anti-deposition or anti-accumulation detergent compositions.

The glucan derivative in some aspects of the anti-deposition detergent composition may be any glucan derivative as disclosed herein (e.g., as it exists before or after being oxidized) so long as it has a DoS with an organic group comprising a carboxylic acid group or sulfonate group of about 0.1 to about 3.0 and the α -glucan from which the α -glucan derivative is derived has a DPw of at least about 50. DoS may be any DoS disclosed herein that falls within a range of 0.1 to 3.0 or a range thereof. For example, doS may be about 0.3-1.0 or 0.3-1.5. The DPw may be any DPw disclosed herein that is at least 50 or a range thereof. For example, DPw may be at least 100. In some aspects, at least 50% of the glycosidic linkages of the α -glucan derivative are α -1,3 linkages.

For example, the glucan derivative of the anti-deposition detergent compositions herein may be substituted with at least one organic group comprising a carboxylic acid group. For example, such organic groups may optionally be bonded to the dextran derivative in an ether, ester, carbamate, or sulfonyl linkage. In some aspects, the organic group may itself be a carboxylic acid group (e.g., carbon 6 of a glucose monomer based on a dextran derivative), or may be an organic group that itself is substituted with a carboxyl group. Examples of this latter type of organic group include carboxyalkyl groups such as carboxymethyl, carboxyethyl, carboxypropyl and carboxybutyl. In some aspects, the glucan derivative is an alpha-glucan derivative (e.g., an ether derivative) (e.g., doS, which may contain at least 50% of alpha-1, 3 linkages as disclosed herein) (e.g., based on an alpha-glucan having a DPw 600-900, 600-850, 600-800, 650-900, 650-850, 650-800, 700-900, 700-850, or 700-800) may be substituted with only carboxyalkyl groups (e.g., carboxymethyl groups) (e.g., with about 0.7-1.1, 0.7-1.0, 0.8-1.1, 0.8-1.0, or 0.85-0.95 DoS), or with carboxyalkyl groups (e.g., carboxymethyl groups) (e.g., 1.6-1.9, 1.6-1.85, 1.6-1.8, 1.65-1.9, 1.65-1.85, 1.65-1.8, 1.7-1.9, 1.7-1.85, or 1.7-1.85) and another organic group (e.15.0.25-0, 0.15.15) such as benzyl groups, 0.15-0.15.0.0, 0.15, 0.95).

Hard surfaces washed or treated in a wash/treat composition comprising an anti-deposition detergent composition herein may have reduced filming, spotting, turbidity, or other deposition. In some aspects, the wash/treat composition may be a wash liquor (grey water) to which the anti-deposition detergent composition has been added (e.g., the detergent may be provided in concentrated form and diluted into the wash/treat composition as the wash is performed). The washing/treatment composition herein may be, for example, a composition used in an automatic dishwashing or laundry machine; the characteristics of such wash/treat compositions may be as disclosed herein for dishwashing and fabric care compositions. In some aspects, the washing/treatment composition comprises at least one cation, and the glucan derivative or oxidized polysaccharide derivative is bound to the cation; this aspect may have any of the features disclosed herein with respect to cation binding.

The anti-deposition detergent composition may be formulated, for example, according to any of the automatic dishwashing or fabric care compositions as disclosed herein or in the incorporated references, and/or contain any of the disclosed ingredients (e.g., surfactants, enzymes, etc.), and/or in any of the forms disclosed herein (e.g., powder, flakes, liquid, unit dose, etc.). (i) The amount of glucan derivative of (a) or oxidized glucan derivative of (ii) can be, for example, about, or at least about 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 4wt% -10wt%, 4wt% -8wt%, 5wt% -12wt%, 5wt% -10wt%, 5wt% -8wt%, 6wt% -12wt%, 6wt% -10wt%, or 6wt% -8wt%. In some aspects, the anti-deposition detergent composition has each of these ingredients listed in table 2 below; the amount (wt%) of each component in such a composition may be within 5%, 10%, 15%, 5% -10%, or 5% -15% (add/subtract) of the corresponding values in table 2.

Some aspects of the present disclosure relate to a method of washing/cleaning or treating a hard surface. Such washing/cleaning or treatment methods may include:

(a) Contacting a hard surface with a wash/treat composition comprising an anti-deposition detergent composition herein, and

(b) Removing all or part of the wash/treat composition from the hard surface (e.g., by rinsing with water with or without rinse aid and/or added salt); thereby washing/cleaning or treating the hard surface, wherein the washed/cleaned/treated hard surface has reduced filming, spotting, cloudiness, or other deposition. Such methods can include, for example, any of the conditions (e.g., temperature, pH, time, salt/buffer, etc.) disclosed herein suitable for washing, treating materials/surfaces, and/or cation binding (e.g., conditions for an automatic dishwasher).

The hard surface treated by the wash/clean method may be any hard surface, such as, or associated/interacted with, the hard surface of an aqueous composition or system as disclosed herein. Examples of hard surfaces include or consist of glass, plastic (e.g., styrene-acrylonitrile, polystyrene, polypropylene, polyethylene, melamine), ceramic, porcelain, metal (e.g., steel, stainless steel, aluminum), or stone (e.g., marble, granite); any of these surfaces may be, for example, the surface of a piece of cutlery as disclosed herein. In some aspects, the hard surface may be a surface found within an automatic dishwasher, washing machine, or similar device (e.g., body/housing), and/or internal components thereof (e.g., duct, sprayer, nozzle, rack, agitator).

In some aspects of the washing/cleaning method in which the automatic dishwasher is operated, the washing cycle may comprise the following successive cycles: (i) Optionally at least one pre-wash period during which water is circulated (e.g., at about 40-70 ℃, 45-70 ℃, 50-70 ℃, or 60-70 ℃) for about 3-15, 3-10, or 3-6 minutes) to loosen food materials on the cutlery; (ii) A main wash period during which the anti-deposition detergent composition herein (e.g., about 10-30, 10-25, 10-20, 15-30, 15-25, or 15-20g, dry weight) (e.g., via an automatic dispenser) is added to water (e.g., at about 40 ℃ -70 ℃, 45 ℃ -70 ℃, or 50 ℃ -70 ℃) (e.g., about 1-2.5, 1-2, 1.5-2.5, or 1.5-2 gallons) for circulation (thereby providing a wash composition) for a suitable amount of time (e.g., about 3-20, 3-15, 3-10, 5-20, 5-15, or 5-10 minutes); (iii) At least one rinse period during which water is circulated (e.g., at about 40-70 ℃, 45-70 ℃, 50-70 ℃, or 60-70 ℃) (e.g., for about 3-15, 3-10, or 3-6 minutes); and (iv) optionally a drying stage. After each of periods (ii) and (iii) of the wash cycle (and optionally after period [ i ]), the circulating liquid is typically removed, such as by pumping and/or draining.

The washing/cleaning methods herein can be performed to wash dishes (e.g., using an automatic dish washer, or manual/hand dish washing). For example, cutlery may be as disclosed herein or in U.S. patent No. 8575083 or U.S. patent application publication No. 2017/0044468, which are incorporated herein by reference. For example, cutlery may include plates, cups, glassware, bowls, tubs, cutlery, spoons, knives, forks, serving utensils, ceramics, plastics, cutting boards, porcelain, ceramic ware, glassware, eating utensils (tableware), cookware (utensilwire), and kitchen ware.

Hard surfaces washed by the washing/cleaning methods herein have reduced filming, spotting, turbidity and/or other deposits. In some aspects, the reduction is about, or at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% compared to that which would be observed using a washing/cleaning method of a detergent composition that does not have (i) a glucan derivative substituted with at least one organic group comprising a carboxylic acid group (carboxyl) or a sulfonate group, and/or (ii) an oxidized polysaccharide derivative; in addition to this, all other features of the comparative washing/cleaning method may be identical. Film formation, spotting, cloudiness and related deposits typically contain one or more insoluble salts (e.g., carbonates such as CaCO ₃ Or MgCO ₃ Hydroxides such as Mg (OH) ₂ Or Ca (OH) ₂ Sulfates such as CaSO ₄ ) And/or other insoluble compounds (e.g., calcium and/or magnesium salts of fatty acids such as stearic acid). Film formation and/or spotting may also optionally be referred to as deposition of scale and/or scale slivers (e.g., soap scum).

The compositions disclosed herein comprising polysaccharide derivatives or oxidized polysaccharide derivatives may, for example, be in the form of oral care compositions. Examples of oral care compositions include dentifrices, toothpastes, mouthwashes, mouth rinses, chewing gums, and edible strips (ediblestrips) that provide some form of oral care (e.g., treating or preventing cavities [ caries ], gingivitis, plaque, tartar, and/or periodontal disease). The oral care composition can also be used to treat "oral surfaces," which encompass any soft or hard surface within the oral cavity, including the following surfaces: the tongue, hard and soft palate, buccal mucosa, gums and surfaces of teeth. "tooth surface" herein is the surface of a natural tooth or the hard surface of an artificial dentition (including, for example, crowns, caps, fillings, bridges, dentures or dental implants).

The oral care compositions herein can comprise, for example, about 0.01wt% to 15.0wt% (e.g., about 0.1wt% to 10wt% or about 0.1wt% to 5.0wt%, about 0.1wt% to 2.0 wt%) of a polysaccharide derivative or oxidized polysaccharide derivative as disclosed herein. Polysaccharide derivatives or oxidized polysaccharide derivatives included in oral care compositions may sometimes be provided therein as thickening and/or dispersing agents that may be used to impart a desired consistency and/or mouthfeel to the composition. One or more other thickening or dispersing agents may also be provided in the oral care compositions herein, such as, for example, carboxyvinyl polymers, carrageenan (e.g., L-carrageenan), natural gums (e.g., karaya gum (karaya), xanthan gum, acacia gum, tragacanth gum), colloidal magnesium aluminum silicate, or colloidal silica.

The oral care composition herein may be, for example, a toothpaste or other dentifrice. Such compositions, as well as any other oral care compositions herein, may additionally comprise, but are not limited to, one or more anticaries agents, antimicrobial or antibacterial agents, anticalculus or tartar control agents, surfactants, abrasives, pH adjusters, foam adjusters, humectants, flavorants, sweeteners, pigments/colorants, whitening agents, and/or other suitable components. Examples of oral care compositions to which the polysaccharide derivatives or oxidized polysaccharide derivatives herein may be added are disclosed in U.S. patent application publication nos. 2006/013025, 2002/0022006, and 2008/0057007, which are incorporated herein by reference.

Anticaries agents herein may be orally acceptable fluoride ion sources. Suitable sources of fluoride ions include, for example, fluorides, monofluorophosphates and fluorosilicates, and amine fluorides, including olafluoro (N '-octadecyltrimethylene diamine-N, N' -tris (2-ethanol) -dihydrofluoride). For example, anticaries agents may be present in an amount that provides the composition with a total of about 100-20000ppm, about 200-5000ppm, or about 500-2500ppm fluoride ions. In oral care compositions where sodium fluoride is the sole source of fluoride ion, for example, an amount of about 0.01 to 5.0wt%, about 0.05 to 1.0wt%, or about 0.1 to 0.5wt% sodium fluoride may be present in the composition.

