Modified sophorolipids with enhanced defoaming properties

Abstract

The present invention provides modified sophorolipids that can eliminate existing foams and / or prevent the formation of new foams. The modification includes peracetylation and / or global conversion of sophorose hydroxyl groups of sophorolipids to ethers to reduce HLB values and produce bio-based antifoams having high bio-based carbon content. The invention also provides compositions comprising modified sophorolipids and methods of inhibiting and / or reducing foam formation using such compositions.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 388,419, filed on July 12, 2022, which is incorporated herein by reference in its entirety. Background Art

[0003] Foam is often an undesirable consequence of the production of various substances (e.g., surfactants and proteins), especially in processes involving significant shear forces near the gas-liquid interface (e.g., processes involving aeration, pumping, or stirring). Foams can cause serious problems in industrial processes such as food processing, water treatment, pulp and paper, paints and coatings, and chemical manufacturing. For example, they can cause defects in surface coatings, prevent efficient filling of containers, and cause pump and sprayer failures. Therefore, defoamers are needed in such industrial processes.

[0004] Defoamers are often developed to eliminate unwanted foam in industrial processes. Defoamers come in many forms, including hydrophobic solids, in-situ formation of hydrophobic solids, surfactant competition, low surface tension liquids, and antagonistic surfactants or polymers. Common defoamers include insoluble oils, polydimethylsiloxanes and other silicones, certain alcohols, stearates, and glycols.

[0005] While defoamers must be able to help control or minimize the amount of foaming that occurs in the intended application, it is equally important that the defoamer not negatively impact the functional properties of the materials with which it is used or the quality of the product. In certain target applications, it may be necessary to remove the defoamer to reduce contamination.

[0006] Since defoamers are often hydrophobic, they can be difficult to sterilize, which can cause problems in the food and pharmaceutical industries, for example. Therefore, chemical defoamers are not always ideal, especially in the food, feed and pharmaceutical industries. In addition, regulatory requirements in these industries limit the chemicals that are acceptable for use in antifoams and defoamers.

[0007] Bio-based defoamers can provide an excellent alternative to existing defoamers on the market. Therefore, there is a need to develop bio-based defoamers for various applications. Summary of the invention

[0008] The present invention provides modified sophorolipids with defoaming properties. The present invention also provides compositions comprising such modified sophorolipids as defoaming agents. The present invention also provides materials and methods for producing sophorolipids that can be modified; and materials and methods for modifying sophorolipids to produce bio-based defoaming agents.

[0009] In one embodiment, the present invention provides compounds useful as foam control agents. In a preferred embodiment, the compounds of the present invention having defoaming properties have a structure selected from the following:

[0010]

[0011] ii) Formula (III)

[0012]

[0013] iii) Formula (V)

[0014]

[0015] iv) Formula (VII)

[0016]

[0017] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, R1 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, substituted heteroaryl; R2 is -(CH2) n -, wherein n≥1; R3 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, substituted heteroaryl; and R4 is selected from amino acid side chains, preferably amino acid side chains with aromatic groups.

[0018] In a preferred embodiment, each R is independently selected from H, R1 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl and R2 is -(CH2) n -, wherein 1≤n≤10; R3 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, isopropyl and isobutyl; and R4 is selected from More preferably, each R is independently selected from

[0019] In a specific embodiment, the compound of the present invention is selected from SH-global ether-COOH, SH-peracetylated-COOH, SH-peracetylated-furfuryl, SH-global ether-furfuryl, global ether lactone, SH-peracetylated-methoxy, SH-peracetylated-ethoxy, SH-peracetylated-O-isobutyl, SH-peracetylated-phenylalanine and SH-peracetylated-tryptophan.

[0020] In one embodiment, the present invention provides a defoaming composition comprising a compound of the present invention and optionally comprising one or more of the following defoaming compounds: silica, hydrophobic silica, polyethylene wax, ethylene bis stearamide wax, polypropylene wax, polydimethylsiloxane, organic modified polydimethylsiloxane and hydrophobic polyoxyethylene glycerol ether.

[0021] In one embodiment, the present invention provides a defoaming detergent composition comprising a compound of the present invention and optionally detergent adjunct components selected from enzymes, oxygen bleaches, bleach activators, fluid reformers and neutral inorganic salts.

[0022] In one embodiment, the present invention provides a method for defoaming a liquid, the method comprising adding the defoaming composition of the present invention to a liquid in need thereof, wherein the defoaming composition comprises a defoaming agent or a foam control agent, and the defoaming agent or the foam control agent comprises one or more modified sophorolipids of the present invention.

[0023] In a particular embodiment, defoaming a liquid may include hindering the formation of foam or entrainment of gas in the liquid during preparation, vacuum stripping, sparging with a gas, or pumping of the liquid.

[0024] In a particular embodiment, the liquid may be selected from, for example, paints, fermentation broths, detergent compositions, crop protection and crop nutrition formulations, fiber finishing and textile treatment formulations, drilling fluids, fracturing fluids, fluids used in pulp / paper processing, and cement compositions.

[0025] In one embodiment, the present invention also provides a method for preventing or reducing foam formation in a liquid, wherein the method comprises combining the liquid with the defoaming composition of the present invention. Preferably, the liquid is selected from paints, fermentation broths, detergent compositions, crop protection and crop nutrition formulations, fiber finishing and textile treatment formulations, drilling fluids, fracturing fluids and cement compositions. DETAILED DESCRIPTION

[0026] The present invention provides a bio-based defoamer or foam control agent, and a composition comprising the bio-based defoamer or foam control agent for industrial use. Advantageously, the bio-based defoamer or foam control agent can eliminate existing foam and / or prevent further foam formation. Preferably, the bio-based defoamer or foam control agent is a modified sophorolipid with reduced foaming properties.

[0027] The present invention provides modified sophorolipids, which are used as defoamers in industrial processes such as food processing, water treatment, pulp and paper processing, paints and coatings, and chemical manufacturing. The present invention also provides defoamer compositions comprising modified sophorolipids for various applications such as agriculture, environmental protection, water treatment, pharmaceutical industry, food processing, petroleum production, and detergent industry.

[0028] The present invention also provides materials and methods for producing sophorolipids that are easily modified; and materials and methods for modifying sophorolipids to produce bio-based defoamers.

[0029] Sophorolipids are one of the most promising and attractive biosurfactants, combining green chemistry with a low carbon footprint. Sophorolipids are glycolipid biosurfactants produced by various yeasts, such as the Saccharomyces clade. Biosurfactants are amphiphilic molecules derived from microorganisms, consisting of a hydrophobic domain (e.g., fatty acids) and a hydrophilic domain (e.g., sugars). The properties of biosurfactants (e.g., antibacterial, emulsifying and wetting properties, low toxicity, biodegradability, and production from renewable resources) make them widely used as wetting agents, emulsifiers, and detergents in industrial production, agriculture, and daily life.

[0030] Sophorolipids are amphiphilic molecules with an inherently hydrophobic half. Sophorolipids include sophorose, which consists of two glucose molecules connected to fatty acids via a glycosidic ether bond. Sophorolipids can be divided into two common forms: the lactone form, in which the carboxyl group in the fatty acid side chain and the sophorose moiety form a cyclic ester bond; and the acidic form or linear form, in which the ester bond is hydrolyzed.

[0031] Sophorolipids consist of disaccharide sophorose connected to long-chain hydroxy fatty acids. They may contain partially acetylated 2-O-β-D-glucopyranosyl-D-glucopyranose units connected to 17-L-hydroxyoctadecanoic acid or 17-L-hydroxy-Δ9-octadecenoic acid via a β-glycosidic bond. Hydroxy fatty acids may have, for example, 11 to 20 carbon atoms and may contain one or more unsaturated bonds.

