EP3003044A1 - Sophorolipides modifiés utilisables en tant qu'agents de solubilisation des huiles - Google Patents

Sophorolipides modifiés utilisables en tant qu'agents de solubilisation des huiles

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Publication number
EP3003044A1
EP3003044A1 EP14803556.1A EP14803556A EP3003044A1 EP 3003044 A1 EP3003044 A1 EP 3003044A1 EP 14803556 A EP14803556 A EP 14803556A EP 3003044 A1 EP3003044 A1 EP 3003044A1
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EP
European Patent Office
Prior art keywords
oil
sophorolipid
modified
natural
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14803556.1A
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German (de)
English (en)
Other versions
EP3003044A4 (fr
Inventor
Richard A. Gross
Thavasi RENGATHAVASI
Amanda KOH
Yifeng PENG
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SyntheZyme LLC
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SyntheZyme LLC
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Publication date
Priority claimed from US13/902,879 external-priority patent/US9650405B2/en
Application filed by SyntheZyme LLC filed Critical SyntheZyme LLC
Publication of EP3003044A1 publication Critical patent/EP3003044A1/fr
Publication of EP3003044A4 publication Critical patent/EP3003044A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/56—Glucosides; Mucilage; Saponins
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds

Definitions

  • the present invention relates generally to the field of sophorolipids (SL) and more specifically to new compositions of matter for uses of modified sophorolipids (MSL) and combination of sophorolipids as solubilizing agents, emulsifiers, dispersants and thereof.
  • SL sophorolipids
  • MSL modified sophorolipids
  • sophorolipids as solubilizing agents, emulsifiers, dispersants and thereof.
  • Sophorolipids are glycolipid biosurfactant molecules produced by yeasts, such as Candida bombicola, Yarrowi alipolytica, Candida apicola, and Candida bogoriensis.
  • Microbial biosurfactants are surface active compounds produced by various microorganisms. They lower surface and interfacial tension and form spherical micelles at and above their critical micelle concentration (CMC).
  • CMC critical micelle concentration
  • Microbial biosurfactants generally have an amphiphilic structure, possessing a hydrophilic moiety, such as an amino acid, peptide, sugar or oligosaccharide, and a hydrophobic moiety including saturated or unsaturated lipid or fatty acids.
  • SLs consist of a hydrophilic carbohydrate head, sophorose, and a hydrophobic fatty acid tail with generally 16 or 18 carbon atoms with saturation or un- saturation.
  • Sophorose is an unusual disaccharide that consists of two glucose molecules linked ⁇ -1 ,2.
  • sophorose in SLs can be acetylated on the 6'- and/or 6"- positions (FIG. 1 ).
  • One fatty acid hydroxylated at the terminal or subterminal ( ⁇ -1 ) positions is ⁇ -glycosidically linked to the sophorose molecule.
  • the fatty acid carboxylic acid group is either free (acidic or open form) or internally esterified generally at the 4"-position (lactonic form) (FIG.
  • the hydroxy fatty acid component of SLs generally has 16 or 18 carbon atoms with generally one unsaturated bond (Asmer et al. 1988; Davila et al. 1993). However, the SL hydroxy fatty acid can also be fully saturated, di-unsaturated or tri-unsaturated. As such, SLs synthesized by C. bombicola consist of a mixture of related molecules. Differences between these molecules are found based on: i) the fatty acid structure (degree of unsaturation, chain length, and position of hydroxylation), whether they are produced in the lactonic or ring-opened form, and ii) the acetylation pattern.
  • lactonic and acidic SLs are synthesized in vivo from stearic acid with similar yields to oleic acid-derived SLs (Felse et al. 2007).
  • physiological variables during fermentations have provided routes to the variation of SL compositions.
  • sophorolipids of different structure As noted above, fermentation by different microorganisms, Candida bombicola, Yarrowi alipolytica, Candida apicola, and Candida bogoriensis, leads to sophorolipids of different structure noted above, the variations in sophorolipids based on fatty acid feedstocks and organisms leads to a wide array of sophorolipids including lactonic and acidic structures.
  • An additional modification that is relevant to acidic sophorolipids is cleavage of the sophorose moiety to the corresponding glucose-based glucolipids.
  • CMC decreased to 1/2 per additional CH 2 group for the methyl, ethyl, and propyl series of chain lengths.