Antimicrobial or antibacterial agents suitable for use in the oral care compositions herein include, for example, phenolic compounds (e.g., 4-allyl catechol; parabens such as benzyl, butyl, ethyl, methyl, and propyl parabens; 2-benzyl phenol; butylated hydroxyanisole; butylated hydroxytoluene; capsaicin; carvacrol; wood-tar alcohol; eugenol; guaiacol; halogenated bisphenols such as hexachlorophene and bromochlorophenol; 4-hexyl resorcinol; 8-hydroxyquinoline and its salts; salicylates such as menthyl, methyl, and phenyl salicylates; phenol; pyrocatechol; salicylanilide; thymol; halogenated diphenyl ether compounds such as triclosan and triclosan monophosphates); copper (II) compounds (e.g., copper (II) chlorides, fluorides, sulfates, and hydroxides); zinc ion sources (e.g., zinc acetate, citrate, gluconate, glycinate, oxide, and sulfate); phthalic acid and salts thereof (e.g., magnesium monopotassium phthalate); bis-octyl hydrogen pyridine; octenib lake; sanguinarine; benzalkonium chloride; the bromination degree is clofenamic; alkylpyridine chlorides (e.g., cetylpyridine chloride, tetradecylpyridine chloride, N-tetradecyl-4-ethylpyridine chloride); iodine; sulfonamide; metformin (e.g., alexidine, chlorhexidine digluconate); azacyclohexane derivatives (e.g., delmopinol, octapetinol); magnolia extract, grape seed extract, rosemary extract, menthol, geraniol, citral, eucalyptol; antibiotics (e.g., wo Gemeng, amoxicillin, tetracycline, doxycycline, minocycline, metronidazole, neomycin, kanamycin, clindamycin), and/or any of the antibacterial agents disclosed in U.S. patent 5776435 (incorporated herein by reference). The one or more antimicrobial agents can optionally be present at about 0.01 to 10wt% (e.g., 0.1 to 3 wt%), such as in the disclosed oral care compositions.

Anticalculus or tartar control agents suitable for use in the oral care compositions herein include, for example, phosphates and polyphosphates (e.g., pyrophosphates), polyaminopropane sulfonic Acid (AMPS), zinc citrate trihydrate, polypeptides (e.g., polyaspartic acid and polyglutamic acid), polyolefin sulfonates, polyolefin phosphates, bisphosphonates (e.g., azacycloalkane-2, 2-bisphosphonates, such as azacycloheptane-2, 2-bisphosphonic acid), N-methylazacyclopentane-2, 3-bisphosphonic acid, ethane-1-hydroxy-1, 1-bisphosphonic acid (EHDP), ethane-1-amino-1, 1-bisphosphonates, and/or phosphonoalkanoic acids and salts thereof (e.g., alkali metal and ammonium salts thereof). Useful inorganic phosphates and polyphosphates include, for example, monobasic, dibasic and tribasic sodium phosphates; sodium tripolyphosphate; tetraphosphate; mono-, di-, tri-and tetra-sodium pyrophosphates; disodium dihydrogen pyrophosphate; sodium trimetaphosphate; sodium hexametaphosphate; or any of these where sodium is replaced by potassium or ammonium. In certain embodiments, other useful anticalculus agents include anionic polycarboxylate polymers (e.g., polymers or copolymers of acrylic acid, methacrylic acid, and maleic anhydride, such as polyvinylmethylether/maleic anhydride copolymers). Other useful anticalculus agents include chelating agents such as hydroxycarboxylic acids (e.g., citric acid, fumaric acid, malic acid, glutaric acid, and oxalic acid and salts thereof) and aminopolycarboxylic acids (e.g., EDTA). One or more anticalculus or tartar control agents may optionally be present at about 0.01 to 50wt% (e.g., about 0.05 to 25wt% or about 0.1 to 15 wt%), e.g., in the disclosed oral care compositions.

Surfactants suitable for use in the oral care compositions herein may be, for example, anionic, nonionic or amphoteric. Suitable anionic surfactants include, but are not limited to, C _8-20 Water-soluble salts of alkyl sulphates, C _8-20 Fatty acid sulfonated monoglycerides, sarcosinates, and taurates. Examples of the anionic surfactant include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl hydroxyethyl sulfonate, sodium polyethylene glycol monolauryl ether carboxylate, and sodium dodecylbenzene sulfonate. Suitable nonionic surfactants include, but are not limited to, poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfoxides. Suitable amphoteric surfactants includeBut are not limited to C having anionic groups such as carboxylate, sulfate, sulfonate, phosphate or phosphonate _8-20 Derivatives of aliphatic secondary and tertiary amines. An example of a suitable amphoteric surfactant is cocoamidopropyl betaine. The one or more surfactants are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.01 to 10wt% (e.g., about 0.05 to 5.0wt% or about 0.1 to 2.0 wt%).

Abrasives suitable for use in the oral care compositions herein can include, for example, silica (e.g., silica gel, hydrated silica, precipitated silica), alumina, insoluble phosphates, calcium carbonate, and resinous abrasives (e.g., urea-formaldehyde condensate products). Examples of insoluble phosphates useful herein as abrasives are orthophosphates, polymetaphosphates and pyrophosphates, and include dicalcium orthophosphate dihydrate, calcium pyrophosphate, beta-calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate and insoluble sodium polymetaphosphate. The one or more abrasives are optionally present in the disclosed oral care compositions, for example, in a total amount of about 5-70wt% (e.g., about 10-56wt% or about 15-30 wt%). In certain embodiments, the average particle size of the abrasive is about 0.1 to 30 microns (e.g., about 1 to 20 microns or about 5 to 15 microns).

In certain embodiments, the oral care composition can comprise at least one pH adjuster. Such agents may be selected to acidify, make more basic, or buffer the pH of the composition to a pH range of about 2-10 (e.g., a pH range from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9). Examples of pH adjusters useful herein include, but are not limited to, carboxylic acids, phosphoric acids, and sulfonic acids; acidic salts (e.g., monosodium citrate, disodium citrate, monosodium malate); alkali metal hydroxides (e.g., sodium hydroxide, carbonates such as sodium carbonate, bicarbonate, sodium sesquicarbonate); a borate; silicate; phosphates (e.g., monosodium phosphate, trisodium phosphate, pyrophosphates); imidazole.

Foam modulators suitable for use in the oral care compositions herein may be, for example, polyethylene glycol (PEG). High molecular weight PEG are suitable, including, for example, those having an average molecular weight of about 200000-7000000 (e.g., about 500000-5000000 or about 1000000-2500000). The one or more PEGs are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.1-10wt% (e.g., about 0.2-5.0wt% or about 0.25-2.0 wt%).

In certain embodiments, the oral care composition may comprise at least one humectant. In certain embodiments, the humectant may be a polyol, such as glycerin, sorbitol, xylitol, or low molecular weight PEG. Most suitable humectants can also be employed as sweeteners herein. The one or more humectants are optionally present in, for example, the disclosed oral care compositions in a total amount of about 1.0 to 70wt% (e.g., about 1.0 to 50wt%, about 2 to 25wt%, or about 5 to 15 wt%).

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

Natural or artificial flavorants may optionally be included in the oral care compositions herein. Examples of suitable flavorants include vanillin; sage (Salvia officinalis); marjoram (Tulip); celery oil; spearmint oil; cinnamon oil; wintergreen oil (methyl salicylate); peppermint oil of capsicum; clove oil; laurel oil; fennel oil; eucalyptus oil; citrus oil; fruit oil; fragrances such as those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, or pineapple; flavoring derived from beans and nuts, such as coffee, cocoa, cola, peanut, or almond; and adsorbed and encapsulated flavorants. Also encompassed within the flavorants herein are ingredients that provide flavor and/or other sensory effects in the mouth, includingCooling or warming effect. Such ingredients include, but are not limited to, menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cinnamon, oxazolidinone (oxanone),Hydroxymethyl anethole, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthane-3-carboxamide, N,2, 3-trimethyl-2-isopropyl butanamide, 3- (1-menthoxy) -propane-1, 2-diol, cinnamaldehyde Glycerol Acetal (CGA) and Menthone Glycerol Acetal (MGA). One or more flavorants are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.01 to 5.0wt% (e.g., about 0.1 to 2.5 wt%).

In certain embodiments, the oral care composition can comprise at least one bicarbonate salt. Any orally acceptable bicarbonate can be used, including, for example, alkali metal bicarbonate salts such as sodium or potassium bicarbonate, and ammonium bicarbonate. For example, one or more bicarbonate salts are optionally present in the disclosed oral care compositions in a total amount of about 0.1-50wt% (e.g., about 1-20 wt%).

In certain embodiments, the oral care composition may comprise at least one whitening agent and/or colorant. Suitable whitening agents are peroxide compounds, such as any of those disclosed in U.S. patent No. 8540971, which is incorporated herein by reference. Suitable colorants herein include, for example, pigments, dyes, lakes, and agents that impart a particular luster or reflectivity, such as pearlizing agents. Specific examples of colorants useful herein include talc; mica; magnesium carbonate; calcium carbonate; magnesium silicate; magnesium aluminum silicate; silicon dioxide; titanium dioxide; zinc oxide; red, yellow, brown, black iron oxide; ferric ammonium ferrocyanide; manganese violet; deep blue; titanium mica; bismuth oxychloride. For example, one or more colorants are optionally present in the disclosed oral care compositions in a total amount of about 0.001 to 20wt% (e.g., about 0.01 to 10wt% or about 0.1 to 5.0 wt%).

Additional components that may optionally be included in the oral compositions herein include, for example, one or more enzymes (above), vitamins, and anti-binders. Examples of vitamins useful herein include vitamin C, vitamin E, vitamin B5, and folic acid. Examples of suitable anti-binders include methyl parahydroxybenzoate (solbrol), ficin and quorum sensing inhibitors.

Further examples of personal care, home care, and other products and ingredients herein may be any as disclosed in U.S. patent No. 8796196, which is incorporated herein by reference. Examples of personal care, home care, and other products and ingredients herein include perfumes, fragrances, air odor reducing agents, insect repellents, and insecticides, foaming agents such as surfactants, pet deodorants, pet insecticides, pet shampoos, disinfectants, hard surface (e.g., floors, bath/shower, sink, toilet bowl, door handle/panel, glass/window, exterior or interior of a car/automobile) treatments (e.g., cleaning, sanitizing, and/or coating agents), wipes and other nonwoven materials, colorants, preservatives, antioxidants, emulsifiers, emollients, oils, pharmaceuticals, flavors, and suspending agents.

The present disclosure also relates to methods of treating materials. The method comprises contacting the material with an aqueous composition comprising a polysaccharide derivative or an oxidized polysaccharide derivative as disclosed herein.

In some aspects, the material contacted with the aqueous composition in the contact methods herein may comprise a fabric. The fabrics herein may comprise natural fibers, synthetic fibers, semisynthetic fibers, or any combinations thereof. The semisynthetic fibers herein are produced using naturally occurring materials that have been chemically derivatized, examples of which are rayon. Non-limiting examples of the types of fabrics herein include fabrics made from: (i) Cellulose fibres such as cotton (e.g. suede, canvas, striped or lattice cloth, chenille, printed cotton, corduroy, large-pattern cord, brocade, jean, flannel, striped cotton, jacquard, knitted fabric, matelase, oxford, high-grade dense cotton, poplin, pleat, cotton satin, seersucker, transparent tissue, terry clothTwill, velvet), rayon (e.g., viscose, modal, lyocell), linen, and(ii) Protein fibers such as silk, wool and related mammalian fibers; (iii) Synthetic fibers such as polyester, acrylic, nylon, and the like; (iv) Long plant fibers from jute, flax, ramie, coir, kapok, sisal, herceptin, abaca, hemp, and tamarix; and (v) any combination of fabrics of (i) - (iv). Fabrics comprising a combination of fiber types (e.g., natural and synthetic) include, for example, those having both cotton fibers and polyester. Materials/articles comprising one or more fabrics herein include, for example, clothing, curtains, furniture upholstery, carpeting, bed sheets, bath towels, tablecloths, sleeping bags, tents, automotive interiors, and the like. Other materials that include natural and/or synthetic fibers include, for example, nonwoven fabrics, liners, papers, and foams.

