Modified sophorolipid with improved defoaming properties

Abstract

The present invention provides modified sophorolipids that can remove existing bubbles and / or prevent the formation of new bubbles. The modification includes peracetylation of the sophorose hydroxyl groups of the sophorolipids and / or global conversion to ethers to produce a biosourced defoamer with a reduced HLB value and a high content of biosourced carbon. The present invention also provides a composition comprising the modified sophorolipids, and a method of using such a composition to suppress and / or reduce the formation of bubbles.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 388,419, filed on July 12, 2022, which is hereby incorporated by reference in its entirety.

Background Art

[0002] Background of the Invention Foam often undesirably occurs in the production of various substances such as surfactants and proteins, especially in processes with high shear forces near the gas - liquid interface, such as those involving aeration, pumping, or agitation. In industrial processes such as food processing, water treatment, pulp and paper, paints and coatings, and chemical manufacturing, foam presents serious problems. For example, it can cause defects in surface coatings, prevent efficient filling of containers, and cause pump and spray failures. Therefore, such industrial processes require defoamers.

[0003] The development of defoamers typically aims to remove unwanted foam in industrial production. Defoamers can be provided in various forms, including hydrophobic solids, in - situ formations of hydrophobic solids, competitors for surfactants, low - surface - tension liquids, and antagonistic surfactants or polymers. Commonly used defoamers include insoluble oils, polydimethylsiloxane and other silicones, certain alcohols, stearates, and glycols.

[0004] Defoamers must be able to control or minimize the amount of foaming that occurs in their intended applications, but it is also important that they do not adversely affect the functional properties of the materials in which they are used or the quality of the product. In certain specific intended applications, it may be necessary to remove the defoamer to reduce contamination.

[0005] Since defoamers are usually hydrophobic, they can be difficult to sterilize, which can be a problem, for example, in the food and pharmaceutical industries. Thus, chemical defoamers are not always desirable, especially in the food, feed, and pharmaceutical industries. Furthermore, the regulatory requirements in these industries limit the chemicals that are allowed for use in defoamers and antifoaming agents.

[0006] Biologically-derived defoamers can provide an excellent alternative to currently available defoamers. Thus, there is a need to develop biologically-derived defoamers for use in various applications.

Summary of the Invention

[0007] The present invention provides modified sophorolipids having defoaming properties. The present invention also provides compositions containing such modified sophorolipids as defoaming agents. The present invention further provides materials and methods for producing easily modifiable sophorolipids, as well as materials and methods for modifying sophorolipids to produce biologically-derived defoamers.

[0008] In one aspect, the present invention provides compounds that can be used as foam control agents. In a preferred aspect, the compounds of the present invention having defoaming properties are i) of formula (II): TIFF2025521965000001.tif49128ii) of formula (III): TIFF2025521965000002.tif77128iii) of formula (V): TIFF2025521965000003.tif44128and iv) of formula (VII): TIFF2025521965000004.tif59128having a structure selected from, wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000005.tif13128selected from; R1 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, and substituted heteroaryl; R2 is -(CH2) n -, where n ≥ 1; R3 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, and substituted heteroaryl; R4 is selected from amino acid side chains, preferably amino acid side chains having an aromatic group.

[0009] In a preferred embodiment, each R is independently selected from H, TIFF2025521965000006.tif31128; R1 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, i-propyl, i-butyl, and TIFF2025521965000007.tif11128; R2 is -(CH2) n -, where 1 ≤ n ≤ 10; R3 is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, i-propyl, and i-butyl; R4 is as follows: TIFF2025521965000008.tif25128. More preferably, each R is independently selected from the following: TIFF2025521965000009.tif19128.

[0010] 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-OMe, SH-peracetylated-Oet, SH-peracetylated-O-i-Bu (isobutyl), SH-peracetylated-phenylalanine, and SH-peracetylated-tryptophan.

[0011] In one embodiment, the present invention relates to a compound of the present invention and optionally the following defoaming compounds: Silica, hydrophobized silica, polyethylene wax, ethylene bis stearamide wax, polypropylene wax, polydimethylsiloxane, organically modified polydimethylsiloxane, and hydrophobized polyethylene oxide glycerol ether Provided is an antifoaming composition comprising one or more of the above and.

[0012] In one aspect, the present invention provides a defoaming detergent composition comprising a compound of the present invention and, optionally, a detergent auxiliary component selected from enzymes, oxygen bleaching agents, bleach activators, fluid modifiers, and neutral inorganic salts.

[0013] In one aspect, the present invention provides a method for defoaming a liquid, comprising the step of adding the antifoaming composition of the present invention to a liquid in need thereof, wherein the antifoaming composition comprises an antifoaming agent or foam control agent comprising one or more of the modified sophorolipids of the present invention.

[0014] In a specific aspect, defoaming the liquid may include inhibiting the formation of foam or the incorporation of gas in the liquid during the preparation, vacuum stripping, sparging with gas, or pumping of the liquid.

[0015] In a specific aspect, the liquid may be selected from, for example, paints, fermentation broths, detergent compositions, crop protection and crop nutrition formulations, textile finishing and fabric treatment formulations, drilling fluids, fracturing fluids, fluids used in pulp / paper processing, and cement compositions.

[0016] In one aspect, the present invention also provides a method for preventing or reducing the formation of foam in a liquid, comprising the step of combining the liquid with the antifoaming composition of the present invention. Preferably, the liquid is selected from paints, fermentation broths, detergent compositions, crop protection and crop nutrition formulations, textile finishing and fabric treatment formulations, drilling fluids, fracturing fluids, and cement compositions.

Mode for Carrying Out the Invention

[0017] Detailed Description The present invention provides a biologically-derived defoaming agent or foam control agent, and a composition comprising the biologically-derived defoaming agent or foam control agent for industrial use. Advantageously, the biologically-derived defoaming agent or foam control agent can remove existing foam and / or prevent further foam formation. Preferably, the biologically-derived defoaming agent or foam control agent is a modified sophorolipid with reduced foaming properties.

[0018] The present invention provides modified sophorolipids as defoaming agents for use in industrial processes such as food processing, water treatment, pulp and paper processing, paints and coatings, chemical manufacturing, etc. The present invention also provides defoaming agent compositions comprising modified sophorolipids for use in various applications, for example, in agriculture, environmental protection, water treatment, the pharmaceutical industry, food processing, oil production, and the detergent industry.

[0019] The present invention further provides materials and methods for producing easily-modifiable sophorolipids, and materials and methods for modifying sophorolipids to generate biologically-derived defoaming agents.

[0020] Sophorolipids are one of the most promising and attractive biosurfactants that combine a low carbon footprint with green chemistry. Sophorolipids are glycolipid biosurfactants produced by various yeasts of the Starmerella clade, for example. Biosurfactants are microbial amphiphilic molecules consisting of both a hydrophobic domain (e.g., fatty acid) and a hydrophilic domain (e.g., sugar). Due to the properties of biosurfactants such as antibacterial, emulsifying and wetting properties, low toxicity, biodegradability, and manufacturability from renewable resources, they are widely used in industrial production, agriculture, and daily life as wetting agents, emulsifiers, and detergents.