[0032] In addition, the sophorose residues may be acetylated at the 6- and / or 6'-positions. The fatty acid carboxyl groups may be free (acidic or linear form) or esterified at the 4"-position (lactone form). In most cases, fermentation of sophorolipids produces a mixture of hydrophobic (water-insoluble) sophorolipids, including, for example, lactone sophorolipids, monoacetylated linear sophorolipids and diacetylated linear sophorolipids, and hydrophilic (water-soluble) sophorolipids, including, for example, non-acetylated linear sophorolipids.

[0033] Sophorolipids are usually produced as a mixture of related molecules. The differences between related molecules mainly come from: their fatty acid structure (unsaturation, chain length, unsaturation position and hydroxylation position); whether they are produced in linear or lactone form; acetylation pattern; the presence of stereoisomers; and / or whether the glycosidic bond on the fatty acid is in the ω-position (e.g., terminal) or the ω-1 position (subterminal).

[0034] The sophorolipid compounds of the present invention have many advantageous properties that make them superior to synthetic surfactants, such as biodegradability, low toxicity, high surface and interfacial activity, and stability over a wide range of temperature, pressure, and ionic strength. On the other hand, the functional properties of sophorolipids may differ between lactone and acidic types. For example, acidic sophorolipids generally have a higher hydrophilic-lipophilic balance (HLB) than lactone sophorolipids, while lactone sophorolipids generally have a lower HLB and greater surface tension reduction properties than acidic sophorolipids. In addition, acidic sophorolipids are generally highly water-soluble due to their free carboxylic acid groups.

[0035] As used herein, the terms "sophorolipid" and "sophorolipid molecule" include all forms of sophorolipid molecules and isomers thereof, including, for example, acidic (linear) sophorolipids and lactone-type sophorolipids. Also included are monoacetylated sophorolipids, diacetylated sophorolipids, esterified sophorolipids, sophorolipids with different hydrophobic chain lengths, sophorolipids with attached fatty acid-amino acid complexes, and other sophorolipids, including sophorolipids described and / or not described in the present disclosure.

[0036] Modified Sophorolipids

[0037] The linear sophorolipid molecule can be represented by the general formula (I):

[0038]

[0039] Where R 1 and R 2 are each independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, alkenyl, and substituted alkenyl; R 3 is hydrogen or alkyl; and R 4 is an alkane, a substituted alkane, an alkylene, a substituted alkylene, an alkenylene or a substituted alkenylene. Preferably, R 1 and R 2 is hydrogen; R 3 It is methyl.

[0040] Sophorolipid molecules can be obtained as a collection of 30 or more molecules with different fatty acid chain lengths and degrees of unsaturation (R 4 ), and in some cases, in R 1 and / or R 2 Acetylated or protonated.

[0041] Examples of the substituent include a halogen atom, a hydroxyl group, a lower (C1-6) alkyl group, a halogenated lower (C1-6) alkyl group, a hydroxy lower (C1-6) alkyl group, a halogenated lower (C1-6) alkoxy group, and the like. 4 Typically, it has 11 to 20 carbon atoms. In a preferred embodiment of the present invention, R 4 It has 16-17 carbon atoms.

[0042] In one embodiment, the present invention provides a modified sophorolipid, wherein the sophorolipid or truncated sophorolipid is linked to an amino acid via a primary amine. "Truncation" means that the carbon chain of the fatty acid is shorter than the carbon chain of the fatty acid normally present in the sophorolipid.

[0043] In one embodiment, the present invention provides a modified sophorolipid. Preferably, the modification includes, for example, full acetylation and esterification. In a preferred embodiment, the modified sophorolipid of the present invention has a general structure of formula (II):

[0044]

[0045] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, and R1 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl and substituted heteroaryl. Preferably, each R is independently selected from and R1 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl and

[0046]

[0047] In one embodiment, the present invention provides a modified sophorolipid having the general structure of formula (III):

[0048]

[0049] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, R2 is -(CH2) n -, wherein n≥1; R3 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl and substituted heteroaryl; and R4 is selected from amino acid side chains, preferably amino acid side chains having aromatic groups, for example, Preferably, each R is independently selected from 1≤n≤10; and R3 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl and

[0050] In one embodiment, the present invention provides a modified sophorolipid having a general structure of formula (IV), which is a cyclic ether analog of a lactone sophorolipid. Therefore, the present invention provides a compound of formula (IV):

[0051]

[0052] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, R5 is hydrogen or alkyl; and A is a saturated or unsaturated aliphatic chain, which may be optionally substituted. Preferably, each R is independently selected from H, And R5 is hydrogen or methyl.

[0053] In a preferred embodiment, the aliphatic chain A has 10 to 21 carbons, such that the total number of carbons in the aliphatic chain A, R5, and the carbon to which R5 is attached is 12 to 22 carbons.

[0054] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and having one, two, or three unsaturations.

[0055] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbons and having one, two, or three unsaturations.

[0056] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 16 carbons and having one, two, or three unsaturations.

[0057] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbons and having one, two, or three unsaturations.

[0058] In some embodiments, R is hydrogen, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and having one, two, or three unsaturations.

[0059] In some embodiments, R is hydrogen, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbons and having one, two, or three unsaturations.

[0060] In other embodiments, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and one unsaturation.

[0061] In other embodiments, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbons and one unsaturation.

[0062] In other embodiments, each R is independently hydrogen or ethyl, R5 is methyl, and A is a fully saturated aliphatic chain having 16 carbons.

[0063] In other embodiments, each R is independently hydrogen or ethyl, R5 is hydrogen, and A is a fully saturated aliphatic chain having 17 carbons.

[0064] In one embodiment, the present invention provides a modified sophorolipid having the general formula (V):

[0065]

[0066] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, Preferably, each R is independently selected from H,

[0067] In one embodiment, the present invention provides a modified sophorolipid having the general formula (VI):

[0068]

[0069] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, R5 is hydrogen or alkyl; and A is a saturated or unsaturated aliphatic chain, which may be optionally substituted. Preferably, each R is independently selected from H, And R5 is hydrogen or methyl.

[0070] In a preferred embodiment, the aliphatic chain A has 10 to 21 carbons, such that the total number of carbons in the aliphatic chain A, R5, and the carbon to which R5 is attached is 12 to 22 carbons.

[0071] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and having one, two, or three unsaturations.

[0072] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbons and having one, two, or three unsaturations.

[0073] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 16 carbons and having one, two, or three unsaturations.

[0074] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbons and having one, two, or three unsaturations.

[0075] In some embodiments, R is hydrogen, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and having one, two, or three unsaturations.

[0076] In some embodiments, R is hydrogen, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbons and having one, two, or three unsaturations.

[0077] In other embodiments, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and one unsaturation.

[0078] In other embodiments, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbons and one unsaturation.

[0079] In other embodiments, each R is independently hydrogen or ethyl, R5 is methyl, and A is a fully saturated aliphatic chain having 16 carbons.

[0080] In other embodiments, each R is independently hydrogen or ethyl, R5 is hydrogen, and A is a fully saturated aliphatic chain having 17 carbons.