The aqueous composition that is contacted with the fabric may be, for example, a fabric care composition (e.g., laundry detergent, fabric softener). Thus, if the fabric care composition is used in a treatment process, the treatment process may be considered a fabric care process or a laundry process in certain embodiments. It is contemplated that the fabric care compositions herein may achieve one or more of the following fabric care benefits (i.e., surface substantive effects): removing wrinkles, reducing fabric wear, resisting fabric wear, reducing fabric pilling, extending fabric life, maintaining fabric color, reducing fabric fading, reducing dye transfer, restoring fabric color, reducing fabric staining, releasing fabric soil, maintaining fabric shape, enhancing fabric smoothness, preventing redeposition of soil on fabric, preventing garment graying, improving fabric hand/feel and/or reducing fabric shrinkage.

Examples of conditions (e.g., time, temperature, wash/rinse volume) for performing a fabric care or laundry process are disclosed herein in WO 1997/003161 and U.S. patent nos. 4794661, 4580421 and 5945394, which are incorporated herein by reference. In other examples, the fabric-containing material may be contacted with the aqueous compositions herein: (i) For at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120 minutes; (ii) At a temperature of at least about 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, or 95 ℃ (e.g., for laundry washing or rinsing: a "cold" temperature of about 15 ℃ to 30 ℃, a "warm" temperature of about 30 ℃ to 50 ℃, a "hot" temperature of about 50 ℃ to 95 ℃); (iii) At a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 (e.g., a pH range of about 2-12 or about 3-11); (iv) At a salt (e.g., naCl) concentration of at least about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 wt.%; or any combination of (i) - (iv).

For example, the contacting step in a fabric care or laundry method may include any of a wash, soak, and/or rinse step. In still further embodiments, contacting with the material or fabric may be by any means known in the art, such as dissolving, mixing, shaking, spraying, treating, dipping, rinsing, pouring or pouring, bonding, painting, coating, applying, pasting, and/or transmitting an effective amount of the polysaccharide derivative or oxidized polysaccharide derivative herein on the fabric or material. In still other embodiments, the fabric may be treated with a contact to provide a surface substantive effect. As used herein, the term "fabric hand" or "feel" refers to the haptic sensory response of an individual to a fabric, which may be physical, physiological, psychological, social, or any combination thereof. In one embodiment, the fabric hand may be used to measure relative hand valuesSystem measurements (Nu Cybertek Co., available from Nu Cybertek, inc. Davis, calif.) (American society of textile chemists and dyeing families (American Association of Textile Chemists and Colorists) [ AATCC test method "202-2012,Relative Hand Value of Textiles:Instrumental Method [ relative hand feel of textiles) ] Value: instrument method]”])。

In some aspects of treating materials comprising fabrics, the polysaccharide derivative or oxidized polysaccharide derivative component of the aqueous composition is adsorbed onto the fabric. This feature is believed to make the polysaccharide derivatives or oxidized polysaccharide derivatives herein useful as anti-redeposition agents and/or anti-graying agents (except for viscosity changes and/or builder action) in the disclosed fabric care compositions. The anti-redeposition or anti-graying agents herein help to prevent redeposition of stains on laundry in the wash water after the stains have been removed. In some aspects, it is further contemplated that adsorbing the polysaccharide derivative or oxidized polysaccharide derivative herein to the fabric enhances the mechanical properties of the fabric.

Adsorption of polysaccharide derivatives or oxidized polysaccharide derivatives onto the fabrics herein may, for example, use colorimetric techniques (e.g., dubois et al, 1956, anal. Chem. [ analytical chemistry ]]28:350-356；Et al, 2006,Lenzinger Berichte [ report of Linz chemical Co., ltd ]]85:68-76; both of which are incorporated herein by reference), or any other method known in the art.

Other materials that may be contacted in the above treatment methods include surfaces that may be treated with a dishwashing detergent (e.g., an automatic dishwashing detergent or a hand dishwashing detergent). Examples of such materials include surfaces of tableware, glassware, pots, pan-like ware, bakeware, cookware and flatware (collectively referred to herein as "foodware") made of ceramic materials, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, polystyrene, melamine, etc.) and wood. Thus, in certain embodiments, the treatment method may be considered, for example, a dishwashing method or a foodware washing method. Examples of conditions (e.g., time, temperature, wash volume) for performing the dishwashing or foodware washing methods herein are disclosed herein as well as in U.S. patent No. 8575083 and U.S. patent application publication No. 2017/0044468, which are incorporated herein by reference. In some aspects, the foodware article may be contacted with the aqueous compositions herein under a suitable set of conditions, such as any of those disclosed above with respect to contact with the fabric-containing material.

Other materials that may be contacted in the above treatment methods include oral surfaces, such as any soft or hard surfaces within the oral cavity, including surfaces of: tongue, hard and soft palate, buccal mucosa, gums and tooth surfaces (e.g., hard surfaces of natural teeth or artificial dentition such as crowns, caps, fillings, bridges, dentures or dental implants). Thus, in certain embodiments, the treatment method may be considered, for example, an oral care method or a dental care method. The conditions (e.g., time, temperature) used to contact the oral surface with the aqueous compositions herein should be suitable for the intended purpose of making such contact. Other surfaces that may be contacted in the treatment process also include the surface of skin systems such as skin, hair or nails.

Accordingly, some aspects of the present disclosure relate to materials (e.g., fabrics, or fibrous products as disclosed herein) comprising the polysaccharide derivatives or oxidized polysaccharide derivatives herein. Such materials may be prepared according to, for example, the material processing methods as disclosed herein. In some aspects, a material may comprise a polysaccharide derivative or an oxidized polysaccharide derivative if the polysaccharide derivative or oxidized polysaccharide derivative is adsorbed to or otherwise in contact with the surface of the material.

Some aspects of the methods of treating a material herein further comprise a drying step, wherein the material is dried after contact with the aqueous composition. The drying step may be performed directly after the contacting step, or after one or more additional steps that may follow the contacting step (e.g., drying the fabric or foodstuff after washing in an aqueous composition herein, such as after rinsing in water). Drying may be performed by any of several methods known in the art, such as air drying (e.g., about 20 ℃ -25 ℃), or at a temperature of at least about 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 170 ℃, 175 ℃, 180 ℃, or 200 ℃, for example. The material that has been dried herein typically has less than 3wt%, 2wt%, 1wt%, 0.5wt%, or 0.1wt% water contained therein. Fabrics are the preferred materials for performing the optional drying step.

The aqueous composition used in the treatment methods herein may be any of the aqueous compositions disclosed herein. Examples of aqueous compositions include detergents (e.g., laundry or dish detergents), fabric softeners, and aqueous dentifrices such as toothpastes.

The present disclosure also relates to a method of preparing an aqueous composition having increased builder capacity. The method comprises, for example, contacting at least one polysaccharide derivative or oxidized polysaccharide derivative as disclosed herein with an aqueous composition, wherein the derivative increases the builder capacity of the aqueous composition compared to the builder capacity of the aqueous composition present prior to the contacting step. Such a process may optionally be characterized as a water (or any other aqueous composition) softening process.

The aqueous composition in the method may be any aqueous composition as disclosed herein, such as, for example, a home care product, a personal care product, an industrial product, a pharmaceutical product or a food product. Examples of suitable home care products include home care or industrial care products such as laundry detergents or fabric softeners, and automatic dishwashing detergents. Examples of suitable personal care products include hair care products (e.g., shampoos, conditioners), dentifrice compositions (e.g., toothpastes, mouthwashes), and skin care products (e.g., hand or body soaps, lotions, cosmetics).

In some aspects, the aqueous composition in the method is a detergent and/or surfactant composition. Such compositions herein may comprise, for example, from about 0.01wt% to 10wt% (e.g., from about 0.05wt% to 5.0wt% or from about 0.1wt% to 2.0 wt%) of at least one detergent/surfactant ingredient, such as any of the present disclosure. Those skilled in the art will recognize all of the different products disclosed herein that make up examples of detergent/surfactant-containing compositions, such as certain home care products (e.g., laundry detergents, dishwashing detergents) and personal care products (e.g., hand soap/bath soaps, dentifrices), particularly those used in cleaning applications.

In some aspects, contacting the aqueous composition with one or more polysaccharide derivatives or oxidized polysaccharide derivatives may increase the builder capacity of the aqueous composition. The increase may be, for example, about, or at least about 1%, 5%, 10%, 25%, 50%, 100%, 500%, or 1000% (or any integer between 1% and 1000%) as compared to the builder capacity of the aqueous composition prior to the contacting step. The degree of increased builder capacity achieved can be measured in a number of ways. For example, the increased builder capacity achieved by a polysaccharide derivative or oxidized polysaccharide derivative herein can be estimated by determining the extent to which the derivative supplies alkalinity to or buffers an aqueous composition to maintain alkalinity. As another example, the increased builder capacity resulting from polysaccharide derivatives or oxidized polysaccharide derivatives herein can be estimated by determining the extent to which the derivatives reduce the hardness of the aqueous composition (by chelation) of hard water cations and/or help remove soil in suspension (this feature is typically applicable to fabric care compositions). As other examples, increased builder capacity can be determined according to the following examples and/or methods (e.g., calcium dispersing capacity, NTU assay, membrane reduction assay) disclosed in U.S. patent application publication No. 2018/0022834 (which is incorporated herein). For example, contacting a polysaccharide derivative or oxidized polysaccharide with an aqueous composition herein may be accomplished by dissolving or dispersing the derivative into the aqueous composition.

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

a composition comprising an oxidized polysaccharide derivative, wherein the oxidized polysaccharide derivative is produced by contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative, and wherein the polysaccharide derivative has a degree of substitution (DoS) with at least one organic group of up to about 3.0.

The composition of embodiment 1a wherein the polysaccharide derivative is a glucan derivative or a soy polysaccharide derivative.

The composition of embodiment 1a or 2a, wherein the polysaccharide derivative is the dextran derivative and the dextran derivative is an alpha-dextran derivative.

The composition of embodiment 3a, wherein at least 50% of the glycosidic linkages of the alpha-glucan derivative are alpha-1, 3, alpha-1, 4, or alpha-1, 6 linkages.

The composition of example 1a, 2a, 3a, or 4a, wherein the oxidized polysaccharide derivative has a biodegradability of at least 10% after 60 or 90 days as determined by a carbon dioxide release test method.

The composition of example 1a, 2a, 3a, 4a, or 5a, wherein the polysaccharide from which the polysaccharide derivative is derived has a weight average degree of polymerization (DPw) of at least about 50.

The composition of example 1a, 2a, 3a, 4a, 5a, or 6a, wherein the organic group is in ether linkage with the polysaccharide derivative.

The composition of embodiment 7a, wherein the organic group comprises a carboxyalkyl group, an alkyl group, a hydroxyalkyl group, or an aryl group.

The composition of embodiment 7a, wherein the organic group comprises a carboxymethyl group.

The composition of examples 1a, 2a, 3a, 4a, 5a, or 6a wherein the organic group is in an ester linkage, a urethane linkage, or a sulfonyl linkage with the polysaccharide derivative.

The composition of examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, or 10a, wherein the agent comprises an N-oxoammonium salt.

The composition of embodiments 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, or 11a, wherein the composition is a home care product, a personal care product, an industrial product, an ingestible product (e.g., a food product), or a pharmaceutical product.