[0021] Sophorolipids are amphiphilic molecules, half of which are essentially hydrophobic. Sophorolipids contain sophorose, which consists of two glucose molecules linked to a fatty acid by a glycoside ether bond. Sophorolipids are classified into two broad forms: a lactone form in which a carboxyl group in the fatty acid side chain and the sophorose moiety form a cyclic ester bond, and an acidic or linear form in which the ester bond is hydrolyzed.

[0022] Sophorolipids consist of the disaccharide sophorose linked to a long-chain hydroxy fatty acid. They may contain a partially acetylated 2-O-β-D-glucopyranosyl-D-glucopyranose unit β-glycosidically linked to 17-L-hydroxyoctadecanoic acid or 17-L-hydroxy-Δ9-octadecenoic acid. The hydroxy fatty acid may have, for example, 11 to 20 carbon atoms and may contain one or more unsaturated bonds.

[0023] Furthermore, the sophorose residue may be acetylated at the 6 and / or 6' positions. The fatty acid carboxyl group may be free (acidic or linear form) or the 4'' position may be internally esterified (lactone form). In most cases, the fermentation of sophorolipids results in a mixture of hydrophobic (water-insoluble) sophorolipids, such as lactonic sophorolipids, monoacetylated linear sophorolipids, and diacetylated linear sophorolipids, and hydrophilic (water-soluble) sophorolipids, such as non-acetylated linear sophorolipids.

[0024] Sophorolipids are often produced as a mixture of related molecules. The differences between the related molecules mainly arise from their fatty acid structure (degree of unsaturation, chain length, position of unsaturation, and position of hydroxylation), whether they are produced in the linear or lactonic form, the acetylation pattern, the presence of stereoisomers, and / or whether the glycoside bond on the fatty acid is at the ω-position (e.g., terminal) or the ω-1 position (sub-terminal).

[0025] The sophorolipid compounds of the present invention have many advantageous characteristics that make them superior to synthetic surfactants, such as biodegradability, low toxicity, high surface and interfacial activity, and stability over a wide range of temperatures, pressures, and ionic strengths. On the other hand, the functional properties of sophorolipids can differ between the lactone form and the acidic form. For example, acidic sophorolipids generally have a higher hydrophilic-lipophilic balance (HLB) than lactonic sophorolipids, while lactonic sophorolipids generally have a lower HLB and greater surface tension lowering properties than acidic sophorolipids. Additionally, acidic sophorolipids are typically highly water-soluble due to their free carboxylic acid groups.

[0026] As used herein, the terms "sophorolipid" and "sophorolipid molecule" include all forms of sophorolipid molecules and their isomers, including, for example, acidic (linear) sophorolipids and lactonic sophorolipids. Further included are monoacetylated sophorolipids, diacetylated sophorolipids, esterified sophorolipids, sophorolipids with different hydrophobic chain lengths, sophorolipids conjugated with fatty acid-amino acid complexes, and others including those described and / or not described within the present disclosure.

[0027] Modified sophorolipid The linear sophorolipid molecule can be represented by the general formula (I): TIFF2025521965000010.tif43128, wherein 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; R 4 is alkane, substituted alkane, alkylene, substituted alkylene, alkenylene or substituted alkenylene. Preferably, R 1 and R 2 are hydrogen; R 3 is methyl.

[0028] Sophorolipid molecules have different fatty acid chain lengths and degrees of unsaturation (R 4 ) and can be obtained as an aggregate of 30 or more molecules that may have R 1 and / or R 2 acetylated or protonated.

[0029] Examples of substituents include halogen atoms, hydroxyl, lower (C1-6) alkyl groups, halo-lower (C1-6) alkyl groups, hydroxy-lower (C1-6) alkyl groups, halo-lower (C1-6) alkoxy groups, etc. R 4 typically has 11 to 20 carbon atoms. In a preferred embodiment of the present invention, R 4 has 16 to 17 carbon atoms.

[0030] In one embodiment, the present invention provides a modified sophorolipid in which a sophorolipid or a cleaved sophorolipid is bound to an amino acid via a primary amine. By "cleaved", it means that the carbon chain of the fatty acid is shorter than the carbon chain of the fatty acid normally present in the sophorolipid.

[0031] In one embodiment, the present invention provides a modified sophorolipid. Preferably, the modification includes, for example, peracetylation and esterification. In a preferred embodiment, the modified sophorolipid of the present invention has the general structure of formula (II): TIFF2025521965000011.tif47128 and wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000012.tif13128; R1 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, and substituted heteroaryl. Preferably, each R is independently selected from the following: TIFF2025521965000013.tif18128; R1 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, i-propyl, i-butyl, and TIFF2025521965000014.tif is selected from 11128.

[0032] In one aspect, the present invention provides a modified sophorolipid having the general structure of formula (III): TIFF2025521965000015.tif provides a modified sophorolipid having 71128, wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000016.tif is selected from 15128; R2 is -(CH2) n -, where n ≥ 1; R3 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, and substituted heteroaryl; R4 is an amino acid side chain, preferably one having an aromatic group, such as the following: TIFF2025521965000017.tif is selected from 25128. Preferably, each R is independently the following: TIFF2025521965000018.tif is selected from 17128; 1 ≤ n ≤ 10; R3 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, i-propyl, i-butyl, and TIFF2025521965000019.tif is selected from 11128.

[0033] In one aspect, the present invention provides a modified sophorolipid having the general structure of formula (IV), which is a cyclic ether analog of a lactonic sophorolipid. Thus, the present invention provides a compound of formula (IV): TIFF2025521965000020.tif provides 58128, wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000021.tif is selected from 15128; R5 is hydrogen or alkyl; A is an optionally substituted saturated or unsaturated aliphatic chain. Preferably, each R is independently H, selected from TIFF2025521965000022.tif17128; R5 is hydrogen or methyl.

[0034] 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, at the carbon to which R5 is attached, and in R5 is 12 to 22 carbons.

[0035] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and 1, 2, or 3 unsaturations.

[0036] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbons and 1, 2, or 3 unsaturations.

[0037] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 16 carbons and 1, 2, or 3 unsaturations.

[0038] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbons and 1, 2, or 3 unsaturations.

[0039] In some embodiments, R is hydrogen, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and 1, 2, or 3 unsaturations.

[0040] In some embodiments, R is hydrogen, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbons and 1, 2, or 3 unsaturations.

[0041] In another embodiment, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbons and 1 unsaturation.

[0042] In another aspect, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbons and one unsaturation.

[0043] In another aspect, each R is independently hydrogen or ethyl, R5 is methyl, and A is a fully saturated aliphatic chain having 16 carbons.

[0044] In another aspect, each R is independently hydrogen or ethyl, R5 is hydrogen, and A is a fully saturated aliphatic chain having 17 carbons.

[0045] In one aspect, the present invention provides a modified sophorolipid having the general formula (V): TIFF2025521965000023.tif44128, wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000024.tif15128. Preferably, each R is independently selected from H, TIFF2025521965000025.tif17128.