[0081] In one embodiment, the present invention provides a modified sophorolipid having the general formula (VII):

[0082]

[0083] wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, Preferably, each R is independently selected from H,

[0084] In one embodiment, the modified sophorolipids of the present invention have a reduced HLB value compared to linear or lactone sophorolipids. In a specific embodiment, the modified sophorolipids of the present invention have an HLB value equal to or less than 6, preferably equal to or less than 5, more preferably equal to or less than 4, most preferably equal to or less than 3.

[0085] In a particular embodiment, the modified sophorolipid is selected from SH-global ether-COOH, SH-peracetylated-COOH, SH-peracetylated-furfuryl, SH-global ether-furfuryl, global ether lactone, SH-peracetylated-methoxy, SH-peracetylated-ethoxy, SH-peracetylated-O-isobutyl, SH-peracetylated-phenylalanine and SH-peracetylated-tryptophan.

[0086] Selected Definitions

[0087] As used herein, the term "foam" refers to a dispersion of gas bubbles in or on a liquid, in a gel, or in a semisolid. The gas bubbles may be dispersed throughout the liquid phase in a heterogeneous or homogeneous manner. Illustrative examples of foams include gases (e.g., air, nitrogen, oxygen, helium, or hydrogen) trapped in a liquid (e.g., water or oil). Foams may be transient, unstable, or stable.

[0088] As used herein, "surfactant" refers to a substance or compound that reduces surface tension when dissolved in water or an aqueous solution, or a substance or compound that reduces interfacial tension between two liquids or between a liquid and a solid. Thus, the term "surfactant" includes cationic, anionic, nonionic, zwitterionic, amphoteric agents, and / or combinations thereof. "Biosurfactant" refers to a surfactant produced by an organism and / or produced using a naturally derived matrix. "Surfactant" and "biosurfactant" also refer to substances that cause foaming.

[0089] As used herein, the term "alkyl" refers to a straight or branched hydrocarbon group. Suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl. The term alkyl can be prefixed with a specified number of carbon atoms to indicate the number of carbon atoms or range of carbon atoms that may be present in the alkyl group, such as C1-C10 alkyl, C1-C20 alkyl and C10-C20 alkyl. For example, C1-C3 alkyl refers to methyl, ethyl, propyl and isopropyl.

[0090] As used herein, an "isolated" or "purified" nucleic acid molecule, polynucleotide, polypeptide, protein, or organic compound (e.g., small molecule) is substantially free of other compounds (e.g., cellular material) with which it is associated in nature. A purified or isolated polynucleotide (ribonucleic acid (RNA) or deoxyribonucleic acid (DNA)) is free of genes or sequences adjacent to it in its naturally occurring state. A purified or isolated polypeptide is free of other molecules or amino acids adjacent to it in its naturally occurring state. An "isolated" strain refers to a strain removed from its naturally occurring environment. Thus, an isolated strain may exist, for example, as a biologically pure culture or spores (or other forms of a strain).

[0091] In some embodiments, the purified compound is at least 60wt% of the target compound. Preferably, the preparation is at least 75wt% of the target compound, more preferably at least 90wt%, most preferably at least 99wt%. For example, the purified compound is at least 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 98wt%, 99wt% or 100wt% (w / w) of the desired compound. Purity is measured by any appropriate standard method, for example, by column chromatography, thin layer chromatography or high performance liquid chromatography (HPLC) analysis.

[0092] The scope provided herein should be understood as the abbreviation of all values ​​in the scope. For example, the scope of 1 to 20 should be understood as including any number, combination of numbers or subranges in the group consisting of all intermediate decimal values ​​(such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 and 1.9) between 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 and the above-mentioned integers. About subrange, special consideration is given to "nested subrange" extending from either end of the scope. For example, the nested subrange of the example scope of 1 to 50 can include 1 to 10, 1 to 20, 1 to 30 and 1 to 40 in one direction, or 50 to 40, 50 to 30, 50 to 20 and 50 to 10 in another direction.

[0093] As used herein, "fermentation" refers to the growth or cultivation of cells under controlled conditions. Growth can be aerobic or anaerobic. Unless the context requires otherwise, the phrase is intended to encompass both the growth phase and the product biosynthesis phase of the process.

[0094] As used herein, "broth", "culture broth" or "fermentation broth" refers to a culture medium containing at least nutrients. If the broth is referred to after the fermentation process, the broth may also contain microbial growth byproducts and / or microbial cells.

[0095] The microbial growth container used according to the present invention can be any fermenter or culture reactor for industrial use. As used herein, the term "reactor", "bioreactor", "fermentation reactor" or "fermentation vessel" includes a fermentation unit composed of one or more containers and / or towers or pipeline arrangements. Examples of such reactors include, but are not limited to, continuous stirred tank reactors (CSTRs), immobilized cell reactors (ICRs), trickle bed reactors (TBRs), bubble columns, gas lift fermenters, static mixers, or other containers or other devices suitable for gas-liquid contact. In some embodiments, the bioreactor may include a first growth reactor and a second fermentation reactor. Therefore, when referring to adding a substrate to a bioreactor or fermentation reaction, it should be understood to include adding a substrate to any one or both of these reactors where appropriate.

[0096] As used herein, "decrease" refers to a negative change and "increase" refers to a positive change, wherein the change is at least 0.001%, 0.01%, 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99% or 100%, including all values ​​in between.

[0097] The terms "subject" or "patient" as used herein describe an organism, including mammals, such as primates. Mammalian species that may benefit from the disclosed treatment methods include, but are not limited to, apes, chimpanzees, orangutans, humans, and monkeys; domesticated animals, such as dogs, cats; livestock, such as horses, cattle, pigs, sheep, goats, and chickens; and other animals, such as mice, rats, guinea pigs, and hamsters.

[0098] The transitional term "comprising," which is synonymous with "including" or "containing," is inclusive or open-ended and does not exclude additional unrecited elements or method steps. In contrast, the transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting essentially of" limits the scope of the claim to the specified materials or steps "and those that do not materially affect the basic and novel characteristics of the claimed invention." Use of the term "comprising" contemplates other embodiments of "consisting of" or "consisting essentially of" the components described.

[0099] Unless expressly stated or obvious from the context, the term "or" as used herein should be construed as inclusive. Unless expressly stated or obvious from the context, the terms "a", "an" and "the" as used herein should be construed as singular or plural.

[0100] Unless expressly stated or obvious from the context, the term "about" as used herein should be understood to mean within the normal tolerance range in the art, such as within 2 standard deviations of the mean. About can be understood to be within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05% or 0.01% of the specified value.

[0101] In any definition of a variable herein, the narration of a list of chemical groups includes defining the variable as any single group or combination of the listed groups. The narration of an embodiment for a variable or aspect herein includes the embodiment as any single embodiment or in combination with any other embodiment or part thereof. All references cited herein are incorporated herein by reference.

[0102] Production of Sophorolipids

[0103] The present invention provides materials and methods for producing and modifying sophorolipids. Advantageously, the present invention is suitable for producing purified sophorolipids on an industrial scale and uses safe and environmentally friendly materials and processes.

[0104] Sophorolipids are usually obtained by microbial fermentation using a fermentation process including wild-type or engineered microorganisms, and microorganisms use pure fatty acids, fatty acid mixtures, pure fatty acid esters, fatty acid ester mixtures, triglycerides as carbon sources and carbohydrate sources such as corn syrup, dextrin and glucose. Sophorolipids are produced using renewable substrates and different microbial species and culture parameters (e.g., incubation time, stirring speed, pH value of culture medium and added nutrients), and compounds with different structures and physical properties can be obtained. This makes it possible to produce a variety of compounds showing different physical, chemical, biochemical and biophysical properties.