The composition of examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a, or 12a, wherein the composition is an aqueous composition.

The composition of example 13a, wherein the aqueous composition further comprises at least one cation and the oxidized dextran derivative is bound to the cation.

The composition of examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a, 12a, 13a, or 14a, wherein the composition is in the form of, or is contained in, a liquid, gel, powder, hydrocolloid, granule, tablet, capsule, bead or lozenge, a single-compartment pouch, a multi-compartment pouch, a single-compartment pouch, or a multi-compartment pouch.

The composition of examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a, 12a, 13a, 14a, or 15a further comprising at least one surfactant.

The composition of examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a, 12a, 13a, 14a, 15a, or 16a, further comprising at least one enzyme.

The composition of embodiment 17a, wherein the enzyme is a cellulase, protease, lipase, amylase, or lipase.

A composition as described in examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a, 12a, 13a, 14a, 15a, 16a, 17a, or 18a, further comprising at least one of the following: complexing agents, soil release polymers, surface active enhancing polymers, bleaching agents, bleach activators, bleach catalysts, fabric conditioners, clays, suds boosters, suds suppressors, anti-corrosion agents, soil suspending agents, anti-soil redeposition agents, dyes, bactericides, tarnish inhibitors, optical brighteners, perfumes, saturated or unsaturated fatty acids, dye transfer inhibitors, chelants, shading dyes, visual signal transmission components, defoamers, structurants, thickeners, anti-caking agents, starches, sand, or gelling agents.

A method of producing an oxidized polysaccharide derivative (e.g., as described in any one of claims 1a-11 a), the method comprising:

(b) Optionally isolating the oxidized polysaccharide derivative.

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

a composition (e.g., a detergent composition) comprising:

(i) A dextran derivative substituted with at least one organic group comprising a carboxylic acid group or a sulfonate group, wherein the degree of substitution (DoS) of the dextran derivative with the organic group is about 0.1 to about 3.0, wherein the dextran from which the dextran derivative is derived has a weight average degree of polymerization (DPw) of at least about 50, and wherein optionally at least 50% of the glycosidic linkages of the dextran derivative are alpha-1, 3, alpha-1, 4, or alpha-1, 6 linkages; and/or

Wherein the hard surface washed or treated in a wash/treat composition comprising the composition has reduced filming, spotting, cloudiness, or other deposition.

The composition of embodiment 1b, comprising the glucan derivative, wherein the glucan derivative is an alpha-glucan derivative and at least about 50% of the glycosidic linkages of the alpha-glucan derivative are alpha-1, 6 linkages.

The composition of embodiment 2b wherein (a) about 3% to about 25% of the glycosidic linkages of the α -glucan derivative are α -1,2 and/or α -1,3 branch points, (b) the DoS of the α -glucan derivative by the organic group is about 0.3 to about 1.0, and/or (c) the α -glucan from which the α -glucan derivative is derived has a DPw of at least about 100.

The composition of embodiment 1b, comprising the glucan derivative, wherein the glucan derivative is an alpha-glucan derivative and at least about 50% of the glycosidic linkages of the alpha-glucan derivative are alpha-1, 3 linkages.

The composition of embodiment 4b wherein (a) the DoS of the α -glucan derivative by the organic group is about 0.3 to about 1.5, and/or (b) the α -glucan from which the α -glucan derivative is derived has a DPw of at least about 100.

The composition of example 1b, 2b, 3b, 4b, or 5b comprising the dextran derivative, wherein the organic group is in ether linkage with the dextran derivative.

The composition of embodiment 6b, wherein the organic group comprises a carboxyalkyl group.

The composition of embodiment 7b wherein the carboxyalkyl group is carboxymethyl.

The composition of embodiment 7b or 8b, wherein the dextran derivative is further substituted with at least one aryl containing organic group.

The composition of embodiment 9b wherein the aryl is benzyl.

The composition of embodiment 1b comprising the oxidized polysaccharide derivative (e.g., as described in any one of embodiments 1a-11 a), optionally wherein the oxidized polysaccharide derivative has a biodegradability of at least 10% after 60 or 90 days as determined by a carbon dioxide release test method.

The composition of embodiments 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, or 11b, wherein the composition is included in the washing/treatment composition, wherein the washing/treatment composition comprises at least one cation, and the dextran derivative or oxidized polysaccharide derivative is bound to the cation.

The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, or 12b, wherein the composition is in the form of, or is contained in, an aqueous composition, a liquid, a gel, a powder, a hydrocolloid, a granule, a tablet, a capsule, a bead or lozenge, a single-compartment pouch, a multi-compartment pouch, a single-compartment pouch, or a multi-compartment pouch.

The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, or 13b, wherein the composition is in the form of, or is contained in, a dishwashing detergent composition.

A composition according to example 14b, wherein the dishwashing detergent composition is an automatic dishwashing detergent composition, optionally wherein the automatic dishwashing detergent composition comprises (a) 2wt% to 12wt% of the glucan derivative of (i) or the oxidized polysaccharide derivative of (ii); (b) 3wt% to 50wt% of methylglycine diacetic acid and/or a salt thereof; (c) 15wt% to 65wt% of one or more builders and/or co-builders; (d) 0.5wt% to 10wt% of one or more nonionic surfactants; (e) 0wt% to 30wt% of one or more bleaching agents and bleach activators; (f) 0wt% to 8wt% of one or more enzymes; and (g) 0wt% to 50wt% of one or more additives.

A method of washing/cleaning or treating a hard surface, the method comprising:

(a) Contacting the hard surface with a wash/treatment composition comprising a composition as described in any one of examples 1b-15b (or as described in example 16 a), and

thereby washing/cleaning or treating the hard surface, wherein the washed/cleaned hard surface or treated hard surface has reduced filming, spotting, cloudiness, or other deposition.

The method of embodiment 16b, wherein step (b) comprises rinsing the hard surface.

The method of embodiment 16b or 17b wherein the hard surface is a hard surface of glass, plastic, ceramic, porcelain, metal, or stone.

The method of embodiment 16b, 17b, or 18b, wherein the hard surface is a hard surface of a cutlery.

The method of example 16b, 17b, 18b, or 19b, which is performed in an automatic dishwasher.

A composition as described in examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, or 15b, or a method as described in examples 16b, 17b, 18b, 19b, or 20b, or as disclosed herein, wherein the composition does not comprise a surfactant, or has less than 5wt%, 4wt%, 3wt%, 2wt%, 1wt%, 0.5wt%, 0.25wt%, 0.1wt%, 0.05wt%, or 0.025wt% of the surfactant.

A composition as described in examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, or 21b, or a method as described in examples 16b, 17b, 18b, 19b, or 20b, or as disclosed herein, comprising the oxidized polysaccharide derivative of (ii), but with the difference that the polysaccharide is not derivatized prior to being oxidized.

Examples

The disclosure is further illustrated in the following examples. It should be understood that while these examples are indicative of certain aspects of the present disclosure, they are presented by way of illustration only. From the foregoing discussion and these examples, one skilled in the art can ascertain the essential characteristics of the disclosed embodiments, and without departing from the spirit and scope thereof, can make various changes and modifications to the disclosed embodiments to adapt it to various uses and conditions.

Materials/methods

Representative preparation of alpha-1, 3-glucan

Alpha-1, 3-glucan having about 100% of alpha-1, 3 glycosidic linkages can be synthesized, for example, according to the procedure disclosed in U.S. application publication No. 2014/0179913 (see, e.g., example 12 therein), which is incorporated herein by reference.

As another example, a slurry of α -1, 3-glucan is prepared from: aqueous solutions (0.5L) containing Streptococcus salivarius gtfJ enzyme (100 units/L) as described in U.S. patent application publication No. 2013/0244188 (incorporated herein by reference), obtained from Omnipur Sucrose Inc (EM 8550) (100 g/L), potassium phosphate buffer (10 mM) obtained from Sigma Aldrich and antimicrobial adjusted to pH 5.5 obtained from DuPont (DuPont)(100 ppm). The resulting enzyme reaction was maintained at 20℃to 25℃for 24 hours. Since the α -1, 3-glucan synthesized in the reaction is water insoluble, a slurry is formed. Alpha-1, 3-glucan solids were then collected on a 40 micron filter paper using a buchner funnel equipped with a 325 mesh screen to form a wet cake containing about 60wt% to 80wt% water.

Representative preparation of alpha-1, 6-glucan having alpha-1, 2 branches

Methods for preparing alpha-1, 6-glucan containing varying amounts of alpha-1, 2 branches are disclosed in U.S. application publication No. 2018/0282385, which is incorporated herein by reference. Reaction parameters such as sucrose concentration, temperature and pH can be adjusted to provide a-1, 6-glucan having various levels of a-1, 2-branching and molecular weight. Representative procedures for preparing alpha-1, 6-glucan having 19% of alpha-1, 2-branches and 81% of alpha-1, 6 bonds are provided below. Using 1D ¹ The distribution of glycosidic bonds was quantified by H-NMR spectroscopy. Additional samples of alpha-1, 6-glucan having alpha-1, 2-branches were similarly prepared. For example, one contains 32% α -1, 2-branches and 68% α -1,6 linkages, and the other contains 10% α -1, 2-branches and 90% α -1,6 linkages.

A stepwise combination of a glucosyltransferase (dextran sucrase) GTF8117 and an alpha-1, 2 branching enzyme GTFJ18T1 was used to prepare a soluble alpha-1, 6-glucan having about 19% of the alpha-1, 2 branches according to the following procedure. The reaction mixture (2L) consisting of sucrose (450 g/L), GTF8117 (9.4U/mL) and 50mM sodium acetate was adjusted to pH 5.5 and stirred at 47 ℃. Aliquots (0.2-1 mL) were removed at predetermined times and quenched by heating at 90 ℃ for 15 minutes. The resulting heat treated aliquot was passed through a 0.45- μm filter. The flow-through was analyzed by HPLC to determine the concentration of sucrose, glucose, fructose, leuconostoc disaccharides, oligosaccharides and polysaccharides. After 23.5 hours, the reaction mixture was heated to 90 ℃ for 30 minutes. An aliquot of the heat treated reaction mixture was passed through a 0.45- μm filter and the flow was analyzed for soluble mono/di, oligo and polysaccharides. The main product is linear dextran with a DPw of 93.

The second reaction mixture was prepared by adding 238.2g sucrose and 210mL of alpha-1, 2-branching enzyme GTFJ18T1 (5.0U/mL) to the remaining heat treated reaction mixture obtained from the GTF8117 reaction just described. The mixture was stirred at 30℃in a volume of about 2.2L. Aliquots (0.2-1 mL) were removed at predetermined times and quenched by heating at 90 ℃ for 15 minutes. The resulting heat treated aliquot was passed through a 0.45- μm filter. The flow-through was analyzed by HPLC to determine the concentration of sucrose, glucose, fructose, leuconostoc disaccharides, oligosaccharides and polysaccharides. After 95 hours, the reaction mixture was heated to 90 ℃ for 30 minutes. An aliquot of the heat treated reaction mixture was passed through a 0.45- μm filter and the flow was analyzed for soluble mono/di, oligo and polysaccharides. The remaining heat treated mixture was centrifuged using a 1-L centrifuge bottle. The supernatant was collected and cleaned more than 200-fold using an ultrafiltration system with a 1-or 5-kDa MWCO cassette and deionized water. Drying the cleaned oligosaccharide/polysaccharide product solution. Then pass through ¹ The dried samples were analyzed by H-NMR spectroscopy to determine the anomeric linkages of the oligosaccharides and polysaccharides.