  • fluorescence spectroscopy Adsorption of SL alkyl esters on hydrophilic solids was also studied to explore the type of lateral associations. These surfactants were found to absorb on alumina but much less on silica. This adsorption behavior on hydrophilic solids is similar to that of sugar-based nonionic surfactants and unlike that of nonionic ethoxylated surfactants. Hydrogen bonding is proposed to be the primary driving force for adsorption of the sophorolipids on alumina. Increase in the n-alkyl ester chain length of SLs caused a shift of the adsorption isotherms to lower concentrations. The magnitude of the shift corresponds to the change in CMC of these surfactants.
  • MSLs modified sophorolipids
  • MSLs have antibacterial, antiviral, and anti-inflammatory properties
  • MSLs were shown to down-regulate expression of pro-inflammatory cytokines including interleukin (Hagler et al. 2007).
  • the antibacterial activity of SLs can be increased by up to 1 ,000 times relative to the natural SL mixture by simple modifications such as esterification of fatty acid carboxyl groups and selective acetylation of disacchahde hydroxyl groups.
  • Table 1 comprises a table of sophorolipid derivatives and sophorolipid components of the natural mixture used in bacterial and fungal plant pathogen assays.
  • the hydroxylated fatty acid of the natural mixture is predominantly 17-hydroxyoleic acid. However, other fatty acid constituents with variations in chain length and unsaturation may also be present.
  • modified SLs e.g., compound 6 with 7
  • modified sophorolipids with natural sophorolipids
  • mixture antimicrobial activity US Patent Application No. 13757762
  • mixing modified SLs or a modified sophorolipids with a natural sophorolipids can result in enhanced performance properties for other applications.
  • unexpected enhanced performance in specific applications may be discovered by exploring the properties of a modified sophorolipid library.
  • US Patent Publication. No. 2010/0098821 A1 discloses a process that solubilizes essential oils to produce clear beverages using ionic and non-ionic emulsifiers.
  • the process described in this invention simplifies the introduction of normally insoluble nutraceuticals, particularly lipophilic ones, into beverages.
  • Many ionic and non-ionic surfactants were described for use in formation of these emulsions such as sorbitan esters, polyglycerol esters, monoglyceride esters, diglyceride esters, polyethylene glycol esters, sucrose esters, dioctyl sodium sulfosuccinate and lecithin. Neither modified nor natural sophorolipids are mentioned in US Patent Publication. No.
  • composition of a flavor oil depends on its origin and processing, the most effective compounds for its solubilization cannot be anticipated by one skilled in the art.
  • availability of safe and effective compounds that prove useful for solubilization of various flavor and fragrance oil compositions are highly useful to formulators.
  • This present disclosure provides methods for the formulation of micro- and nanoemulsions using one or mixtures of modified sophorolipids, mixtures of modified sophorolipids and natural sophorolipids, as well as mixtures containing one or move modified and/or natural sophorolipid with other molecules that are already known by one skilled in the art as being useful for solubilization of flavor and fragrance oils.
  • US patent No 6,214,957 B1 disclosed the use of solubilizers, emulsifiers and dispersing agents having the effects of moisturizing the skin when used as washing agents and having the character of elevating the concentration of a material to be solubilized, emulsified or dispersed in solvents including water as compared with the case where the material is employed alone, or elevating the apparent concentration of a material to be emulsified or dispersed in solvents by increasing homogeneity of the emulsion or dispersion which contain as the active ingredient polymers obtained by polymerizing monomer compositions containing at least one hydrophilic monomer (a i.e., 2-(methacryloyloxy)ethyl-2'-(alkyl-substituted or non-substituted ammonio)ethyl phosphate) having a group represented by general formula (1 ) in the side chain, wherein R1 , R2 and R3 represent each H or C 1 -4 alky
  • solubilizers, emulsifiers and dispersing agents having the effects of moisturizing the skin described in US patent No 6,214,957 B1 have no or low bio-based content and are not fully biodegradable.
  • present disclosure discloses MSLs with different chemical compositions that can be used in various combinations of other compounds, are highly effective molecules for a wide range of oil types such as fragrance, flavor and nutraceuticals compounds.
  • modified sophorolipids are fully or highly bio-based and are completely biodegradable when disposed in many environments including in waste-water systems.
  • the present invention is on application of MSLs either alone or in formulations with combinations of compounds that can consist of other MSLs, natural SLs and other known surface active compounds for use as solubiiizing, emulsification, dispersing and surface active agents.
  • MSLs, and mixtures thereof with natural and other modified sophorolipids outperform natural SLs for solubilization or emulsification of various compounds such as crude oils, hydrocarbons, and food oils.