[0105] In a preferred embodiment of the invention, the method of the invention initially comprises the production of a standard sophorolipid molecule which is then used to produce a modified sophorolipid. In certain embodiments, this requires culturing a sophorolipid-producing yeast in a submerged fermentation reactor containing a customized oleochemical feedstock to produce a yeast culture product comprising a fermentation broth, yeast cells, and a sophorolipid having a mixture of two or more molecular structures.

[0106] The molecular structure mixture can include, for example, lactone sophorolipids, linear sophorolipids, deacetylated sophorolipids, monoacetyl sophorolipids, diacetyl sophorolipids, esterified sophorolipids, sophorolipids with different hydrophobic chain lengths, sophorolipids with attached fatty acid-amino acid complexes, and other sophorolipids, including sophorolipids described and / or not described in the present disclosure.

[0107] In certain embodiments, the distribution of the mixture of sophorolipid molecules can be altered by adjusting fermentation parameters (eg, feedstock, fermentation time, and dissolved oxygen levels).

[0108] Sophorolipids according to the present invention can be obtained from recombinant organisms or naturally produced sophorolipids by fermentation process. The non-limiting example of the organism producing sophorolipids includes Candida bombicola, Candida apicola, Candida bogoriensis, Yarrowia lipolytica, Starmerella bombicola, Starmerella clade, Rhodotorula bogoriensis, Wickerhamiella domericqiae and Wickerhamomyces anomalus. It is reported that some recombinant microorganisms producing sophorolipids allow control of sophorolipid structure. As a non-limiting example, some recombinant bumblebee raw Starmer yeast strains can be used to produce only lactones or only acidic sophorolipids. In addition, the recombinant bumblebee raw Candida strains of acetyltransferase gene knockout can be used to produce no acetylated sophorolipids.

[0109] In a preferred embodiment, the microorganism is a yeast or fungus. Examples of yeast and fungal species suitable for use according to the invention include, but are not limited to, Asessile Aspergillus, Aspergillus, Pullulan (e.g., Pullulan), Blakeslea, Candida (e.g., Candida albicans, Candida mellifera), Cryptococcus, Debaryomyces (e.g., Debaryomyces hansenii), Entomophthora, Fusarium, Hansenula spores (e.g., Hansenula spores), Hansenula, Issaffron, Kluyveromyces, Mortierella, Mucor (e.g., Mucor piriformis), Meyer's yeast (e.g., Meyer's yeast guillemot), Penicillium, Pythium,

[00136] The present invention relates to yeasts comprising the genera Pichia, Pichia (e.g., Pichia anomala, Pichia guilliermondii, Pichia occidentalis, Pichia kudriazia), Saccharomyces (e.g., Saccharomyces aphidoides), Rhizopus, Saccharomyces (Saccharomyces cerevisiae, Saccharomyces boulardii, Torulaspora), Starmosaccharomyces (e.g., Starmosaccharomyces bombus), Torulopsis, Chytridiomyces, Trichoderma (e.g., Trichoderma reesei, Trichoderma harzianum, Trichoderma viride), Ustilago (e.g., Ustilago maydis), Wickham's yeast (e.g., Wickham's yeast anomala), Willemsus, and Zygosaccharomyces (e.g., Zygosaccharomyces beijerinckii).

[0110] In a preferred embodiment, the microorganism is selected from, for example, the genus Starmosaccharomyces, yeasts and / or yeasts of the genus Candida, such as Bombus spp. Starmosaccharomyces (Candida), Candida mellifera, Candida batistae, Candida floricola, Candida riodocensis, Candida asteroidea and Candida kuoi. In a specific embodiment, the microorganism is Bombus spp. Starmosaccharomyces, such as strain ATCC 22214.

[0111] In one embodiment, the fermentation reactor may have, or may be connected to, functional controls / sensors to measure important factors in the culture process, such as pH, oxygen, pressure, temperature, agitator shaft power, humidity, viscosity and / or microbial density and / or metabolite concentration.

[0112] In yet another embodiment, the container can also monitor the growth of microorganisms in the container (e.g., measuring cell number and growth stage). Alternatively, samples can be taken from the container for counting, purity measurement, sophorolipid concentration and / or visible oil level monitoring. For example, in one embodiment, samples can be taken every 24 hours.

[0113] The microbial inoculum according to the present method preferably comprises cells and / or propagules of the desired microorganism, which may be prepared using any known fermentation method. If desired, the inoculum may be premixed with water and / or liquid growth medium.

[0114] The microorganism used according to the present invention can be natural or genetically modified. For example, a microorganism can be transformed with a specific gene to exhibit specific characteristics. The microorganism can also be a mutant of a desired strain.

[0115] In one embodiment, a single type of microorganism is grown in a reactor system. In alternative embodiments, multiple microorganisms can be grown in a single reactor system, and these microorganisms can be grown together without adversely affecting growth or the resulting products. For example, 2 to 3 or more different microorganisms can be grown simultaneously in a single reactor. In some embodiments, more than one microorganism is grown symbiotically in a reactor.

[0116] In certain embodiments, the culture may be supplemented with a carbon source. The carbon source may be: a carbohydrate such as glucose, dextrose, sucrose, lactose, fructose, trehalose, mannose, mannitol and / or maltose; an organic acid such as acetic acid, fumaric acid, citric acid, propionic acid, malic acid, malonic acid and / or pyruvic acid; an alcohol such as ethanol, propanol, butanol, pentanol, hexanol, isobutanol and / or glycerol; fats and oils such as rapeseed oil, soybean oil, rice bran oil, olive oil, corn oil, sunflower oil, sesame oil and / or linseed oil; molasses powder, etc. These carbon sources may be used alone or in combination of two or more.

[0117] In certain embodiments, the culture can be supplemented with a high oleic and / or pure oleic oleochemical feedstock, which results in a yeast culture product containing a narrower diversity of sophorolipid molecular structures than feedstocks containing other fatty acid sources, wherein the predominant sophorolipid molecules produced contain an 18C carbon chain and a single unsaturated bond at the ninth carbon.

[0118] In one embodiment, the liquid growth medium comprises a nitrogen source. The nitrogen source can be, for example, yeast extract, potassium nitrate, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonia, urea and / or ammonium chloride. These nitrogen sources can be used alone or in combination of two or more.

[0119] In one embodiment, the liquid growth medium may further include one or more inorganic salts. The inorganic salts may include, for example, potassium dihydrogen phosphate, monopotassium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium chloride, magnesium sulfate, magnesium chloride, iron sulfate, iron chloride, manganese sulfate, manganese chloride, zinc sulfate, lead chloride, copper sulfate, calcium chloride, calcium carbonate, calcium nitrate, magnesium sulfate, sodium phosphate, sodium chloride and / or sodium carbonate. These inorganic salts may be used alone or in combination of two or more.

[0120] In one embodiment, the culture medium comprises growth factors and micronutrients of microorganisms. The culture medium may also comprise inorganic nutrients, including trace elements, such as iron, zinc, copper, manganese, molybdenum and / or cobalt. In addition, the culture medium may also comprise sources of vitamins, essential amino acids, proteins and trace elements, such as corn flour, peptone, yeast extract, potato extract, beef extract, soybean extract, banana peel extract, etc., or in purified form. Amino acids may also be included, such as amino acids that can be used for protein biosynthesis.

[0121] The culture method can further provide oxygenation for the growing culture. One embodiment utilizes the slow movement of air to remove low oxygen air and introduce oxygenated air. The oxygenated air can be ambient air that is replenished daily by a mechanism that includes an impeller for mechanically agitating the liquid and an air sparger for providing bubbles to the liquid to dissolve oxygen into the liquid.