Preparation of carboxymethyl alpha-1, 6-glucan

A three-necked 2-L round bottom flask equipped with an overhead stirrer was charged with 267g of 37.5wt% alpha-1, 6-glucan solution (53 kDa,6.4% alpha-1, 2-branched). To the solution was added, with stirring, 50wt% sodium hydroxide solution (199 g) via an addition funnel over 15 minutes. To this stirred solution was added chloroacetic acid solution (116 g dissolved in 77g water) via an addition funnel over 30 minutes. The solution was heated to 55 ℃ under nitrogen for 5 hours. The resulting amber solution was cooled and neutralized to pH 7 with 18wt% HCl. The resulting pale yellow solution was diluted to 3L and purified by diafiltration (3 XMWCO 30-kDa PES membrane, approximately 9L of water was passed through). The solution was concentrated with a rotary evaporator and frozenDrying to give a white powder. By passing through ¹ H-NMR analysis confirmed that the degree of substitution of the carboxymethyl alpha-1, 6-glucan product thus prepared was 0.51.

Preparation of carboxymethyl alpha-1, 3-glucan (dos 0.91)

To a metal/mechanical stirrer bar, thermocouple, addition funnel and top with N ₂ The 4-neck, 2-L round bottom flask of the inlet condenser was charged with alpha-1, 3-glucan (DPw 650, 110 g) and water (110 g). The mixture was left at room temperature overnight. Ethanol (220 g,92 wt%) was added at room temperature. The mixture was stirred at 200rpm and sodium hydroxide (191.1 g,50wt% solution) was added over a period of 20 minutes (25 ℃ C. To 37 ℃ C.). The white slurry was stirred for an additional 10 minutes. A solution containing 112.2g of chloroacetic acid in 50g of 92wt% ethanol was added over a period of 20 minutes (35℃to 55 ℃). The white slurry was heated at 58-60 ℃ for 3 hours using a heating mantel. The reaction was cooled to 45 ℃ and sodium hydroxide (108.6 g,50wt% solution) was added over 10 minutes followed by a solution containing 64.13g chloroacetic acid in 35g 92wt% ethanol. The resulting formulation was heated at 58 ℃ to 65 ℃ for 2 hours. Large agglomerates are formed in the reaction. The liquid (about 500 mL) of the reaction was decanted. Methanol (400 mL) was added and the pH of the mixture was adjusted to about 7 by addition of HCl (18.5 wt%,13.5 g). The liquid was decanted. The resulting solid was washed with 90wt% methanol (700 mL), twice with 80wt% methanol (700 mL each wash), and filtered to give a solid which was dried overnight under full vacuum to give 148.5g of the product (carboxymethyl α -1, 3-glucan). By passing through ¹ H-NMR analysis confirmed that the degree of substitution of the carboxymethyl alpha-1, 3-glucan product thus prepared was 0.91.

Preparation of benzyl alpha-1, 3-glucan (dos 0.57)

Alpha-1, 3-glucan (180 g of 27.5wt% solids wet cake [ balance water ]]) Is charged into a 3-neck 1-L reactor. To this was added 110mL of water. The mixture was cooled to 18 ℃ to 21 ℃ in an ice water bath. 63g of 50% by weight sodium hydroxide solution were added thereto, and the mixture was stirred for 30 minutes. Water (150 mL) was then added and the reactor mixture was heated to 48℃and added over 40 minutesBenzyl chloride (89 g) was added. The reaction formulation was then heated to 78 ℃ for 3 hours, after which it was cooled, neutralized to pH 7.0, and filtered. The resulting solid was washed 3 times with cold 20% aqueous methanol and dried in a vacuum oven at 40 ℃ to give 53g of yellow solid. By passing through ¹ H-NMR analysis confirmed that the degree of substitution of the thus-prepared benzyl alpha-1, 3-glucan product was 0.57.

Preparation of carboxymethyl benzyl alpha-1, 3-glucan

Benzyl alpha-1, 3-glucan prepared as above (DoS 0.57) was used to prepare carboxymethyl benzyl alpha-1, 3-glucan. Benzyl alpha-1, 3-glucan (53 g) was suspended in 410mL of 92wt% aqueous ethanol and stirred at room temperature. The mixture was cooled to 15-19 ℃ with an ice water bath. To the cooled stirred suspension was added 48g of 50wt% sodium hydroxide solution over 20 minutes. The formulation was removed from the ice water bath and stirred for 25 minutes. The formulation was then cooled in an ice-water bath and 30.9g chloroacetic acid (in 30g 92wt% ethanol) was added in two portions: the first two thirds of the addition and then stirring at 15 ℃ for 15 minutes followed by the remaining one third. After the reaction formulation was removed from the ice water bath, and the reaction formulation was stirred at 300rpm for 15 minutes at room temperature. The reaction formulation was then immersed in an oil bath preheated at 90 ℃. The reaction formulation was then heated at 74 ℃ (internal temperature) for 3 hours. The reaction formulation was then cooled, diluted with 53g of water and neutralized with 10wt% hcl to pH 6.7. The reaction formulation was filtered and the solid was washed with 70% aqueous methanol to give a brown solid. The solid material was dissolved in 200mL of water, adjusted to pH 8 with 0.1N NaOH, and then added to cold methanol. The resulting suspension was stirred at 10℃for 1 hour. The liquid was decanted from the suspension and more cold methanol was added to the residual solids followed by another decantation. This procedure was repeated twice. The final fraction was obtained by adding 2-propanol to the residual solid, yielding an off-white solid (carboxymethyl benzyl alpha-1, 3-glucan product) isolated by filtration. The solids were combined to give 40g. By passing through ¹ H-NMR confirmed that the carboxymethyl substitution degree of the product was 0.59.

Preparation of benzyl alpha-1, 3-glucan (dos 0.17)

980mL of water and poly alpha-1, 3-glucan (DPw about 740, 270g of a wet cake containing 40wt% glucan and 60wt% water) were added in portions to a 4-neck, 2-L flask with stirring. Sodium hydroxide (55 g of 50wt% aqueous solution) was added dropwise over a period of 10 minutes while stirring the mixture at 20℃to 25℃and then at room temperature for 2 hours. The formulation was heated to 75 ℃ and then benzyl chloride (77 g) was added. The reaction was heated to 85 ℃ and held at that temperature for 3.5 hours. The reaction was then cooled and filtered. The solid was washed with water (3X 700 mL), ethanol (50 wt%,800 mL), methanol (80 wt%,800 mL), acetone (800 mL) and hexane (2X 500 mL). The resulting solid was placed on a frit under vacuum and N ₂ Drying under purge for 3 hours provided a white solid material (benzyl alpha-1, 3-glucan product). The product was dried under vacuum at 80 ℃ overnight with a nitrogen purge to provide 96g of product. By passing through ¹ H-NMR analysis confirmed that the degree of substitution of the thus-prepared benzyl alpha-1, 3-glucan product was 0.17.

Preparation of carboxymethyl benzyl alpha-1, 3-glucan (dos 1.92)

Benzyl alpha-1, 3-glucan prepared as above (DoS 0.17) was used to prepare carboxymethyl benzyl alpha-1, 3-glucan. A4-neck, 250-mL round bottom flask was equipped with an overhead mechanical stirrer, thermocouple and N ₂ An inlet. Ethanol (92 wt%) and benzyl alpha-1, 3-glucan (20 g) were added to the flask. The mixture was stirred at room temperature for 30 minutes. Sodium hydroxide (40 g of a 50wt% aqueous solution) was added dropwise over a period of 10 minutes while stirring. The slurry was stirred at room temperature for 15 minutes. Chloroacetic acid (11.6 g in 5g 92wt% ethanol) was added over 5 minutes. The reaction was stirred at 63℃to 65℃for 3 hours. After cooling to 30 ℃, the pH of the reaction was adjusted to about 7 by adding 18.5wt% hcl solution. The solids were collected by filtration and reslurried with warm methanol (90 wt%,150 mL) and then filtered to give a wet cake. The wet cake was washed with methanol (90 wt%,3×150 mL) by reslurrying and filtration, and then dried under vacuum to give a solid material (22.3g) It was further purified by TFF (nanofiltration: film: PES,5K MWCO) was purified with about 5L water exchange, and then further purified using a 10K MWCO membrane. The retentate was concentrated and dried to provide carboxymethyl benzyl alpha-1, 3-glucan (18.1 g). By passing through ¹ The degree of substitution with carboxymethyl was 1.75 as determined by H-NMR. The total DoS of carboxymethyl benzyl alpha-1, 3-glucan was 1.92.

Preparation of benzyl alpha-1, 3-glucan (dos 0.5)

Alpha-1, 3-glucan (53 kg of wet cake containing 89wt% glucan and 11wt% water) was charged to a 150-gallon reactor under nitrogen, followed by water (2216 kg). To the mixture was added 10wt% sodium hydroxide solution (202 kg), and the mixture was stirred at room temperature under nitrogen for 2 hours. The reactor was heated to 65 ℃ and benzyl chloride (58.5 kg) was added to the reactor. The reactor temperature was raised to 80-85 ℃ and the reaction was heated for 3.5 hours. The reactor was cooled to 70 ℃ and the pH of the reaction was adjusted to pH 3 using 3M sulfuric acid. The reaction solid (benzyl α -1, 3-glucan) was washed with methanol/water (5:1), acetone (2X), methanol, and then dried. By passing through ¹ H-NMR confirmed that the degree of substitution of the benzyl alpha-1, 3-glucan product was 0.5.

Preparation of carboxymethyl benzyl alpha-1, 3-glucan

Benzyl alpha-1, 3-glucan prepared as above (DoS 0.5) was used to prepare carboxymethyl benzyl alpha-1, 3-glucan. A4-neck, 250-mL round bottom flask was equipped with an overhead mechanical stirrer, thermocouple and N ₂ An inlet. Ethanol (92 wt%,120 mL) and benzyl alpha-1, 3-glucan (20 g) were added to the flask. The mixture was stirred at room temperature for 30 minutes. Sodium hydroxide (20 g,50wt% aqueous solution) was added dropwise over a period of 10 minutes while stirring. The slurry was stirred at room temperature for 15 minutes. Chloroacetic acid (11.6 g in 5g 92wt% ethanol) was added over 5 minutes. The reaction was stirred at 60℃to 62℃for 4 hours. The solids in the reaction are not completely soluble in water. After cooling to 35 ℃, sodium hydroxide (11.5 g,50w% aqueous solution) and chloroacetic acid (6.8 g in 3g of 92wt% ethanol) were added. The resulting formulation was stirred at 60 ℃. At 60℃for 1.5 hours Thereafter, large agglomerates are formed. The heating is turned off. The top liquid was decanted, methanol (50 w%,150 mL) was added, and the pH of the resulting mixture was adjusted to about 7 by the addition of 18.5wt% hcl solution. The mixture was slowly stirred at room temperature overnight to form a gel. Methanol (50 mL) was slowly added while stirring the gel. A soft solid precipitated. The top liquid was decanted. Methanol (90 wt%,150 mL) was added. The solid was collected by filtration and washed with methanol (90 wt%,3×100 mL) and then dried in vacuo to give a brown solid product (20.5 g). The product was further purified by ultrafiltration. The product was dissolved in about 1.5L of water. The solution was purified by TFF (nanofiltration, membrane: regenerated cellulose, 10K MWCO) exchange with about 5L of water. The retentate was concentrated and dried to give carboxymethyl benzyl alpha-1, 3-glucan product (16.8 g). By passing through ¹ H-NMR determined that the degree of substitution with carboxymethyl was 0.95.