[0046] In one aspect, the present invention provides a modified sophorolipid having the general formula (VI): TIFF2025521965000026.tif60128, wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000027.tif15128; R5 is hydrogen or alkyl; A is an optionally substituted saturated or unsaturated aliphatic chain. Preferably, each R is independently selected from H, TIFF2025521965000028.tif16128; R5 is hydrogen or methyl.

[0047] In a preferred embodiment, the aliphatic chain A has 10 to 21 carbon atoms such that the total number of carbon atoms in the aliphatic chain A, R5, and the carbon to which R5 is attached is 12 to 22 carbon atoms.

[0048] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbon atoms and 1, 2, or 3 unsaturations.

[0049] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbon atoms and 1, 2, or 3 unsaturations.

[0050] In some embodiments, R is ethyl, R5 is hydrogen, and A is an unsaturated aliphatic chain having 16 carbon atoms and 1, 2, or 3 unsaturations.

[0051] In some embodiments, R is ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbon atoms and 1, 2, or 3 unsaturations.

[0052] In some embodiments, R is hydrogen, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbon atoms and 1, 2, or 3 unsaturations.

[0053] In some embodiments, R is hydrogen, R5 is hydrogen, and A is an unsaturated aliphatic chain having 17 carbon atoms and 1, 2, or 3 unsaturations.

[0054] In another embodiment, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 16 carbon atoms and 1 unsaturation.

[0055] In another embodiment, each R is independently hydrogen or ethyl, R5 is methyl, and A is an unsaturated aliphatic chain having 17 carbon atoms and 1 unsaturation.

[0056] In another aspect, each R is independently hydrogen or ethyl, R5 is methyl, and A is a fully saturated aliphatic chain having 16 carbons.

[0057] In another aspect, each R is independently hydrogen or ethyl, R5 is hydrogen, and A is a fully saturated aliphatic chain having 17 carbons.

[0058] In one aspect, the present invention provides a modified sophorolipid having the general formula (VII): TIFF2025521965000029.tif59128, wherein each R is independently selected from hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, TIFF2025521965000030.tif13128. Preferably, each R is independently selected from H, TIFF2025521965000031.tif18128.

[0059] In one aspect, the modified sophorolipid of the present invention has a lower HLB value compared to linear or lactonic sophorolipids. In a specific aspect, the modified sophorolipid of the present invention has an HLB value of 6 or less, preferably 5 or less, more preferably 4 or less, and most preferably 3 or less.

[0060] In a specific aspect, 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-OMe, SH-peracetylated-Oet, SH-peracetylated-O-i-Bu (isobutyl), SH-peracetylated-phenylalanine, and SH-peracetylated-tryptophan.

[0061] Selected definitions As used herein, the term "foam" refers to the dispersion of gas bubbles within or on a liquid, within a gel, or within a semi-solid. The gas bubbles may be dispersed throughout the liquid phase in a non-uniform or uniform manner. Examples of foams include air, nitrogen, oxygen, helium, or hydrogen gas trapped within a liquid such as water or oil. The foam may be temporary, unstable, or stable.

[0062] As used herein, the term "surfactant" refers to a substance or compound that reduces the surface tension when dissolved in water or an aqueous solution, or reduces the interfacial tension between two liquids or between a liquid and a solid. Thus, the term "surfactant" includes cationic, anionic, non-ionic, zwitterionic, amphoteric agents and / or combinations thereof. The term "biosurfactant" means a surfactant produced by a living organism and / or a surfactant produced using a natural-derived substrate. "Surfactants" and "biosurfactants" are also related to substances that cause foaming.

[0063] As used herein, the term "alkyl" refers to a straight-chain or branched hydrocarbon group. Suitable alkyl groups include, without limitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl. The term "alkyl" may be preceded by a specified number of carbon atoms or a range of carbon atoms to indicate the number 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.

[0064] As used herein, an "isolated" or "purified" nucleic acid molecule, polynucleotide, polypeptide, protein, or organic compound, such as a small molecule, is substantially free of other compounds with which it is associated in nature, such as cellular material. A purified or isolated polynucleotide (ribonucleic acid (RNA) or deoxyribonucleic acid (DNA)) does not contain the genes or sequences that flank it in its natural state. A purified or isolated polypeptide does not contain the other molecules, i.e., amino acids, that flank it in its natural state. An "isolated" strain means a strain removed from its natural environment. Thus, an isolated strain may exist, for example, as a biologically pure culture or as spores (or other forms of the strain).

[0065] In certain embodiments, a purified compound is present at least 60% by weight of the compound of interest. Preferably, the preparation is at least 75%, more preferably at least 90%, and most preferably at least 99% by weight of the compound of interest. For example, a purified compound is a compound that is at least 90%, 91%, 92%, 93%, 94%, 95%, 98%, 99%, or 100% (w / w) of the compound of interest by weight. Purity is measured by any suitable standard method, such as by column chromatography, thin layer chromatography, or high performance liquid chromatography (HPLC) analysis.

[0066] The ranges provided herein are to be understood as shorthand for all values within the range. For example, a range of 1 to 20 includes any number, combination of numbers, or sub-range from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, as well as all fractional values between said integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, "nested sub-ranges" extending from either endpoint of the range are specifically contemplated. For example, nested sub-ranges within the exemplary range of 1 to 50 may include, in one direction, 1 to 10, 1 to 20, 1 to 30, and 1 to 40, or in the other direction, 50 to 40, 50 to 30, 50 to 20, and 50 to 10.

[0067] As used herein, "fermentation" refers to the growth or cultivation of cells under controlled conditions. The growth can be aerobic or anaerobic. Unless specifically required by the context, the expression is intended to encompass both the growth stage and the product biosynthesis stage of the process.

[0068] As used herein, "broth", "culture broth", or "fermentation broth" refers to a culture medium containing at least nutrients. When the broth is referred to after a fermentation process, the broth may also contain microbial growth by-products and / or microbial cells.

[0069] The microbial growth vessel used in accordance with the present invention may be any fermenter or culture reactor for industrial use. As used herein, the terms "reactor", "bioreactor", "fermentation reactor" or "fermentation vessel" include a fermentation apparatus consisting of one or more vessels and / or towers or piping configurations. Examples of such reactors include, without limitation, continuous stirred tank reactors (CSTRs), immobilized cell reactors (ICRs), trickle bed reactors (TBRs), bubble columns, gas lift fermenters, static mixers, or other vessels or other devices suitable for gas-liquid contact. In some embodiments, the bioreactor may include a first growth reactor and a second fermentation reactor. Thus, when referring to the addition of a substrate to a bioreactor or fermentation reaction, it should be understood to include addition to any or both of these reactors, where appropriate.

[0070] As used herein, "decrease" means a negative change and "increase" means a positive change, where 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%, and all values in between are included.

[0071] The term "subject" or "patient", as used herein, refers to an organism, including mammals such as primates. Mammalian species that may benefit from the disclosed treatment methods include apes, chimpanzees, orangutans, humans, and monkeys; domesticated animals such as dogs and cats; livestock such as horses, cows, pigs, sheep, goats, and chickens; and other animals such as mice, rats, guinea pigs, and hamsters, without limitation.