[0122] In one embodiment, the microorganisms may be grown on a solid or semi-solid substrate, such as a diet of corn, wheat, soy, chickpeas, beans, oatmeal, pasta, rice and / or flour or any of these or other similar substances.

[0123] In one embodiment, inorganic salts may also be included. Available inorganic salts may be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, magnesium sulfate, magnesium chloride, ferric sulfate, ferric chloride, manganese sulfate, manganese chloride, zinc sulfate, lead chloride, copper sulfate, calcium chloride, calcium carbonate, sodium chloride and / or sodium carbonate. These inorganic salts may be used alone or in combination of two or more.

[0124] In some embodiments, for example, when the microorganism used to inoculate the substrate is in spore form (e.g., bacterial endospores), a germination enhancer can be added to the substrate. Examples of germination enhancers according to the present invention include, but are not limited to, L-alanine, manganese, L-valine, and L-asparagine or any other known germination promoter.

[0125] The pH value of the culture should be suitable for the target microorganism. Buffers and pH regulators (such as carbonates and phosphates) can be used to stabilize the pH value near the preferred value. In some embodiments, an alkaline solution is used to adjust the pH value of the culture to a favorable level, such as using 15% to 30% or 20% to 25% NaOH solution. The alkaline solution can be included in the growth medium and / or can be sent to a fermentation reactor during the culture to adjust the pH as needed. When metal ions are present in high concentrations, it may be necessary to use a chelating agent in the liquid culture medium.

[0126] The methods and apparatus for microbial cultivation and microbial byproduct production may be performed as a batch, quasi-continuous, or continuous process.

[0127] In one embodiment, the culturing method is carried out at about 5°C to about 100°C, about 15°C to about 60°C, about 20°C to about 45°C, about 22°C to about 35°C, or about 24°C to about 28°C. In one embodiment, the culturing can be carried out continuously at a constant temperature. In another embodiment, the culturing can be subjected to a varying temperature.

[0128] According to the methods of the present invention, the microorganisms may be cultured in a fermentation system for a period of time sufficient to achieve a desired effect, for example, to produce a desired amount of cell biomass or a desired amount of sophorolipids.

[0129] In certain embodiments, the fermentation of the yeast culture lasts for about 40 to 150 hours, or about 48 to 140 hours, or about 72 to 130 hours, or about 96 to 120 hours. In certain specific embodiments, the fermentation time ranges from 48 to 72 hours, or 96 to 120 hours.

[0130] In some embodiments, the sophorolipid produced by the target microorganism can be retained in the microorganism or secreted into its growth medium. The sophorolipid content can be, for example, at least 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%.

[0131] The growth medium may contain compounds that stabilize the activity of the sophorolipids.The sophorolipids may be purified, or the sophorolipids may be used in crude form, meaning that they are not isolated from the fermentation broth in which they are produced.

[0132] In certain embodiments, the sophorolipids are isolated and / or purified from the growth medium produced by the fermentation of the microorganisms producing the biosurfactant. Isolation and purification can be easily achieved using standard methods or techniques described in the literature. If necessary, the sophorolipids can be further concentrated.

[0133] Sophorolipid modification

[0134] In one embodiment, the present invention provides a synthetic procedure to create a sophorolipid scaffold to add modifications to the fatty acid ends to enhance defoaming ability. The "scaffold" is the starting point for creating structure-activity relationships, for example, determining how each small modification contributes to defoaming ability. For example, converting carboxylic acids to methyl, ethyl or isobutyl esters can be used to create defoamers from fatty acids (e.g., stearic acid).

[0135] In some embodiments, the modified sophorolipid according to the present invention is obtained by chemically modifying a sophorolipid obtained from a fermentation product of a microorganism producing sophorolipid. The sophorolipid to be chemically modified can be obtained by a fermentation method and process as described above and / or any other method known in the art. Any suitable technique and chemical reaction known in the art can be used for modifying sophorolipid.

[0136] Chemical modifications may also be performed, for example to change the degree of unsaturation on the fatty acid chain. Commonly known hydrogenation or dehydrogenation reactions, or addition or elimination reactions may be used.

[0137] Sophorolipids containing unsaturated bonds at specific positions allow for site-specific functionalization of the sophorolipid molecule. In certain embodiments, the linear sophorolipid is ozonated with ozone gas. During the ozonolysis of the linear sophorolipid, the olefin portion of the sophorolipid molecule is converted into an ozonide, i.e., a reactive five-membered ring. In a preferred embodiment, the sophorolipid containing an ozonide is reduced to provide an aldehyde handle. In a specific embodiment, the reducing agent is triphenylphosphine used in an equimolar concentration with the sophorolipid-ozonide.

[0138] In certain embodiments, the reactive aldehyde handle, whether generated by ozonolysis or oxidative cleavage, is then used as a site for the addition of, for example, a primary amine by reductive amination. In certain embodiments, the reductive amination comprises introducing a primary amine into a sophorolipid-aldehyde under reducing conditions. This generates a stable secondary amine that serves as a covalent bond between the sophorolipid scaffold and the cargo (e.g., an amino acid) of the primary amine.

[0139] In certain embodiments, the reducing agent is sodium cyanoborohydride, sodium triacetoxyborohydride or sodium borohydride. In some embodiments, the linear sophorinaldehyde is extracted from the aqueous mixture with ethyl acetate and concentrated and dried at a temperature of about 35 to 45° C. under reduced pressure (e.g., about 200 to 250 mbar, or about 240 mbar). The dried crude linear sophorinaldehyde can then be dissolved in a reaction medium comprising tetrahydrofuran (THF) and water. The percentage of water used as the reaction medium is preferably no more than 50% water, and is typically 0 to 25%.

[0140] In some embodiments, the amide coupling addition of amino acids (e.g., phenylalanine methyl ester and tryptophan methyl ester) can retain the bio-based carbon of the amino acids while adding aromatic rings to keep the HLB of the sophorolipids within the defoaming range. Bio-based carbon is carbon directly from, for example, agricultural sources (e.g., sugar-based fermentation products). The bio-based carbon in the molecule is directly separated from the molecule due to the biological process. Bio-based carbon can be quantitatively measured by C14 radiocarbon testing.

[0141] In one embodiment, the modified sophorolipid of the present invention incorporates an amino acid in its structure, which is connected to the fatty acid chain of the sophorolipid structure through a primary amine. By covalently linking an amino acid to a sophorolipid or a truncated sophorolipid, the modified sophorolipid exhibits defoaming ability. In addition, the addition of amino acids contributes to bio-based carbon rather than synthetic carbon, thereby increasing the percentage of bio-based carbon in the modified sophorolipid, which enhances the defoaming performance of the modified sophorolipid. The percentage of bio-based carbon represents the number of bio-based carbons in the total number of atoms in the molecule (e.g., percentage of bio-based carbon = (number of bio-based carbons / total number of atoms) x 100).

[0142] Amino acids used herein have at least one amino group and at least one acid (e.g., carboxyl group) in their backbone, and different side chains for each amino acid. The side chains can be various substituents, including, but not limited to, hydrogen (e.g., as in glycine), organic, semi-organic or inorganic substituents, and rings cyclized to the amine (e.g., as in proline).

[0143] The amino acid used herein can be an L-amino acid or a D-amino acid. It can be a natural amino acid (e.g., an essential amino acid, a non-essential amino acid, or a conditional amino acid) or a synthetic / modified amino acid that does not exist in nature. The present invention encompasses amino acids that are incorporated into proteins and amino acids that are not incorporated into proteins. The amino acids that exist in nature can be purified products, or can be artificially synthesized.