Example 1

Synthesis of oxidized carboxymethyl alpha-1, 3-glucan (ADW 10)

A4-neck, 250-mL round bottom flask equipped with a stir bar, thermocouple, addition funnel, and air inlet was charged with an aqueous solution of carboxymethyl α -1, 3-glucan (10 g, DPw 800, doS 0.48; denoted herein as "ADW 10-contrast") in 90mL of DI-water. 2, 6-tetramethylpiperidine 1-oxyl (TEMPO, 0.1 g) and NaBr (1 g) were then added. To the stirred mixture (TEMPO not completely dissolved at this stage) was added NaClO (10 wt% to 15wt%,38 mL) dropwise over 0.5 hours. The pH of the formulation was then adjusted to 10.7 using NaOH (2N, 15 mL). The thus prepared oxidation reaction was stirred at room temperature for three hours. The crude material was then diluted in 1 gallon DI-water, stirred at room temperature for 3 hours, filtered, purified by ultrafiltration (pelrich MINI, with 5kDa MWCO cartridge), and freeze-dried to provide 10.7g of oxidation product. The total carboxyl DoS of the oxidized carboxymethyl alpha-1, 3-glucan product (referred to herein as "ADW 10") as contributed by a single carboxymethyl and a single carboxyl group passes ¹³ C-NMR (nuclear magnetic resonance) analysis was determined to be 0.66. Its Mw was determined by Size Exclusion Chromatography (SEC) to be 37kDa. Thus, it was found that the ADW10 product was at least further substituted with carboxyl groups, whichIs compared to its parent compound (ADW 10-control).

Example 2

Synthesis of oxidized carboxymethyl alpha-1, 6-glucan (ADW 18)

A4-neck, 500-mL round bottom flask equipped with a stir bar, thermocouple, addition funnel and air inlet was charged with 62.3g of a 32.1wt% aqueous solution of alpha-1, 6-glucan (200 kDa,20% alpha-1, 2 branches). To this was added sodium hydroxide solution (30 g of 50wt% NaOH solution). The solution was stirred overnight. The solution was heated in a 50 ℃ oil bath and a monochloroacetic acid (MCA) solution (12 grams MCA in 8 grams DI-water) was added via an addition funnel. The solution was then heated in an oil bath at 65 ℃ for 2 hours. The solution was cooled to room temperature and neutralized with 18wt% hcl (20 mL). A10-mL sample of this reaction was harvested and its carboxymethyl alpha-1, 6-glucan product (denoted herein as "ADW 18-control") was purified in methanol. By passing through ¹³ C-NMR analysis determined the carboxymethyl DoS of the product to be 0.38.

TEMPO (0.15 g) and NaBr (1.5 g) were added to the above reaction. NaClO (10 wt% to 15wt%,150 mL) was then added dropwise over 0.5 hours. NaOH (2N, 50 mL) was used to adjust the pH. The final pH was 10.2. The thus prepared oxidation reaction was stirred at room temperature for 2 hours. The crude material was diluted in 1 gallon DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI, with 5kDa MWCO cartridge), and freeze-dried to provide 22.6g of oxidation product. The total carboxyl DoS of the oxidized carboxymethyl alpha-1, 6-glucan product (referred to herein as "ADW 18") as contributed by a single carboxymethyl and a single carboxyl group passes ¹³ C-NMR analysis was found to be 0.58. Its Mw was determined by SEC to be 32kDa. Thus, the ADW18 product was found to be at least further substituted with carboxyl groups, as compared to its parent compound (ADW 18-control).

Example 3

Synthesis of oxidized carboxymethyl cellulose (ADW 28)

To a 4-neck, 250-port equipped with stirring rod, thermocouple, addition funnel and air inletThe mL round bottom flask was charged with an aqueous solution of carboxymethyl cellulose (10 g, sigma-Aldrich, product number CMC419311, — Mw 250kDa, doS 0.7, referred to herein as "ADW 28-contrast") in 110mL of DI-water. TEMPO (0.05 g) and NaBr (0.5 g) were then added. To this stirred solution was added NaClO (10 wt% to 15wt%,50 mL) dropwise over 0.5 hours. The pH of the solution was then adjusted to 10.7 using NaOH (25 wt%,2 mL). The thus prepared oxidation reaction was stirred at room temperature for two hours. The crude material was then precipitated in methanol (500 mL), washed three times with methanol (100 mL/each) and dried under vacuum to provide 10g of oxidation product. Total carboxyl DoS pass of oxidized carboxymethyl cellulose product (herein referred to as "ADW 28") as contributed by a single carboxymethyl group and a single carboxyl group ¹³ C-NMR analysis was found to be 1.60. Its Mw was determined by SEC to be 21kDa. The ADW28 product is believed to be further substituted with at least carboxyl groups, as compared to its parent compound (ADW 28-control).

Example 4

Synthesis of oxidized carboxymethyl starch (ADW 31)

A4-neck, 500-mL round bottom flask equipped with a stir bar, thermocouple, addition funnel and air inlet was charged with starch (20 g, sigma-Aldrich product number S9765, soluble starch). To this was added sodium hydroxide solution (34 g of 50wt% NaOH solution). The solution was stirred overnight. The solution was heated in a 50 ℃ oil bath and a monochloroacetic acid (MCA) solution (16 grams MCA in 8 grams DI-water) was added via an addition funnel. The solution was then heated in an oil bath at 65 ℃ for 2 hours. The solution was cooled to room temperature and neutralized with 18wt% hcl (13 mL). A10-mL sample of the reaction was harvested and its carboxymethyl starch product (denoted herein as "ADW 31-comparative") was purified in methanol. By passing through ¹³ C-NMR analysis determined the carboxymethyl DoS of the product to be 0.62.

TEMPO (0.1 g) and NaBr (1.0 g) were added to the above reaction. NaClO (10 wt% to 15wt%,100 mL) was then added dropwise over 0.5 hours. NaOH (2N, 17 mL) was used to adjust the pH. The final pH was 9.9. Oxygen thus prepared The reaction was stirred at room temperature for 1.5 hours. The crude material was diluted in 1 gallon DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI, with 5kDa MWCO cartridge), and freeze-dried to provide 21.2g of oxidation product. Total carboxyl DoS pass of oxidized carboxymethyl starch product (herein referred to as "ADW 31") as contributed by a single carboxymethyl and a single carboxyl group ¹³ C-NMR analysis was found to be 0.67. Its Mw was determined by SEC to be 53kDa. Thus, the ADW31 product was found to be at least further substituted with carboxyl groups, as compared to its parent compound (ADW 31-comparison).

Example 5

Synthesis of oxidized carboxymethyl dextran (ADW 36)

A4-neck, 500-mL round bottom flask equipped with a stir bar, thermocouple, addition funnel, and air inlet was charged with dextran (20 g) produced using Glucosyltransferase (GTF) 0768 as described in U.S. patent application publication 2016/012445, incorporated herein by reference. To this was added sodium hydroxide solution (34 g of 50wt% NaOH solution). The solution was stirred overnight. The solution was heated in a 50 ℃ oil bath and a monochloroacetic acid (MCA) solution (16 grams MCA in 8 grams DI-water) was added via an addition funnel. The solution was then heated in an oil bath at 65 ℃ for 2 hours. The solution was cooled to room temperature and neutralized with 18wt% hcl (17 mL). A10-mL sample of this reaction was harvested and its carboxymethyl dextran product (denoted herein as "ADW 36-comparative") was purified in methanol. By passing through ¹³ C-NMR analysis determined the carboxymethyl DoS of the product to be 0.46.

TEMPO (0.1 g) and NaBr (1.0 g) were added to the above reaction. NaClO (10 wt% to 15wt%,90 mL) was added dropwise over 0.5 hours. NaOH (2N, 15 mL) was used to adjust the pH. The final pH was 9.6. The thus prepared oxidation reaction was stirred at room temperature for 1.5 hours. The crude material was diluted in 1 gallon DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI, with 5kDa MWCO cartridge), and freeze-dried to provide 17.8g of oxidation product. Oxidized carboxymethyl dextran product (referred to herein as "ADW 36") as defined by a singleTotal carboxyl DoS contributed by carboxymethyl and Single carboxyl passes ¹³ C-NMR analysis was found to be 0.51. Its Mw was determined by SEC to be 49kDa. Thus, the ADW36 product was found to be at least further substituted with carboxyl groups, as compared to its parent compound (ADW 36-control).

Example 6

Synthesis of oxidized carboxymethyl dextran (ADW 39)

A4-neck, 500-mL round bottom flask equipped with a stir bar, thermocouple, addition funnel and air inlet was charged with dextran (30 g, sigma-Aldrich product number D5376, leuconostoc mesenteroides, mw 150-280 ten thousand Da) and DI-water (120 mL). To this was added sodium hydroxide solution (51 g of 50wt% NaOH solution). The solution was stirred overnight. The solution was heated in a 50 ℃ oil bath and a monochloroacetic acid (MCA) solution (24 grams MCA in 12 grams DI-water) was added via an addition funnel. The solution was then heated in an oil bath at 65 ℃ for 2 hours. The solution was cooled to room temperature and neutralized with 18wt% hcl (23 mL). A10-mL sample of this reaction was harvested and its carboxymethyl dextran product (denoted herein as "ADW 39-control") was purified in methanol. By passing through ¹³ C NMR analysis determined the carboxymethyl DoS of the product to be 0.58.

TEMPO (0.15 g) and NaBr (1.5 g) were added to the above reaction. NaClO (10 wt% to 15wt%,135 mL) was added dropwise over 0.5 hours. NaOH (2N, 20 mL) was used to adjust the pH. The final pH was 9.6. The thus prepared oxidation reaction was stirred at room temperature for 1.5 hours. The crude material was diluted in 1 gallon DI-water, stirred at room temperature for 1 hour, filtered, purified by ultrafiltration (PELLICON MINI with 5KDa MWCO cartridge), and freeze-dried to provide 32.5g of oxidation product. The total carboxyl DoS of the oxidized carboxymethyl dextran product (referred to herein as "ADW 39") as contributed by a single carboxymethyl and a single carboxyl group passes ¹³ C-NMR analysis was found to be 0.67. Its Mw was determined by SEC to be 27kDa. Thus, the ADW39 product was found to be at least further substituted with carboxyl groups, as compared to its parent compound (ADW 39-control).

Example 7

Synthesis of cyanoethyl carboxyethyl alpha-1, 3-glucan oxide (ADW 7)

A4-neck, 1-L round bottom flask equipped with a mechanical stirrer bar, thermocouple and addition funnel was charged with 260g of an alpha-1, 3-glucan (DPw 800) wet cake (38.5 wt% glucan) and 550g of DI-water. The mixture was stirred at room temperature while 64g of 50wt% sodium hydroxide solution were added over a period of 15 minutes. Acrylonitrile (64 g) was then slowly added at 25℃over 10 minutes. The cyanoethylation reaction thus prepared was stirred at room temperature for 3.5 hours. HCl (18.5 wt%,135 g) was then added to bring the pH of the reaction to about 7. The crude product was precipitated and washed in methanol to provide 124 grams of cyanoethyl carboxyethyl α -1, 3-glucan (denoted herein as "ADW 7-contrast"). By passing through ¹³ C NMR analysis of the product confirmed a DoS with cyanoethyl and carboxyethyl groups of 0.90 and 0.12, respectively. Due to basic aqueous conditions, carboxyethyl groups are formed in the above reaction via hydrolysis of some of the cyano groups.