[0072] 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 material not specified in the claim. The transitional phrase "consisting essentially of" limits the scope of the claim to the specified substance or step and those that do not "materially affect the basic and novel characteristics" of the claimed invention. The use of the term "comprising" contemplates other aspects "consisting of" or "consisting essentially of" the recited components.

[0073] As used herein, unless specifically recited or apparent from context, the term "or" is understood to be inclusive. As used herein, unless specifically recited or apparent from context, the terms "a", "an", and "the" are understood to be singular or plural.

[0074] As used herein, unless specifically recited or apparent from context, the term "about" is understood to be within the ordinary tolerance in the art, e.g., within 2 standard deviations of the mean value. "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 recited value.

[0075] The recitation of a list of chemical groups in any definition of a variable herein includes the definition of that variable as any single group or combination of the recited groups. The recitation of an aspect for each variable or aspect herein includes that aspect as any single aspect or in combination with any other aspect or portion thereof. All references cited herein are incorporated herein by reference.

[0076] Production of sophorolipids The present invention provides substances and methods for producing and modifying sophorolipids. Advantageously, the present invention is suitable for industrial-scale production of purified sophorolipids, using safe and environmentally friendly substances and processes.

[0077] Sophorolipids are generally obtained from the fermentation of microorganisms using a fermentation process involving wild-type or genetically engineered microorganisms, with a carbohydrate source such as corn syrup, dextrin, and glucose, and using a pure fatty acid, fatty acid mixture, pure fatty acid ester, mixture of fatty acid esters, triglyceride as a carbon source. The use of renewable substrates and different microbial species, as well as various culture parameters (such as culture time, stirring speed, pH value of the medium, and added nutrients), enables the acquisition of compounds with clearly different structural and physical properties. This allows for the production of a wide range of compounds exhibiting different physical, chemical, biochemical, and biophysical properties.

[0078] In a preferred embodiment of the present invention, the method includes first generating a standard sophorolipid molecule used to produce a modified sophorolipid. In a particular embodiment, this includes culturing sophorolipid-producing yeast in a submerged fermentation reactor containing a suitable oleochemical raw material to produce a yeast culture product, wherein the yeast culture product includes fermentation broth, yeast cells, and sophorolipids having a mixture of two or more molecular structures.

[0079] The mixture of molecular structures can include, for example, lactonic sophorolipids, linear sophorolipids, deacetylated sophorolipids, monoacetylated sophorolipids, diacetylated sophorolipids, esterified sophorolipids, sophorolipids with different hydrophobic chain lengths, sophorolipids conjugated with fatty acid - amino acid complexes, and other substances including those described and / or not described within the present disclosure.

[0080] In a particular embodiment, the distribution of the mixture of sophorolipid molecules can be modified by adjusting fermentation parameters such as, for example, raw materials, fermentation time, and dissolved oxygen concentration.

[0081] The sophorolipids according to the present invention can be derived via a fermentation process from recombinant organisms or by strains that inherently produce sophorolipids. Non-limiting examples of sophorolipid-producing organisms include Candida bombicola, Candida apicola, Candida bogoriensis, Yarrowia lipolytica, Starmerella bombicola, Starmerella clade, Rhodotorula bogoriensis, Wickerhamiella domericqiae, and Wickerhamomyces anomalus. Some recombinant sophorolipid-producing microorganisms have been reported to enable control of the sophorolipid structure. As non-limiting examples, certain recombinant S. bombicola strains can be utilized to produce sophorolipids that are either fully lactonic or fully acidic. Furthermore, recombinant Candida bombicola strains with the acetyltransferase gene knocked out can be used to produce sophorolipids without using acetylation.

[0082] In a preferred embodiment, the microorganism is a yeast or a fungus. Examples of yeast and fungal species suitable for use in the present invention include Acaulospora, Aspergillus, Aureobasidium (e.g., A. pullulans), Blakeslea, Candida (e.g., C. albicans, C. apicola), Cryptococcus, Debaryomyces (e.g., D. hansenii), Entomophthora, Fusarium, Hanseniaspora (e.g., H. uvarum), Hansenula, Issatchenkia, Kluyveromyces, Mortierella, Mucor (e.g., M. piriformis), Meyerozyma (e.g., M. guilliermondii), Penicillium, Phythium, Phycomyces, Pichia (e.g., P. anomala, P. guilliermondii, P. occidentalis, P. kudriavzevii), Pseudozyma (e.g., P. aphidis), Rhizopus, Saccharomyces (S. cerevisiae, S. boulardii sequela, S. torula), Starmerella (e.g., S. bombicola), Torulopsis, Thraustochytrium, Trichoderma (e.g., T.It includes, without limitation, Trichoderma reesei, T. harzianum, T. virens, Ustilago (e.g., U. maydis), Wickeria (e.g., W. anomalus), Williopsis, and Zygosaccharomyces (e.g., Z. bailii).

[0083] In a preferred embodiment, the microorganism is selected from, for example, yeasts of the genus Starmerella and / or the genus Candida, such as Starmerella (Candida) bombicola, Candida apicola, Candida batistae, Candida floricola, Candida riodocensis, Candida stellate, and Candida kuoi. In a specific embodiment, the microorganism is Starmerella bombicola, such as the ATCC 22214 strain.

[0084] In one embodiment, the fermenter may have or be connected to a functional control device / sensor for measuring important elements in the culture process, such as pH, oxygen, pressure, temperature, stirrer output, humidity, viscosity, and / or microorganism density and / or metabolite concentration.

[0085] In a further embodiment, the container can also monitor the growth of the microorganism in the container (e.g., measuring the cell number and growth stage). Alternatively, samples may be taken from the container for counting, purity measurement, sophorolipid concentration, and / or visual monitoring of the oil amount. For example, in one embodiment, sampling can be performed every 24 hours.

[0086] The microbial inoculum according to the present method preferably contains cells and / or propagules of a desired microorganism that can be prepared using any known fermentation method. The inoculum can be pre-mixed with water and / or a liquid growth medium, if desired.

[0087] The microorganism utilized according to the present invention may be a natural or genetically recombinant microorganism. For example, the microorganism may be transformed with a specific gene to exhibit specific characteristics. The microorganism may also be a variant of a desired strain.

[0088] In one embodiment, a single type of microorganism is cultured in a reactor system. In an alternative embodiment, multiple microorganisms that can be grown together without adversely affecting the growth or resulting product can be grown in a single reactor system. For example, two or more different microorganisms may be grown simultaneously in a single reactor. In some embodiments, more than one type of microorganism grows symbiotically in the reactor.