[0144] In some embodiments, the amino acid according to the present invention is an α-amino acid, which contains an amino group and a carboxyl group, which are connected to the same carbon adjacent to the carboxyl group designated as the α-carbon. Non-limiting examples of α-amino acids include, for example, glycine, methionine, lysine, phenylalanine, tyrosine, tryptophan and glutamine.

[0145] Other non-limiting examples of amino acids that can be used in the present invention include, but are not limited to, alanine, β-alanine, arginine, asparagine, aspartic acid, cysteine, homocysteine, glutamic acid, histidine, homotaurine, isoleucine, leucine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, theanine, D-2-amino-3-guanidinopropionic acid, GABA, citrulline, tranexamic acid, aminocaproic acid, 4-amino-5-hexenoic acid, 4-hydroxyproline, 4-thioproline, 2-azaproline, 4-hydroxyproline Acid, 1,5-disubstituted tetrazole, 2-aminoisobutyric acid, sarcosine, 1-aminocyclopentane-1-carboxylic acid, β-alanine, 2-aminocyclopentanecarboxylic acid (β-proline), 5-hydroxylysine, hydroxylysine-5-sulfate, hydroxylysine-5-nitrate, hydroxylysine-5-phosphate, serine-3-sulfate, threonine-3-sulfate, serine-3-nitrate, threonine-3-nitrate, serine-3-phosphate, threonine-3-phosphate, 2-hydroxyalkanoic acid, 5-aminovaleric acid and 5-amino-2-oxopentanoic acid.

[0146] In some embodiments, the modified sophorolipid with an attached amino acid can be further esterified by a functional group through the carboxyl group of the amino acid. The functional group includes, but is not limited to, for example, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl and

[0147] Lactones themselves produce low HLB values, so peracetylation or global conversion of the sophorose hydroxyl groups to ethers will also reduce the HLB value, resulting in a bio-based defoamer with a high carbon percentage (ie, carbon %).

[0148] In one embodiment, the modified sophorolipids of the invention have a biobased carbon content of, for example, about 50% to about 100%, about 50% to about 95%, about 50% to about 90%, about 50% to about 80%, about 50% to about 70%, about 50% to about 60%, about 55% to about 90%, about 55% to about 85%, about 55% to about 80%, about 55% to about 75%, about 60% to about 85%, about 60% to about 80%, about 60% to about 75%, or about 60% to about 70%.

[0149] One embodiment relates to a method for producing a modified sophorolipid, comprising: obtaining linear sophorolipid molecules; functionalizing the linear sophorolipid molecules by converting all or most of the linear sophorolipid molecules into modified sophorolipid molecules.

[0150] Composition and use thereof

[0151] The present invention provides compositions for industrial use comprising the bio-based defoamers or foam control agents of the present invention. The bio-based defoamers or foam control agents eliminate existing foam and prevent further foam from forming. Advantageously, in preferred embodiments, the bio-based defoamers or foam control agents are biodegradable and do not need to be removed from the materials or final products with which they are used.

[0152] In one embodiment, the present invention provides a defoamer composition comprising a modified sophorolipid of the present invention. In one embodiment, the present invention provides a defoaming detergent composition comprising a modified sophorolipid of the present invention. In one embodiment, the present invention provides a cleaning composition comprising a modified sophorolipid of the present invention. In one embodiment, the present invention provides a coating composition, preferably a paint, comprising a modified sophorolipid of the present invention. Advantageously, the use of the present invention does not cause harm to the user, nor does it release large amounts of pollutants and toxic compounds into the environment.

[0153] In a further embodiment, the modified sophorolipids of the invention can be used in pulp and paper processing.

[0154] In some embodiments, the compositions of the invention comprise a modified sophorolipid, for example, at least 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70% by weight of the composition.

[0155] In certain embodiments, the compositions of the invention comprise a modified sophorolipid, for example, from about 0.001 to about 70%, from about 0.01 to about 60%, from about 0.1 to about 50%, from about 0.1 to about 45%, from about 0.1 to about 40%, from about 0.1 to about 35%, from about 0.1 to about 30%, from about 0.1 to about 25%, from about 0.1 to about 20%, from about 0.1 to about 20%, from about 0.1 to about 15%, from about 0.1 to about 10%, from about 0.1 to about 9.0%, from about 0.1 to about 8.0%, from about 0.1 to about 7.0%, from about 0.1 to about 6.0%, from about 0.1 to about 5.0%, from about 0.1 to about %, about 10 to about 40%, about 10 to about 40%, about 10 to about 30%, about 10 to about 20%, about 20 to about 30%, about 20 to about 40%, about 10 to about 30%, about 10 to about 20%, about 20 to about 30%, about 20 to about 40%, about 20 to about 50%, about 30 to about 50%, or about 30 to about 40%.

[0156] Other active antifoam compounds can be used in combination with the bio-based antifoam agents or foam control agents according to the present invention, such as silica, hydrophobic silica, polyethylene wax, ethylene bis stearamide wax, polypropylene wax, polydimethylsiloxane, organic modified polydimethylsiloxane and hydrophobic polyoxyethylene glycerol ether.

[0157] Optionally, the composition may further comprise one or more other components, including, for example, a carrier (e.g., water), other biosurfactants, other surfactants (e.g., polyalkyl glucosides, such as octyl glucoside and dodecyl glucoside), hydrophilic and / or hydrophobic synthetics, chelating agents, builders (e.g., potassium carbonate, sodium hydroxide, glycerol, citric acid, lactic acid), solvents (e.g., water, ethanol, methanol, isopropanol), organic and / or inorganic acids (e.g., lactic acid, citric acid, boric acid), essential oils, plant extracts, crosslinking agents, chelating agents (e.g., potassium citrate), fatty acids, alcohols, pH adjusters, reducing agents, calcium salts, carbonates, buffers, enzymes, dyes, colorants, fragrances, preservatives (e.g., octylisothiazolinone, methylisothiazolinone), terpenes (e.g., d-limonene), sesquiterpenes, terpenoids, emulsifiers, demulsifiers, bleaching agents, polymers, thickeners and / or viscosity increasing agents (e.g., xanthan gum, cardamom gum).

[0158] In some embodiments, the composition comprises an additional biosurfactant. The additional biosurfactant according to the present invention may include, for example, glycolipids, lipopeptides, yellow lipids, phospholipids, fatty acid esters and high molecular weight biopolymers, such as lipoproteins, lipopolysaccharide-protein complexes and / or polysaccharide-protein-fatty acid complexes.

[0159] In one embodiment, the additional biosurfactant is a glycolipid, for example, a rhamnolipid (RLP), a cellobiose lipid, a trehalose lipid and / or a mannosylerythritol lipid (MEL). In one embodiment, the biosurfactant is a lipopeptide, for example, a surfactin, iturin, fengycin, anthrofactin, amphisin, mucin, lichenin, paenibacterin, polymyxin and / or battacin.

[0160] In certain embodiments, the composition further comprises a detergent auxiliary component. Preferably, the detergent auxiliary component is selected from the group consisting of enzymes, oxygen bleaching agents, bleach activators, fluid reformers and neutral inorganic salts. Examples of enzymes include amylases, proteases, cellulose, lipases, pullulanase, isopulanase, isoamylase, catalase, peroxidase, etc. Examples of oxygen bleaching agents include peroxides that produce hydrogen peroxide in aqueous solution, such as perborate, percarbonate, persulfate, etc. Bleach activators are used to improve bleaching effects, such as tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), diacetyldioxyhexahydrotriazine (DADHT), glucose pentaacetate (GPA), sodium nonanoyloxybenzene sulfonate (SNOBS), etc. Neutral inorganic salts include sodium sulfate, potassium sulfate, etc. Fluid reformers can be silicon powder, anhydrous silicate, etc.