A4-neck, 250-mL round bottom flask equipped with a stir bar, thermocouple, addition funnel and air inlet was charged with an aqueous solution of the cyanoethyl carboxyethyl α -1, 3-glucan product prepared above (5 g, ADW 7-comparative) in 50mL of DI-water. TEMPO (0.1 g) and NaBr (1 g) were then added to the solution. To this stirred solution was added NaClO (10 wt% to 15wt%,25 mL) dropwise over 0.5 hours. The pH of the solution was then adjusted to 10.5 using NaOH (2N, 13 mL). The thus prepared oxidation reaction was stirred at room temperature for three hours. The crude material was then diluted in 1 gallon DI-water, stirred at room temperature for 6 hours, filtered, purified by ultrafiltration (pelrich MINI with 5KDa MWCO cartridge), and freeze-dried to provide 3.7g of oxidation product. By passing through ¹³ C-NMR analysis the DoS of the oxidation product (denoted herein as "ADW 7") was determined to be 0.61/0.61 (cyanoethyl/carboxyl) (carboxyl DoS reported as contributed by a single carboxyethyl group and a single carboxyl group). Its Mw was determined by SEC to be 37kDa.

Example 8

Oxidized polysaccharide derivatives can reduce the effect of hard water cations in aqueous compositions

This example shows that simultaneously (i) derivatizing with one or more organic groups and (ii) oxidizing the polysaccharide can reduce the effect of hard water cations in an aqueous composition. In particular, each of the oxidized polysaccharide derivatives prepared in examples 1-7 above exhibited enhanced ability to reduce turbidity caused by calcium carbonate formation as compared to its respective non-oxidized counterpart. Thus, oxidized polysaccharide derivatives as disclosed herein may be used to reduce or prevent the negative effects from hard water cations in aqueous compositions.

Oxidized polysaccharide derivatives from examples 1-7 above and their respective non-oxidized counterparts (20 mg) were dissolved alone in Deionized (DI) -water (45 mL) overnight. An aqueous sodium carbonate solution (5 mL of a 0.6wt% aqueous solution) was then added to each solution to form a clear formulation. While stirring (600 rpm), each formulation (14 mL thereof) was titrated with a calcium chloride solution (2 wt% in DI-water) at 10. Mu.L/sec over 160 seconds. The turbidity of each sample was then measured at 400 seconds using a calibrated turbidimeter (HACH 2100P). This test was repeated three times for each polysaccharide derivative compound and the average turbidity was reported in nephelometric turbidity units (NTU, table 1). The data provided in table 1 shows that water treatment with each oxidized polysaccharide derivative sample, with its non-oxidized counterpart, resulted in lower NTU measurements, indicating better binding of the oxidized sample to calcium cations. This combination forms soluble polysaccharide-calcium complexes that can be readily removed (e.g., by rinsing) with reduced formation of calcium carbonate (and other insoluble hard water cation salts, when applicable) that would otherwise form undesirable deposits. In addition, it is believed that oxidized polysaccharide derivatives may exhibit beneficial effects by interacting with insoluble calcium carbonate to better stabilize, disperse, and/or prevent deposition of the salt; the benefits apply equally to other hard water cation-carbonates. Thus, the polysaccharide derivatives of the present disclosure may exert beneficial effects by (i) blocking/reducing hard water cationic carbonate production and/or (ii) interacting with any hard water cationic carbonate formed.

TABLE 1

Example 9

Polysaccharide derivatives provide benefits to dishwashing formulations

This example shows that polysaccharide derivatives can provide anti-accumulation/film/scale activity to dishwashing detergents. In particular, cleaning dishes using an automatic dish detergent comprising carboxymethyl alpha-1, 3-glucan or carboxymethyl benzyl alpha-1, 3-glucan results in reduced deposits on the cleaned dishes.

Carboxymethyl alpha-1, 3-glucan (DoS 0.91) and carboxymethyl benzyl alpha-1, 3-glucan (DoS 1.92) prepared according to the above materials/methods were tested separately in the following phosphate-free automatic dishwashing detergent formulations (table 2).

TABLE 2

^a Table 3 below lists the dispersant polymers used in each formulation.

Comparative experiments were performed in a dishwasher using the automatic dishwashing detergent compositions specified in table 2 above. The purpose of this experiment was to establish the anti-accumulation properties of the functionalized alpha-1, 3-glucan derivatives versus petroleum-based sulfonated acrylate copolymers described in the above materials/methods in automatic dishwashing detergents. Examples of commercially available sulfonated acrylate copolymers are ACUSOL 588G (Dow), and SOKALAN CP 50 (BASF).

The following experimental conditions were applied. Automatic dishwashing detergent is placed in the MIELE GSL2 dishwasher for six consecutive cycles. No rinse aid or salt was added to the machine. The dishwasher program for each cycle was operated at 50 ℃ during main wash with a hold time of 8 minutes and a rinse temperature of 65 ℃. The water hardness was set at 36℃German hardness (645 ppm, ca) ²⁺ :Mg ²⁺ 2:1). At the beginning of each cycle, 19g of the detergent composition (table 2) and 50g of frozen IKW ballast soil were dosed into the machine. The IKW ballast soil was placed in the upper housing of a dishwasher and its composition was published in SOFW journal 06/16 (incorporated herein by reference) as "Recommendations for the Quality Assessment of the Cleaning Performance of Dishwasher Detergents [ quality assessment suggestion of cleaning performance of dishwasher detergent ]](section B, 2015 update) ".

The cutlery product was placed in the machine before the first wash and removed after the sixth wash cycle as follows: (i) In the upper frame, four pieces of flat bottom glass (long drink), MEPAL plastic food container (styrene-acrylonitrile) and stainless steel knife; (ii) In the lower frame, food boxes (polypropylene), blue plastic trays (melamine) and black plastic cutting boards (polyethylene); (iii) A virtual load consisting of porcelain and glass plate is added in the lower frame, and four porcelain tea cups are placed in the upper frame.

The flat bottom glass and plastic container were removed from the dishwasher after final washing and after open air drying, film formation was rated according to ASTM method D3556-14 (incorporated herein by reference), ranging from 1 (no film) to 5 (severe film formation). The average of 1 to 5 film formation was determined as reported in table 3 below.

TABLE 3 Table 3

Measuring accumulation (filming) left by dishwashing detergent composition

It was concluded that automatic dishwashing detergent compositions having one or more dextran carboxylate derivatives as dispersant polymer ingredient show improved anti-filming properties. For example, an automatic dishwashing detergent with carboxymethyl benzyl alpha-1, 3-glucan appears on glass at least comparable to an automatic dishwashing detergent with petroleum-based dispersant ACUSOL 588G. Carboxymethyl alpha-1, 3-glucan also provides anti-film-forming activity on glass. On plastics, both carboxymethyl benzyl and carboxymethyl alpha-1, 3-glucan perform better than petroleum-based dispersants in reducing film formation. It is contemplated that, based on the results in table 1, other polysaccharide compounds disclosed herein having substitution with one or more organic groups having carboxylic acid groups (e.g., oxidized polysaccharide derivatives, carboxyalkyl dextran derivatives) may also be used to provide anti-film forming activity to automatic dishwashing detergent compositions.

Example 10

Scale inhibition performance of various dextran anionic ether derivatives

Scale formation is a serious problem from energy and water to many industries, such as home care and personal care. . Scale is caused by the formation of inorganic salt deposits created by divalent ions dissolved in the aqueous phase, which combine to form insoluble salts. These salts may deposit on surfaces present in systems containing an aqueous phase. For example, in oilfield tops and related facilities, these surfaces may be the inner walls of the pipeline or the internal working surfaces of the pump. Another problem is the formation of small inorganic salt particles that can pass through the system with the flow of liquid (also known as suspended solids) over time and clog filters or cause clogging problems. Another system in which scale formation is a problem is an industrial cooling system. Scale formation is also a problem in home and personal care applications such as automatic dishwashing. For example, scale deposition may leave undesirable films on glassware and other eating utensils. Examples of inorganic salts that may be found in scale include CaCO ₃ 、CaSO ₄ 、Fe ₂ O ₃ FeS and FeS ₂ 。

Scale inhibitors include polymers containing a large number of charged groups. The anionic polymer has negatively charged groups (e.g., carboxyl groups) and the cationic polymer has positively charged groups (e.g., amine groups). Such polymers may provide competitive binding sites for ions and prevent them from binding to each other to form scale. The scale inhibiting polymer with bound scale ions typically remains in solution and thus prevents the formation of deposits. Acrylic acid-based polymers are the standard for scale inhibition (e.g., with acrylamide as the base monomer) in several industries today. In addition to being hydrocarbon-based (i.e., non-renewable) and non-biodegradable, acrylic-based polymers also have environmental toxicity problems due to their bioaccumulation and nucleophilic attack by the polymer (e.g., by H ₂ S) resulting in release of monomers.

The dextran derivatives herein represent an opportunity to replace the current scale resistant polymers with biodegradable and renewable alternatives. As shown in this example, the various dextran derivatives have the same or better anti-scale function than the function of the hydrocarbon-based, currently used acrylic acid-based anti-scale compounds.

Experimental procedure:

the following system was used to test the scale inhibiting activity of various dextran derivatives such as alpha-dextran derivatives. Preparation of 0.06% w/w Na ₂ CO ₃ Samples of aqueous solutions (50 mL) were dissolved in alpha-glucan carboxymethyl ether derivative, carboxymethyl cellulose, or active acrylate (ACUSOL 420, dow company (Dow, inc.) alone to 400mg/L (or no compound added as a control). Table 4 below describes each of these compounds. Shortly after each formulation was mixed, 14mL was removed and placed in a clear 20-mL glass vial and stirred. Then 2% w/w CaCl ₂ Solutions (4×400 μl) were slowly pipetted into each Na ₂ CO ₃ Vial of compound solution. Using a HACH nephelometer (determination of the introduction by insoluble particlesLight scattering [ i.e., turbidity ]]Spectrophotometer of (c) to observe and measure insoluble CaCO ₃ Particle formation and the results were measured as FNU (foromazine turbidity units). The FNU level (turbidity) is related to the amount of scale that may be formed (e.g., a low FNU score means lower scale producing activity).

Results:

table 4 shows the turbidity measurements taken above. All dextran compounds tested were anionic due to substitution with carboxymethyl groups.

TABLE 4 Table 4

₃ Measuring the effect of various compounds on turbidity caused by CaCO formation

^a Two separate FNU (Fulmahydrazine turbidity units) measurements were taken for each sample, denoted 1 and 2.

^b NA, inapplicable.

^c The alpha-glucan and cellulose compounds tested were Carboxymethyl (CM) ether derivatives with the degree of substitution (DoS) listed.

^d RV, reduced viscosity as measured for α -glucan prior to ether derivatization.

^e IV, intrinsic viscosity as measured for α -glucan prior to ether derivatization.

^f GT48, a dextran-alpha-1, 3-glucan graft copolymer having a dextran backbone content of about 48wt% and an alpha-1, 3-glucan side chain content of about 52 wt%. The graft copolymer is generally prepared according to the procedure as disclosed in U.S. patent application publication 2020/0165360, which is incorporated herein by reference. Typically, the graft copolymer is prepared by first incorporating water, sucrose and a glucosyltransferase enzyme (GTF 0768, disclosed in U.S. Pat. No. 10059779 as SEQ ID NO:1 and 2, which are incorporated by reference hereinIncorporated herein) to synthesize dextran. Using dextran as primer/acceptor, then synthesizing alpha-1, 3-glucan in a similar manner as described in U.S. patent application publication No. 2020/0165360 (above) or 2019/0078063 (which are incorporated herein by reference); thus, the α -1, 3-glucan side chains (each having 100% α -1,3 linkages) were synthesized from the dextran backbone to form the dextran- α -1, 3-glucan graft copolymer.