[0089] In certain embodiments, the culture may be supplemented with a carbon source. The carbon source may be carbohydrates such as glucose, dextrose, sucrose, lactose, fructose, trehalose, mannose, mannitol, and / or maltose; organic acids such as acetic acid, fumaric acid, citric acid, propionic acid, malic acid, malonic acid, and / or pyruvic acid; alcohols such as ethanol, propanol, butanol, pentanol, hexanol, isobutanol, and / or glycerol; oils and fats such as canola oil, soybean oil, rice bran oil, olive oil, corn oil, sunflower oil, sesame oil, and / or linseed oil; powdered molasses, etc. These carbon sources may be used alone or in combination of two or more.

[0090] In certain embodiments, the culture may be supplemented with oleochemical raw materials that are high in oleic acid and / or contain only oleic acid, which results in a yeast culture product with less variation in the sophorolipid molecular structure than raw materials containing other fatty acid sources, where the main sophorolipid molecules produced contain an 18C carbon chain and one unsaturated bond at the 9th carbon.

[0091] In one embodiment, the liquid growth medium contains 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 independently or in combination of two or more.

[0092] In one embodiment, one or more inorganic salts may also be included in the liquid growth medium. The inorganic salts can 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 can be used alone or in combination of two or more.

[0093] In one embodiment, the medium contains growth factors and micronutrients for each microorganism. Inorganic nutrients containing trace elements such as iron, zinc, copper, manganese, molybdenum and / or cobalt may also be included in the medium. Furthermore, sources of vitamins, essential amino acids, proteins and microelements can be included, for example, in corn flour, peptone, yeast extract, potato extract, beef extract, soybean extract, banana peel extract, etc., or in purified form. For example, amino acids such as those useful for protein biosynthesis can also be included.

[0094] The culturing method can further provide oxygen to the growth medium. One embodiment is to slowly move the air to remove air with low oxygen content and introduce air containing oxygen. The air containing oxygen may be ambient air that is replenished daily through a mechanism including an impeller for mechanically agitating the liquid and an air sparger for supplying gas bubbles to the liquid to dissolve oxygen in the liquid.

[0095] In one embodiment, the microorganism can be grown on a solid or semi-solid substrate such as, for example, corn, wheat, soybeans, chickpeas, beans, oatmeal, pasta, rice, and / or powders or meals of these or other similar substances.

[0096] In one embodiment, inorganic salts may also be included. Usable inorganic salts can be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, magnesium sulfate, magnesium chloride, iron sulfate, iron 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.

[0097] In some embodiments, for example, when the microorganism used to inoculate the substrate is in the form of spores (e.g., bacterial spores), a germination promoter can be added to the substrate. Examples of germination promoters 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.

[0098] The pH of the culture medium should be suitable for the target microorganism. To stabilize the pH near a preferred value, buffers and pH adjusters such as carbonates and phosphates may be used. In certain embodiments, a base solution, for example, a 15% - 30% or 20% - 25% NaOH solution, is used to adjust the pH of the culture medium to a preferred level. The base solution can be included in the growth medium during cultivation and / or supplied to the fermenter to adjust the pH as needed. When metal ions are present at high concentrations, it may be necessary to use a chelating agent in the liquid medium.

[0099] The methods and apparatuses for culturing microorganisms and generating microbial by-products can be carried out in batch, semi - continuous, or continuous processes.

[0100] In one aspect, the culturing method is carried out at about 5° to about 100°C, about 15° to about 60°C, about 20° to about 45°C, about 22° to about 35°C, or about 24° to about 28°C. In one aspect, the culturing may be carried out continuously at a constant temperature. In another aspect, the culturing may be subjected to temperature changes.

[0101] According to this method, the microorganism can be cultured in the fermentation system for a period sufficient to achieve the desired effect, such as the production of a desired amount of cell biomass or a desired amount of sophorolipid.

[0102] In certain aspects, the fermentation of the yeast culture is carried out for about 40 - 150 hours, or about 48 - 140 hours, or about 72 - 130 hours or about 96 - 120 hours. In certain specific aspects, the fermentation time ranges from 48 - 72 hours or 96 - 120 hours.

[0103] In some aspects, the sophorolipids produced by the target microorganism may be retained within the microorganism or secreted into their growth medium. The sophorolipid content can be, for example, at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

[0104] The growth medium may contain a compound that stabilizes the activity of the sophorolipid. The sophorolipids can be purified or used in a crude form, meaning they are not separated from the fermentation broth in which they were produced.

[0105] In certain aspects, the sophorolipids are isolated and / or purified from the growth medium resulting from the fermentation of the biosurfactant - producing microorganism. Isolation and purification can be readily achieved using standard methods or techniques described in the literature. If desired, the sophorolipids can be further concentrated.

[0106] Modification of Sophorolipids In one aspect, the present invention provides a synthetic procedure for creating a sophorolipid scaffold for modifying the fatty acid terminus to improve defoaming ability. A "scaffold" serves as a starting point for creating structure-activity relationships, e.g., determining how small modifications each contribute to defoaming ability. For example, converting a carboxylic acid to a methyl, ethyl, or isobutyl ester can be used to create defoamers from fatty acids such as stearic acid.

[0107] In some aspects, the modified sophorolipids according to the present invention are obtained by chemically modifying sophorolipids obtained from the products of fermentation by sophorolipid-producing microorganisms. The sophorolipids to be chemically modified may be obtained by the fermentation methods and processes described above, and / or by other methods known in the art. Any suitable techniques and chemical reactions known in the art may be used to modify the sophorolipids.

[0108] For example, chemical modification can also be performed to modify the degree of unsaturation of the fatty acid chain. Commonly known hydrogenation or dehydrogenation reactions, or addition or elimination reactions, may be used.

[0109] Sophorolipids containing unsaturated bonds at specific positions enable site-directed functionalization of the sophorolipid molecule. In certain aspects, linear sophorolipids are ozonized with ozone gas. During the ozonolysis of linear sophorolipids, the olefin moiety of the sophorolipid molecule is converted to an ozonide, which is a reactive five-membered ring. In a preferred aspect, the sophorolipid containing the ozonide is reduced to obtain an aldehyde handle. In certain aspects, the reducing agent is triphenylphosphine used at an equimolar concentration with the sophorolipid-ozonide.

[0110] In certain embodiments, the reactive aldehyde handle, whether generated by ozonolysis or oxidative cleavage, is then used as a site for the addition of a primary amine, for example, via reductive amination. In certain embodiments, reductive amination involves introducing a primary amine to the sulfobetaine lipid-aldehyde under reducing conditions. This produces a stable secondary amine that functions as a covalent bond between the sulfobetaine lipid scaffold and the payload of the primary amine (e.g., an amino acid).

[0111] In certain embodiments, the reducing agent is sodium cyanoborohydride, sodium triacetoxyborohydride, or sodium borohydride. In some embodiments, the linear sulfobetaine lipid aldehyde is extracted from the aqueous mixture with ethyl acetate and concentrated to dryness under reduced pressure (e.g., about 200 - 250 mbar, or about 240 mbar) at a temperature of about 35 - 45 °C. The dried crude linear sulfobetaine lipid aldehyde can then be dissolved in a reaction medium containing tetrahydrofuran (THF) and water. The proportion of water used as the reaction medium preferably does not exceed 50%, and is typically 0 - 25%.