[0161] The composition may also include additional active or inactive ingredients suitable for the mode of administration and intended purpose, as long as such addition does not adversely interfere with the function of the modified sophorolipid.

[0162] The cleaning compositions of the present invention can be formulated, for example, as microemulsions, dissolvable powders and / or granules, compressed powders, loose powders, dilute sprays, concentrates, aerosols, foams, toilet bowl cleaners, laundry detergents, dishwashing detergents, encapsulated dissolvable capsules, gels, and / or pre-moistened or water-activated cloths, sponges, paper towels or other substrates.

[0163] In some embodiments, the composition can also include an acceptable carrier, which depends on the form of the composition. Acceptable carriers include but are not limited to inert diluents, disintegrating agents, adhesives, lubricants, flavoring agents, coloring agents and preservatives. Suitable inert diluents include sodium carbonate and calcium carbonate, sodium phosphate and calcium phosphate and lactose, while corn starch and alginic acid are suitable disintegrating agents. Adhesives can include starch and gelatin, and lubricants (if present) are typically magnesium stearate, stearic acid or talcum powder.

[0164] In some embodiments, the composition is in solid form, suitable for reconstitution in a solvent. In other embodiments, the composition further comprises a solvent. Suitable solvents can be aqueous or non-aqueous. In a particular embodiment, the solvent is an aqueous solvent. Examples of suitable solvents include water, buffer, acetonitrile, water and alcohol mixtures, such as aqueous methanol, aqueous ethanol and aqueous isopropanol.

[0165] Non-biological surfactants can also be added to the composition. Examples of surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates (e.g., sodium / ammonium lauryl sulfate and sodium / ammonium laureth sulfate), amphoteric surfactants (e.g., amphoacetates and amphopropionates), sulfosuccinates, alkyl polyglycosides, betaines (e.g., cocamidopropyl betaine), sulfobetaines, sarcosinates, isethionates, taurates, ethoxylated sorbitol esters, alkanolamides, and amino acid-based surfactants.

[0166] Viscosity modifiers may also be added to the composition and include, for example, cocamide DEA, oleamide DEA, sodium chloride, cellulosic polymers, polyacrylates, ethoxylates, alcohols, ethylene glycol, xylene sulfonates, polysorbate 20, alkanolamides, and cellulose derivatives (e.g., hydroxypropyl methylcellulose and hydroxyethyl cellulose).

[0167] Polymers may also be added including, for example, xanthan gum, cardamom gum, polyquaternium-10, PEG-120 methyl glucose dioleate, PEG-150 distearate, PEG-150 polyglyceryl-2 tristearate, and PEG-150 pentaerythritol tetrastearate.

[0168] In some embodiments, the composition can optionally include a preservative. Generally speaking, preservatives can be divided into specific categories, including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, biguanides, anilines, organic sulfur and sulfur nitrogen compounds, alkyl parahydroxybenzoates and miscellaneous compounds. Some non-limiting examples of phenolic antimicrobial agents include pentachlorophenol, o-phenylphenol, chloroxylenol, p-chlorometa-cresol, p-chlorophenol, chlorothymol, m-cresol, o-cresol, p-cresol, isopropyl cresol, mixed cresols, phenoxyethanol, phenoxyethyl parabens, phenoxyisopropyl alcohol, phenyl parabens, resorcinol and derivatives thereof. Some non-limiting examples of halogen compounds include trichlorohydroxydiphenyl ether (triclosan), sodium trichloroisocyanurate, sodium dichloroisocyanurate, iodine-polyvinylpyrrolidone complex and bromine compounds (such as 2-bromo-2-nitropropane-1,3-diol), and derivatives thereof. Some non-limiting examples of quaternary ammonium compounds include benzalkonium chloride, benzethonium chloride, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, and derivatives thereof. Some non-limiting examples of amines and nitro-containing compounds include hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates (such as sodium dimethyldithiocarbamate), and derivatives thereof. Some non-limiting examples of biguanides include polyaminopropyl biguanide and chlorhexidine gluconate. Some non-limiting examples of alkyl parabens include methyl, ethyl, propyl and butyl parabens. The preservative is preferably present in the composition in an amount of about 0 to about 3 wt %, about 0.1 to about 2 wt %, and about 0.2 to about 1 wt %.

[0169] The composition may include a pH adjusting agent (e.g., citric acid, ethanolamine, sodium hydroxide, etc.) to prepare a wide range of pH levels. In certain embodiments, the pH range of the composition is 2.0 to 11.0, 2.5 to 10, 3.0 to 9.0, 3.0 to 8.0, 3.0 to 7.0, 4.0 to 7.0, 5.0 to 7.0, 6.0 to 7.0, 6.0 to 8.0, or 6.0 to 9.0. Other pH ranges suitable for the composition of the present invention include 3.5 to 7.0 or 7.0 to 10.5. Suitable pH adjusting agents, such as sodium hydroxide, citric acid, and triethanolamine may be added to make the pH within the desired range.

[0170] The composition can be placed in a container of appropriate size, taking into account, for example, the intended use and the intended method of application. Thus, the container in which the composition is placed can be, for example, 0.1 gallons to 1000 gallons or larger. The composition can also be placed in smaller containers, such as bottles (e.g., 1.5 ounces, 500 milliliters, and 1 liter bottles) to dispense a single dose of the composition.

[0171] In some embodiments, the modified sophorolipids of the present invention are provided in the form of pharmaceutically acceptable salts. For example, if the side chain of an amino acid contains an appropriate functional group, it can also form a corresponding salt. Salts can be formed by steps well known and described in the art. Examples of pharmaceutically acceptable cations of salts include, but are not limited to, aluminum, arginine, benzathine, calcium, chloroprocaine, choline, diethanolamine, ethanolamine, ethylenediamine, lysine, magnesium, histidine, lithium, meglumine, potassium, procaine, sodium, triethanolamine, and zinc.

[0172] Depending on the chemical properties of the amino acids in the modified sophorolipids, acid addition salts can be formed. Examples of pharmaceutically acceptable acid addition salts include, but are not limited to, non-toxic inorganic and organic acid addition salts such as acetate derived from acetic acid, aconate derived from aconitic acid, ascorbate derived from ascorbic acid, benzenesulfonate derived from benzenesulfonic acid, benzoate derived from benzoic acid, cinnamate derived from cinnamic acid, citrate derived from citric acid, pamoate derived from pamoic acid, heptanoate derived from heptanoic acid, formate derived from formic acid, fumarate derived from fumaric acid, glutamate derived from glutamic acid, glycolate derived from glycolic acid, hydrochloride derived from hydrochloric acid, hydrobromic acid derived from hydrobromic acid. Salts derived from lactic acid, maleates derived from maleic acid, malonates derived from malonic acid, mandelates derived from mandelic acid, methanesulfonates derived from methanesulfonic acid, naphthalene-2-sulfonates derived from naphthalene-2-sulfonic acid, nitrates derived from nitric acid, perchlorates derived from perchloric acid, phosphates derived from phosphoric acid, phthalates derived from phthalic acid, salicylates derived from salicylic acid, sorbates derived from sorbic acid, stearates derived from stearic acid, succinates derived from succinic acid, sulfates derived from sulfuric acid, tartrates derived from tartaric acid, p-toluenesulfonates derived from p-toluenesulfonic acid, and the like.