^g Glucan P, a dextran-alpha-1, 3-glucan graft copolymer prepared generally following the procedure as disclosed in U.S. patent application publication No. 2019/0185893, which is incorporated herein by reference. Briefly, the GlucanP graft copolymer comprises (a) an α -1, 6-glucan backbone (100% of α -1, 6-linkages prior to the α 0-1,3 branching), which (i) has been branched by about 16% of the α -1,3 linkages (i.e., the backbone comprises about 84% of the α -1,6 linkages and about 16% of the α -1,3 linkages in total) and (ii) has a Mw of about 20.2kDa, and (B) has a few α -1, 3-glucan side chains (each having 100% of the α -1,3 linkages) extending from some of the α -1,3 branches. The GlucanP graft copolymer is water insoluble prior to carboxymethylation.

The data in table 4 support the following conclusions, for example:

each of the tested alpha-glucan CM ether derivatives (high DPw alpha-1, 3-glucan, GT48, glucan P) was prepared by reducing CaCO ₃ The formation to control haze formation is significantly superior to the commercially available acrylic-based compounds.

Each branched α -glucan CM ether derivative (GlucanP and GT 48) exhibits similar turbidity control activity as exhibited by carboxymethyl cellulose, although the charge of the branched α -glucan derivative is lower (lower CM DoS) compared to the cellulose derivative. Thus, it is expected that α -glucan derivatives may provide good anti-scale activity while providing better biodegradability properties due to lower DoS. The latter applies equally to high DPwα -1, 3-glucan CM derivatives.

By varying the DoS and/or the degree of branching of this type of α -glucan compound, it is possible to optimize the anti-scale activity of the GlucanP ether.

In general, anionic α -glucan ethers represent a new class of scale-inhibiting compounds that can be further developed for this field of application.

Example 11

Flocculation of calcium carbonate using oxidized alpha-1, 3-glucan

Calcium carbonate (CaCO) ₃ ) And other types of inorganic scale precipitation are problems in several processes. One example is the paper industry, where it is desirable to remove calcium carbonate from industrial liquid streams. However, inorganic salts such as calcium carbonate precipitate in a colloidal form, which can present challenges for their removal from liquid streams. Another industry in which scale removal is important is the petroleum industry. The water produced by flocculation-based treatment of the liquid stream is then used in other parts of the petroleum production process.

Oxidized alpha-1, 3-glucan polymers can be prepared via functionalization of linear alpha-1, 3-glucan. In this example, oxidized alpha-1, 3-glucan was shown to be capable of capturing calcium ions while allowing calcium to bind to its carbonate counter ion to provide calcium carbonate. This process triggers the precipitation of the alpha-1, 3-glucan/calcium carbonate complex; thus, oxidizing alpha-1, 3-glucan can flocculate calcium carbonate. This process represents a new method for removing calcium carbonate from industrial streams where inorganic scale is not desired.

Synthesis of oxidized alpha-1, 3-glucan (sample 1):

dried water insoluble α -1, 3-glucan (10 g) (about 100% α -1,3 glycosidic linkages) and 4-acetamide-TEMPO (0.97 g) were suspended in 500mL acetate buffer (0.2 m, ph 4.6). To this formulation was added 11.2g sodium chlorite (14.7 mL). The flask was then capped with a stopper. The oxidation reaction was stirred at 40 ℃ for 24 hours. The oxidation reaction was then quenched with the addition of excess ethanol followed by the addition of 80% aqueous ethanol. The isolated oxidized alpha-1, 3-glucan product was dried in a vacuum oven at 40 ℃. The oxidation degree of the product was measured to be 0.39DO _COONa 。(COO ^- Average occurrence of (c) per glucose monomer of glucan).

Synthesis of oxidized alpha-1, 3-glucan (sample 2):

the procedure used for the preparation of sample 1 above was followed except that 9.44g of sodium chlorite was added and the oxidation reactant was stirred at 60 ℃ for 18 hours. DO (DO) _COONa Not measured.

Experiment:

separate solutions (445 ppm) of the oxidized alpha-1, 3-glucan products of samples 1 and 2 were prepared in demineralised water.

With 5mL of 0.6wt% Na ₂ CO ₃ Solutions Each solution (45 mL) was modified to give a solution having 400ppm polymer and 600ppm Na ₂ CO ₃ Is a solution of (a) and (b). Then, 14mL of each solution was taken, and 1800. Mu.L of 2wt% CaCl was slowly added thereto with a pipette ₂ A solution. At the time of adding CaCl ₂ Thereafter, the turbidity of each formulation was determined using a Hach turbidimeter. Sample 1 had a turbidity of 40.1FNU (fomamzine turbidity units) while sample 2 had a turbidity of 150 FNU. Each formulation was left for 15 minutes to monitor floc formation activity.

The capture of calcium carbonate by oxidized alpha-1, 3-glucan proceeds through multiple stages (fig. 1):

first, ca ²⁺ Captured by the dissolved oxidized alpha-1, 3-glucan.

Then, precipitation was slowly started, and an opaque substance (turbidity) was formed in the preparation.

Sedimentation results in the formation of flocs, which settle to the bottom, producing a clear top phase (clear water).

It was observed with a stereomicroscope (400 x, data not shown) that calcium carbonate crystals formed predominantly spherical, colloidally insoluble structures in the absence of oxidized alpha-1, 3-glucan. However, in the presence of oxidized alpha-1, 3-glucan, oxidized glucan encapsulates itself around colloidal crystals to provide flocculated sediment. Such materials allow for better handling and removal of the combined precipitate.

Example 12

Polysaccharide derivative (Carboxylic acid nail)Radical or carboxylmethyl oxide) and their benefits for dishwashing formulations

This example shows that polysaccharides that have been (i) derivatized with one or more organic groups comprising carboxylic acid groups, or (ii) derivatized with one or more organic groups and then oxidized, can reduce the effects of hard water cations and provide benefits for scale inhibition and dishwashing formulations.

The above procedure was used to produce various polysaccharide derivatives (listed in table 5) and dissolved separately (20 mg) in Deionized (DI) -water (45 mL) overnight. An aqueous sodium carbonate solution (5 mL of a 0.6wt% aqueous solution) was then added to each solution to form a clear formulation. In the grade-1 test, each formulation (14 mL thereof at a polysaccharide derivative concentration of 400 ppm) was titrated with a calcium chloride solution (2 wt% in DI-water) at 10. Mu.L/sec over 160 seconds while stirring (600 rpm). The turbidity of each sample was then measured at 400 seconds using a calibrated nephelometer (HACH 2100P or HACH 2100P). The test was repeated at least once for each polysaccharide derivative compound and the average turbidity was reported in nephelometric turbidity units (NTU, table 5). In the class-2 test, concentration-dependent tests were performed using formulations with various sample concentrations (250 ppm, 200ppm, 150ppm, 100ppm, 85ppm, 71ppm and 50 ppm). The minimum concentration required to prevent phase separation during the test period was determined (table 5).

The data in table 5 shows that inclusion of the polysaccharide derivative results in lower NTU measurements compared to the negative control (no added polysaccharide derivative), indicating that the polysaccharide derivative binds to calcium cations. This combination forms soluble polysaccharide-calcium complexes that can be readily removed (e.g., by rinsing) with reduced formation of calcium carbonate (and other insoluble hard water cation salts, when applicable) that would otherwise form undesirable deposits. In addition, it is believed that polysaccharide derivatives may exhibit beneficial effects by interacting with insoluble calcium carbonate (e.g., as observed in example 11) to better stabilize, disperse, and/or prevent deposition of the salt; the benefits apply equally to other hard water cation-carbonates. Thus, the polysaccharide derivatives of the present disclosure may exert beneficial effects by (i) blocking/reducing hard water cationic carbonate production and/or (ii) interacting with any hard water cationic carbonate formed. Polysaccharide derivatives also show excellent calcium cation dispersing ability by requiring much less material to prevent phase separation in this test.

TABLE 5

^a The alpha-1, 6-glucan contains about 100% alpha-1, 6 glycosidic linkages (prior to alpha-1, 2-branching, etherification and oxidation (as applicable).

^b The alpha-1, 3-glucan contains about 100% of alpha-1, 3 glycosidic linkages (in the case of benzyl groups [ Bz ]]And carboxymethyl [ CM ]]Before etherification).

^c Alpha-1, 6-glucan is produced as described using GTF 0768 as described in U.S. patent application publication No. 2016/012445 (incorporated herein by reference).

Claims

1. A composition comprising an oxidized polysaccharide derivative, wherein the oxidized polysaccharide derivative is produced by contacting a polysaccharide derivative under aqueous conditions with at least one agent capable of oxidizing the polysaccharide derivative, and wherein the polysaccharide derivative has a degree of substitution (DoS) with at least one organic group of up to about 3.0.

2. The composition of claim 1, wherein the polysaccharide derivative is a dextran derivative or a soybean polysaccharide derivative.

3. The composition of claim 2, wherein the polysaccharide derivative is the dextran derivative and the dextran derivative is an alpha-dextran derivative.

4. The composition of claim 3, wherein at least 50% of the glycosidic linkages of the alpha-glucan derivative are alpha-1, 3, alpha-1, 4, or alpha-1, 6 linkages.

5. The composition of claim 1, wherein the oxidized polysaccharide derivative has a biodegradability of at least 10% after 60 or 90 days as determined by a carbon dioxide release test method.

6. The composition of claim 1, wherein the polysaccharide from which the polysaccharide derivative is derived has a weight average degree of polymerization (DPw) of at least about 50.

7. The composition of claim 1, wherein the organic group is in ether linkage with the polysaccharide derivative.

8. The composition of claim 7, wherein the organic group comprises a carboxyalkyl, alkyl, hydroxyalkyl, or aryl group.

9. The composition of claim 7, wherein the organic group comprises a carboxymethyl group.

10. The composition of claim 1, wherein the organic group is in an ester linkage, a urethane linkage, or a sulfonyl linkage with the polysaccharide derivative.

11. The composition of claim 1, wherein the agent comprises an N-oxo ammonium salt.

12. The composition of claim 1, wherein the composition is a home care product, a personal care product, an industrial product, an ingestible product (e.g., a food product), or a pharmaceutical product.

13. The composition of claim 1, wherein the composition is an aqueous composition.

14. The composition of claim 13, wherein the aqueous composition further comprises at least one cation, and the oxidized polysaccharide derivative is bound to the cation.

15. The composition of claim 1, wherein the composition is in the form of, or is contained in, a liquid, gel, powder, hydrocolloid, granule, tablet, capsule, bead or lozenge, single-compartment pouch, multi-compartment pouch, single-compartment pouch, or multi-compartment pouch.

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

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

18. The composition of claim 17, wherein the enzyme is a cellulase, protease, lipase, amylase, or lipase.

19. The composition of claim 1, further comprising at least one of: complexing agents, soil release polymers, surface active enhancing polymers, bleaching agents, bleach activators, bleach catalysts, fabric conditioners, clays, suds boosters, suds suppressors, anti-corrosion agents, soil suspending agents, anti-soil redeposition agents, dyes, bactericides, tarnish inhibitors, optical brighteners, perfumes, saturated or unsaturated fatty acids, dye transfer inhibitors, chelants, shading dyes, visual signal transmission components, defoamers, structurants, thickeners, anti-caking agents, starches, sand, or gelling agents.

20. A method of producing an oxidized polysaccharide derivative, the method comprising:

(b) Optionally isolating the oxidized polysaccharide derivative.