[0112] In some embodiments, amide coupling addition of amino acids such as phenylalanine methyl ester and tryptophan methyl ester can add an aromatic ring that maintains the HLB of the sulfobetaine lipid within the defoaming range while retaining the biogenic carbon of the amino acid. Biogenic carbon is, for example, carbon obtained directly from agricultural resources, such as fermentation products derived from sugars. The biogenic carbon within the molecule is directly separated from the molecule by biological processes. Biogenic carbon can be quantitatively measured by C14 radiocarbon testing.

[0113] In one aspect, the modified sophorolipids of the present invention incorporate, within their structure, an amino acid bonded to the fatty acid chain of the sophorolipid structure via a primary amine. By covalently bonding an amino acid to a sophorolipid or a cleaved sophorolipid, the modified sophorolipid exhibits defoaming ability. Further, the addition of the amino acid contributes to bio-derived carbon in place of synthetic carbon, increasing the percentage of bio-derived carbon in the modified sophorolipid, which improves the defoaming properties of the modified sophorolipid. The percentage of bio-derived carbon represents the number of bio-derived carbons out of the total number of atoms in the molecule (e.g., percentage of bio-derived carbon = (number of bio-derived carbons / total number of atoms) × 100).

[0114] The amino acids used herein have at least one amino group and at least one acid, e.g., a carboxyl group, in their backbone and have different side chains for each amino acid. The side chains can be various substituents including, without limitation, hydrogen (e.g., in the case of glycine), organic, semi-organic or inorganic substances, and rings cyclized on the amine (e.g., in the case of proline).

[0115] The amino acids used herein may be L-amino acids or D-amino acids. These can be natural amino acids (such as essential amino acids, non-essential amino acids, or conditionally essential amino acids) or synthetic / modified amino acids that do not occur naturally. The present invention encompasses both amino acids incorporated into proteins and amino acids not incorporated into proteins. Naturally occurring amino acids may be purified products or may be artificially synthesized.

[0116] In some aspects, the amino acids according to the present invention are alpha (α)-amino acids, which contain an amino group and a carboxyl group bonded 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.

[0117] Other non-limiting examples of amino acids that can be used in the present invention include 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-oxaproline, 4-thioproline, 2-azaproline, 4-hydroxyproline, 1,5-disubstituted tetrazole, 2-aminoisobutyric acid, sarcosine, 1-aminocyclopentane-1-carboxylic acid, beta-alanine, 2-amino-cyclopentanecarboxylic acid (beta-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-aminopentanoic acid, and 5-amino-2-oxopentanoic acid, including but not limited to these.

[0118] In some embodiments, the modified sophorolipid to which the amino acid is attached can be further esterified by a functional group via the carboxyl group of the amino acid. The functional group includes, for example, methyl, ethyl, propyl, butyl, pentyl, i-propyl, i-butyl, and TIFF2025521965000032.tif11128, including but not limited to these.

[0119] Since the lactone species essentially results in a lower HLB value, the HLB value will also decrease by the peracetylation of the sophorose hydroxyl group or the global conversion to an ether, and a biosurfactant with a high carbon ratio (i.e., carbon %) is produced.

[0120] In one aspect, the modified sophorolipids of the present invention have a content of bioderived carbon 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%.

[0121] One aspect is directed to a method for producing a modified sophorolipid, which includes a step of obtaining a linear sophorolipid molecule and a step of functionalizing the linear sophorolipid molecule by converting all or most of the linear sophorolipid into a modified sophorolipid molecule.

[0122] Compositions and their uses The present invention provides a composition for industrial use, which includes the bioderived defoamer or foam control agent of the present invention. The bioderived defoamer or foam control agent removes the existing foam and prevents the formation of further foam. Advantageously, in a preferred aspect, the bioderived defoamer or foam control agent is biodegradable and does not need to be removed from the materials or final products in which they are used.

[0123] In one aspect, the present invention provides an antifoaming agent composition containing the modified sophorolipid of the present invention. In one aspect, the present invention provides a defoaming cleaning agent composition containing the modified sophorolipid of the present invention. In one aspect, the present invention provides a cleaning composition containing the modified sophorolipid of the present invention. In one aspect, the present invention provides a coating composition, preferably a paint, containing the modified sophorolipid of the present invention. Advantageously, the present invention can be used without harming the user and without releasing a large amount of pollutants and toxic compounds into the environment.

[0124] In a further aspect, the modified sophorolipids of the present invention can be used in the processing of pulp and paper.

[0125] In some embodiments, the composition of the present invention comprises a modified sophorolipid, based on the weight of the composition, 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%.

[0126] In certain embodiments, the composition of the present invention comprises 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 4.0%, from about 0.1% to about 3.0%, from about 0.1% to about 2.0%, from about 1.0% to about 9.0%, from about 1.0% to about 5.0%, from about 1.0% to about 3.0%, from about 3.0% to about 10%, from about 3.0% to about 7.0%, from about 5.0% to about 10%, from about 5.0% to about 9.0%, from about 6.0% to about 10%, from about 7.0% to about 10%, from about 8.0% to about 10%, from about 5% to about 40%, from about 10% to about 40%, from about 10% to about 30%, from about 10% to about 20%, from about 20% to about 30%, from about 20% to about 40%, from about 20% to about 50%, from about 30% to about 50%, or from about 30% to about 40%.

[0127] Other active defoaming compounds such as silica, hydrophobized silica, polyethylene wax, ethylene bisstearamide wax, polypropylene wax, polydimethylsiloxane, organically modified polydimethylsiloxane, and hydrophobized polyethylene oxide glycerol ether may be used in combination with the biologically derived defoaming agent or foam control agent according to the invention.

[0128] Optionally, the composition may further comprise one or more other components, such as, for example, a carrier (e.g., water), other biocompatible surfactants, other surfactants (e.g., polyalkyl glucosides such as capryl glucoside and lauryl glucoside), hydrophilic and / or hydrophobic compounds, sequestering agents, builders (e.g., potassium carbonate, sodium hydroxide, glycerin, 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., octyl isothiazolinone, methyl isothiazolinone), terpenes (e.g., d-limonene), sesquiterpenoids, terpenoids, emulsifiers, demulsifiers, foaming agents, defoaming agents, bleaching agents, polymers, thickeners and / or viscosifiers (e.g., xanthan gum, guar gum).

[0129] In some embodiments, the composition comprises an additional biocompatible surfactant. The additional biocompatible surfactant according to the present invention may include, for example, glycolipids, lipopeptides, flavolipids, phospholipids, fatty acid esters, and high molecular weight biopolymers such as lipoproteins, lipopolysaccharide-protein complexes, and / or polysaccharide-protein-fatty acid complexes.

[0130] In one embodiment, the additional biocompatible surfactant is a glycolipid such as, for example, rhamnolipid (RLP), cellobiose lipid, trehalose lipid and / or mannosylerythritol lipid (MEL). In one embodiment, the biocompatible surfactant is a lipopeptide such as, for example, surfactin, iturin, fengycin, altrofactin, amphisin, viscosin, lichenysin, paenibactin, polymyxin and / or butyracin.