[0173] The modified sophorolipids of the present invention can be provided in a non-solvated or solvated form with a pharmaceutically acceptable solvent such as water, ethanol, etc. The solvated form may also include a hydrated form such as a monohydrate, a dihydrate, a hemihydrate, a trihydrate, a tetrahydrate, etc.

[0174] The modified sophorolipids of the present invention have excellent defoaming and antifoaming properties as defoamers or foam control agents. Defoamers or foam control agents containing the modified sophorolipids of the present invention can be used to inhibit or reduce foam formation in, for example, detergents, foods, beverages, pharmaceuticals, cleaning products, industrial processes and biotechnology.

[0175] In one embodiment, the defoamer or foam control agent comprising the modified sophorolipid of the present invention can be used to control the foaming of paint / coating products. In one embodiment, the defoamer or foam control agent comprising the modified sophorolipid of the present invention can be used as an additive in applications where foaming is not required and / or where the formation of foam needs to be suppressed.

[0176] In one embodiment, the antifoaming agent or foam control agent comprising the modified sophorolipid of the present invention can be used as an ingredient in food and an ingredient in materials for food preparation.

[0177] In one embodiment, during the treatment of industrial wastewater, a defoamer or foam control agent comprising the modified sophorolipid of the present invention may be added to inhibit or reduce foam formation.

[0178] In one embodiment, the defoamer or foam control agent comprising the modified sophorolipid of the present invention can be used in the oil and gas industry, for example, in oil drilling and well treatment, to inhibit or reduce foam formation.

[0179] Typically, defoaming compositions are used to reduce interfacial tension in liquids. By reducing interfacial tension, defoaming compositions can allow gases to escape from liquids. Therefore, the defoaming compositions of the present invention can be used in well treatment fluids (e.g., drilling fluids, fracturing fluids, cement compositions, etc.) to prevent foaming or air entrainment during stirring, mixing or pumping of such fluids.

[0180] Defoamers or foam control agents comprising the modified sophorolipids of the present invention can also be used in many other industrial processes and products, such as wood pulp, paper, paint, machine tool industry, petroleum cutting tools and hydraulics.

[0181] In one embodiment, the present invention provides a method for defoaming a liquid, the method comprising combining / mixing the liquid with the defoaming composition of the present invention, wherein the defoaming composition comprises a defoaming agent or a foam control agent comprising the modified sophorolipid of the present invention.

[0182] In one embodiment, the present invention provides a method for defoaming a liquid, the method comprising adding the defoaming composition of the present invention to a liquid in need thereof, wherein the defoaming composition comprises a defoaming agent or a foam control agent comprising the modified sophorolipid of the present invention.

[0183] In a particular embodiment, defoaming a liquid may include hindering the formation of foam or hindering the entrainment of gas in the liquid during the preparation or pumping of the liquid.

[0184] In a particular embodiment, the liquid may be selected from, for example, paints, fermentation broths, detergent compositions, drilling fluids, crop protection and crop nutrition formulations, fiber finishing and textile treatment formulations, fracturing fluids, fluids used in pulp / paper processing, and cement compositions.

[0185] In one embodiment, the present invention also provides a method for preventing or reducing foam formation in a liquid, wherein the method comprises combining the liquid with the defoaming composition of the present invention. Preferably, the liquid is selected from paints, fermentation broths, detergent compositions, drilling fluids, crop protection and crop nutrition formulations, fiber finishing and textile treatment formulations, fracturing fluids and cement compositions.

[0186] Example

[0187] The following are exemplary compounds of the present invention, which are provided by way of illustration and are not intended to limit the present invention.

[0188] Through experimental techniques, Ferma SL and Ferma SH showed lower HLB values ​​than their calculated / theoretical HLB. This could be due to a number of reasons, including the carboxylic acid portion of SH not playing much of a role in the HLB contribution, to the hydroxyl groups on the sophorose being masked by the fatty acid chain / lactone. Sophorose containing the hydrophilic half can be peracetylated to significantly reduce its hydrophilicity, thereby reducing the HLB from 10 (for linears) and 7 (for lactones) to below 3, which bodes well for defoamers.

[0189] Table 1. Exemplary compounds

[0190]

[0191]

[0192]

[0193] All patents, patent applications, provisional applications, and publications mentioned or cited herein are incorporated by reference in their entirety, including all figures, to the extent they do not contradict the explicit teachings of this specification.

[0194] It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes thereto may be thought of by those skilled in the art and are included within the spirit and scope of the present application.

Claims

1. A compound whose structure is selected from: i) Formula (II): ii) Formula (III) iii) Formula (V) and iv) Formula (VII) wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, R1 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl and substituted heteroaryl; R2 is -(CH2) n -, wherein n≥1; R3 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl and substituted heteroaryl; and R4 is selected from amino acid side chains.

2. The compound according to claim 1, wherein each R is independently selected from H, 3. The compound according to claim 1, wherein R1 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl and 4. The compound according to claim 1, wherein R2 is -(CH2) n -, where 1≤n≤10.

5. The compound of claim 1, wherein R3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, isopropyl and isobutyl.

6. The compound according to claim 1, wherein R4 is selected from 7. The compound according to claim 1, wherein each R is independently selected from 8. The compound according to claim 1, which is selected from SH-global ether-COOH, SH-peracetylated-COOH, SH-peracetylated-furfuryl, SH-global ether-furfuryl, global ether lactone, SH-peracetylated-methoxy, SH-peracetylated-ethoxy, SH-peracetylated-O-isobutyl, SH-peracetylated-phenylalanine and SH-peracetylated-tryptophan.

9. The compound according to claim 1, which has a hydrophile-lipophile balance (HLB) value of ≤4.

10. The compound of claim 1 having a biobased carbon content of about 50% to about 80%.

11. The compound of claim 1 having a biobased carbon content of about 60% to about 75%.

12. A defoaming composition comprising the compound of claim 1.

13. The defoaming composition according to claim 12, further comprising one or more of the following defoaming compounds: silicon dioxide, hydrophobic silicon dioxide, polyethylene wax, ethylene bis stearamide wax, polypropylene wax, polydimethylsiloxane, organic modified polydimethylsiloxane, hydrophobic polyoxyethylene glycerol ether.

14. A defoaming detergent composition comprising the compound of claim 1 and detergent adjunct components.

15. A defoaming detergent composition according to claim 14, wherein the detergent adjunct components are selected from enzymes, oxygen bleaches, bleach activators, fluid reformers and neutral inorganic salts.

16. A cleaning composition comprising the compound of claim 1 and one or more of the following additional components: water, solvents, additional biosurfactants, additional surfactants, synthetic adjuvants, chelating agents, builders, preservatives, dyes, essential oils, substrates, enzymes, disinfectants, bleaching agents, and / or thickeners and / or viscosity enhancers.

17. A method for defoaming a liquid, wherein the method comprises combining the liquid with the defoaming composition of claim 12.

18. The method of claim 17, wherein the liquid is selected from the group consisting of paints, fermentation broths, detergent compositions, drilling fluids, fracturing fluids, and cement compositions.

19. A method for preventing or reducing the formation of foam in a liquid, wherein the method comprises combining the liquid with the antifoam composition of claim 12.

20. The method of claim 19, wherein the liquid is selected from the group consisting of paints, fermentation broths, detergent compositions, drilling fluids, fracturing fluids, and cement compositions.

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