[0131] In certain embodiments, the composition further comprises a detergent adjunct ingredient. Preferably, the detergent adjunct ingredient is selected from the group consisting of enzymes, oxygen bleaches, bleach activators, fluid modifiers, and neutral inorganic salts. Examples of enzymes include amylase, protease, cellulose, lipase, pullulanase, isopullulanase, isoamylase, catalase, peroxidase, and the like. Examples of oxygen bleaches include peroxides that generate hydrogen peroxide in aqueous solution, such as perborates, percarbonates, persulfates, and the like. Bleach activators include tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), glucose pentaacetate (GPA), sodium nonanoyloxybenzenesulfonate (SNOBS), and the like, which are used to improve the bleaching effect. Neutral inorganic salts include sodium sulfate, potassium sulfate, and the like. The fluid modifier may be silica powder, anhydrous silicate, or the like.

[0132] The composition may further comprise additional active or inactive ingredients suitable for the mode of administration and the intended purpose, provided that such addition does not adversely affect the function of the modified sophorolipid.

[0133] The cleaning composition of the present invention can be formulated, for example, as microemulsions, soluble powders and / or granules, compressed powders, loose powders, diluted sprays, concentrates, aerosols, foams, toilet cleaners, laundry detergents, dishwashing detergents, encapsulated soluble pods, as gels, and / or as pre-moistened or water-activated cloths, sponges, wipes or other substrates.

[0134] In certain embodiments, the composition may further comprise an acceptable carrier, depending on the form of the composition. Acceptable carriers include, without limitation, inert diluents, disintegrants, binders, lubricants, flavoring agents, coloring agents, and preservatives. Suitable inert diluents include sodium and calcium carbonates, sodium and calcium phosphates, and lactose, while corn starch and alginic acid are suitable disintegrants. The binder may include starch and gelatin, while the lubricant, when present, is generally magnesium stearate, stearic acid, or talc.

[0135] In some embodiments, the composition is in solid form and is suitable for reconstitution in a solvent. In another embodiment, the composition further comprises a solvent. Suitable solvents may be aqueous or non-aqueous. In certain embodiments, the solvent is an aqueous solvent. Examples of suitable solvents include water, buffer solutions, acetonitrile, water, and alcohol mixtures such as aqueous methanol, aqueous ethanol, and aqueous isopropanol.

[0136] Non-biological surfactants may also be added to the composition. Examples of surfactants include, without limitation, alkyl sulfates, alkyl ether sulfates (e.g., sodium / ammonium lauryl sulfate and sodium / ammonium laureth sulfate), amphoterics (e.g., amphoacetates, amphopropionates), sulfosuccinates, alkyl polyglucosides, betaines (e.g., cocamidopropyl betaine), sultaines, sacrosinates, isethionates, taurates, ethoxylated sorbitan esters, alkanolamides, and amino acid-based surfactants.

[0137] For example, viscosity modifiers including, but not limited to, cocamide DEA, oleamide DEA, sodium chloride, cellulose polymers, polyacrylates, ethoxylated esters, alcohols, glycols, xylene sulfonates, polysorbate 20, alkanolamides, and cellulose derivatives (e.g., hydroxypropyl methylcellulose and hydroxyethyl cellulose) may also be added to the composition.

[0138] For example, polymers including xanthan gum, guar gum, polyquaternium-10, PEG-120 methyl glucose dioleate, PEG-150 distearate, PEG-150 polyglyceryl-2 tristearate, and pentaerythrityl tetra-stearate PEG-150 may also be added.

[0139] In some embodiments, the composition may optionally contain a preservative. Generally, preservatives are classified into specific classes including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, biguanides, anilides, organic sulfur and sulfur-nitrogen compounds, alkyl parabens, and various compounds. Some non-limiting examples of phenolic antibacterial agents include pentachlorophenol, orthophenylphenol, chloroxylenol, p-chloro-m-cresol, p-chlorophenol, chlorothymol, m-cresol, o-cresol, p-cresol, isopropyl cresol, mixed cresols, phenoxyethanol, phenoxyethyl paraben, phenoxyisopropanol, phenyl paraben, resorcinol, and their derivatives. Some non-limiting examples of halogen compounds include bromine compounds such as trichlorohydroxydiphenyl ether (triclosan), sodium trichloroisocyanurate, sodium dichloroisocyanurate, iodine-poly(vinylpyrrolidone-one) complex, and 2-bromo-2-nitropropane-1,3-diol, and their derivatives. Some non-limiting examples of quaternary ammonium compounds include benzalkonium chloride, benzethonium chloride, behentrimonium chloride, cetrimonium chloride, and their derivatives. 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 their derivatives. 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%.

[0140] The composition may contain a pH adjuster (e.g., citric acid, ethanolamine, sodium hydroxide, etc.) so as to be formulated within a wide range of pH levels. In certain embodiments, the pH of the composition ranges from 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 suitable pH ranges for the present composition include 3.5 to 7.0 or 7.0 to 10.5. Suitable pH adjusters such as sodium hydroxide, citric acid, and triethanolamine may be added to bring the pH within the desired range.

[0141] The composition may be contained in a container of appropriate size, for example, taking into account the intended use and the intended application method. Thus, the container for containing the composition may be, for example, from 0.1 gallon to 1,000 gallons or more. The composition may be further contained in smaller containers such as bottles (e.g., 1.5 oz, 500 ml, and 1 liter bottles) for dispensing individual doses of the composition.

[0142] In some embodiments, the modified sophorolipids of the present invention are provided in the form of pharmaceutically acceptable salts. For example, the side chains of amino acids may also form the corresponding salts when containing appropriate functional groups. The salts may be formed by procedures well-known and described in the art. Examples of pharmaceutically acceptable cations for the salts include, without limitation, aluminum, arginine, benzathine, calcium, chloroprocaine, choline, diethanolamine, ethanolamine, ethylenediamine, lysine, magnesium, histidine, lithium, meglumine, potassium, procaine, sodium, triethanolamine, and zinc.

[0143] Depending on the chemical characteristics of the amino acids in the modified sophorolipids, acid addition salts may be formed. Examples of pharmaceutically acceptable addition salts include acetates derived from acetic acid, aconitates derived from aconitic acid, ascorbates derived from ascorbic acid, benzenesulfonates derived from benzenesulfonic acid, benzoates derived from benzoic acid, cinnamates derived from cinnamic acid, citrates derived from citric acid, embonates derived from embonic acid, enanthates derived from enanthic acid, formates derived from formic acid, fumarates derived from fumaric acid, glutamates derived from glutamic acid, glycolates derived from glycolic acid, hydrochlorides derived from hydrochloric acid, hydrobromides derived from hydrobromic acid, lactates 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, toluene-p-sulfonates derived from p-toluenesulfonic acid, etc., including non-toxic inorganic and organic acid addition salts without limitation.

[0144] The modified sophorolipids of the present invention may be provided in an unsolvated or solvated form together with pharmaceutically acceptable solvents such as water and ethanol. The solvated form may also include hydrated forms such as monohydrates, dihydrates, hemihydrates, trihydrates, tetrahydrates, etc.

[0145] The modified sophorolipids of the present invention have excellent defoaming and foam suppression performance as defoamers or foam control agents. The defoamer or foam control agent containing the modified sophorolipids of the present invention may be used, for example, in detergents, foods, beverages, pharmaceuticals, cleaning products, industrial processes, and biotechnology to suppress or reduce foam formation.

[0146] In one aspect, the defoaming agent or foam control agent comprising the modified sophorolipid of the present invention may be useful for controlling foaming in paint / coating products. In one aspect, the defoaming agent or foam control agent comprising the modified sophorolipid of the present invention may be used as an additive in applications where foaming is undesirable and / or suppression of foam formation is required.

[0147] In one aspect, the defoaming agent or foam control agent comprising the modified sophorolipid of the present invention may be used as a component in foods and in materials for food preparation.

[0148] In one aspect, the defoaming agent or foam control agent comprising the modified sophorolipid of the present invention may be added to the process of industrial wastewater treatment to suppress or reduce foam formation.

[0149] In one aspect, the defoaming agent or foam control agent comprising the modified sophorolipid of the present invention may be used in the oil and gas industry, such as in oil drilling and well treatment, to suppress or reduce foam formation.

[0150] Generally, defoaming compositions act to lower the interfacial tension in liquids. By lowering the interfacial tension, the defoaming composition may allow gas to escape from the liquid. Thus, the defoaming composition of the present invention may be useful for inhibiting foaming or air entrainment when agitating, mixing, or pumping such fluids in well treatment fluids (e.g., drilling fluids, fracturing fluids, cement compositions, etc.).

[0151] The defoaming agent or foam control agent comprising the modified sophorolipid of the present invention can also be used in many other industrial processes and products, such as wood pulp, paper, paints, machine tool industries, oils, cutting tools, and hydraulic equipment.

[0152] In one aspect, the present invention provides a method for defoaming a liquid, comprising the step of combining / mixing the defoaming composition of the present invention with the liquid, wherein the defoaming composition comprises a defoaming agent or foam control agent comprising the modified sophorolipid of the present invention.

[0153] In one aspect, the present invention provides a method for defoaming a liquid, comprising the step of 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.

[0154] In a specific aspect, defoaming the liquid may include inhibiting the formation of bubbles or the incorporation of gas in the liquid during the preparation or pumping of the liquid.

[0155] In a specific aspect, the liquid may be selected from, for example, paints, fermentation broths, detergent compositions, drilling fluids, crop protection and crop nutrition formulations, textile finishing and fabric treatment formulations, crushing fluids, fluids used in pulp / paper processing, and cement compositions.

[0156] In one aspect, the present invention also provides a method for preventing or reducing the formation of bubbles in a liquid, comprising the step of 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, textile finishing and fabric treatment formulations, crushing fluids, and cement compositions.

Examples

[0157] The following are exemplary compounds of the present invention, presented for illustrative purposes and not intended to limit the invention.

[0158] According to experimental methods, Ferma SL and Ferma SH exhibit HLB values lower than their calculated / theoretical HLB. This can be due to various reasons, such as the carboxylic acid moiety of SH not playing as significant a role in the HLB contribution compared to the hydroxyl groups on sophorose covered by fatty acid chains / lactones. The hydrophilic half containing sophorose can be peracetylated, significantly reducing its hydrophilicity, and the HLB can decrease from 10 (for linear species) and 7 (for lactone species) to less than 3, which means a defoaming agent.

[0159] Compounds exemplified in (Table 1) TIFF2025521965000033.tif248161TIFF2025521965000034.tif202161

[0160] All patents, patent applications, provisional applications, and publications mentioned or cited in this specification are hereby incorporated by reference in their entirety, including all figures and tables, to the extent they do not conflict with the explicit teachings of this specification.

[0161] It should be understood that the examples and embodiments described in this specification are for illustrative purposes only, and that various modifications or changes may be suggested to those skilled in the art in view of them and are within the spirit and scope of this application.

Claims

1. i) Formula (II): ii) Formula (III): iii) Formula (V): and iv) Formula (VII): A compound having a structure selected from: wherein each R is independently hydrogen, alkyl, substituted alkyl, acyl, substituted acyl, selected from: R 1 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, and substituted heteroaryl; R 2 is -(CH2) n -, where n ≧ 1; R 3 is selected from hydrogen, alkyl, substituted alkyl, heteroaryl, and substituted heteroaryl; R 4 is selected from amino acid side chains, Compound.

2. Each R is independently H, The compound according to claim 1, selected from:

3. R 1 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, i-propyl, i-butyl, and The compound according to claim 1, selected from:

4. R 2 is -(CH2) n -, where 1 ≦ n ≦ 10, the compound according to claim 1.

5. R 3 The compound according to claim 1, wherein R is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, i-propyl, and i-butyl.

6. R 4 is as follows: The compound according to claim 1, selected from:

7. Each R is independently the following: The compound according to claim 1, selected from:

8. SH - global ether - COOH, SH - peracetylated - COOH, SH - peracetylated - furfuryl, SH - global ether - furfuryl, global ether lactone, SH - peracetylated - OMe, SH - peracetylated - Oet, SH - peracetylated - O - i - Bu (isobutyl), SH - peracetylated - phenylalanine, and SH - peracetylated - tryptophan, the compound according to claim 1.

9. The compound according to claim 1, having a hydrophilic - lipophilic balance (HLB) value of ≤ 4.

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

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

12. An antifoaming composition comprising the compound according to claim 1.

13. The following antifoaming compounds: Silica, hydrophobized silica, polyethylene wax, ethylene bisstearaamide wax, polypropylene wax, polydimethylsiloxane, organically modified polydimethylsiloxane, hydrophobized polyethylene oxide glycerol ether The antifoaming composition according to claim 12, further comprising one or more of the above.

14. A defoaming detergent composition comprising the compound according to claim 1 and a detergent auxiliary component.

15. The defoaming detergent composition according to claim 14, wherein the detergent auxiliary component is selected from enzymes, oxygen bleaching agents, bleach activators, fluid modifiers, and neutral inorganic salts.

16. The compound according to claim 1 and the following additional components: Water, solvent, additional biobased surfactants, additional surfactants, synthetic surfactants, chelating agents, builders, preservatives, dyes, essential oils, substrates, enzymes, disinfectants, bleaching agents, and / or thickeners and / or viscosifiers A cleaning composition comprising one or more of

17. A method for defoaming a liquid, comprising the step of combining the defoaming composition according to claim 12 with the liquid.

18. The method according to claim 17, wherein the liquid is selected from a paint, a fermentation broth, a cleaning agent composition, a drilling fluid, a fracturing fluid, and a cement composition.

19. A method for preventing or reducing the formation of bubbles in a liquid, comprising the step of combining the defoaming composition according to claim 12 with the liquid.

20. The method according to claim 19, wherein the liquid is selected from a paint, a fermentation broth, a cleaning agent composition, a drilling fluid, a fracturing fluid, and a cement composition.

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