  • SLs and natural SLs that are useful in this invention and thereby incorporated herein are shown in FIGs. 1 to 1 1 , Scheme 1 and 2, and Table 1 .
  • SLs that are useful in this invention include the following and their esters:
  • X 1 or X 2 is oxymethyl (-CH 2 O-) or methylene (-CH 2 -);
  • R 1 and/or R 2 are selected from the group of functional groups consisting of: hydrogen, acetyl, acryl, urethane, hydroxyalkyl, ether, halide, and carboxyalkyl or alkyl containing heteroatoms ( , 2 ° , and 3 ° amino, tetraalkylammonium, sulfate, phosphate).
  • R 1 and/or R 2 are selected from the group consisting of: hydroxyl, amide, alkanamide, alkanamide containing heteroatoms ( , 2 ° , and 3 ° amino, tetraalkylammonium), alkylsulfate, alkylphosphate, carbohydrate, and mono- or oligopeptide.
  • R 3 is a hydrogen or alkyl group
  • the methods involved in performing these chemical transformations are well known to those skilled in the art;
  • X 3 contains heteroatoms (e.g., O, S, NH);
  • X 3 R 3 is selected from the group of functional groups consisting of: hydroxy, alkanethiolate, amide, alkanamide, alkanamide containing heteroatoms ( , 2 ° , and 3 ° amino, tetraalkylammonium), alkylsulfate, alkylphosphate, carbohydrate, and mono- or oligopeptide with 2 - 50 amino acids.
  • Table 1 comprises a table of Modified Sophorolipids (MSLs) and sophorolipid components of the natural mixture incorporated for use in this invention.
  • MSLs Modified Sophorolipids
  • the hydroxylated fatty acid of the natural mixture is predominantly 17-hydroxyoleic acid.
  • Table 2 comprises CMC values for SL-amides (from this invention) as well as SL-esters (from earlier publication in Colloids and surface 2004, 240, 75) for which surface activity but not interfacial activity was studied.
  • Table 3 comprises solubility results for SL-amides (compounds 22, 23, 24, and 25), SL-esters (compounds 6, 7, 8, and16), unmodified natural SLs (compounds 1 , 2, and 3) and SDS.
  • Table 4 comprises average droplet size determined by a Coulter LS 230 analyzer for paraffin oil-to-water (7:3 v/v) 24 hours after preparation stored at room temperature (25°C).
  • Table 5 comprises average droplet size determined by a Coulter LS 230 analyzer for paraffin oil-to-water (7:3 v/v) emulsions aged for 3-months at room temperature (25°C).
  • Table 6 comprises droplet size distribution of emulsions at different storage time for lemon oil solubilization by SL-hexyl ester (16), SL-octyl ester SL (17), SL- dodecyl ester (18), Tween 60 and Rhamnolipid.
  • Table 7 comprises crude oil clearing/displacement activity of MSLs.
  • Table 8 comprises crude oil emulsificalion activity of MSLs.
  • Scheme 1 shows a summary of chemo-enzymatic chemistry developed to prepare a library of sophorolipid analogs (see Azim et al. 2006, Singh et al., 2003, Bisht et al, 2000, Bisht et al., 1999).
  • Scheme 2 shows a synthesis of diamide derivatives from lactonic sophorolipid using transalkylidenation followed by amidation reactions.
  • FIG. 1 shows the structure of lactonic and acidic forms of sophorolipid mixture produced by Candida bombicola.
  • FIG. 2 shows general formulas for sophorolipids and sophorolipid analogs of the present invention.
  • FIG. 3 shows natural sophorolipids in the lactonic form (Compound 2).
  • FIG. 4 shows sophorolipids in the open chain (acidic) form (Compound 3).
  • FIG. 5 shows representative ester derivatives of the open chain form.
  • FIG. 6 shows amide and related derivatives of the open chain form.
  • FIG. 9 shows peptide derivatives of the open chain form.
  • FIG. 10 shows trans alkylidenation derivatives of lactonic and open chain SLs.
  • FIG. 1 1 shows electrophile derivatives at sophorose ring.
  • FIG. 12 shows CMC of SL-amides, SL-esters and alkyl glucoside as a function of alkyl chain length.
  • FIG. 13 shows dilution test for O/W emulsions.
  • FIG. 15 shows Emulsion phase separation for emulsions prepared using natural and modified sophorolipids 3 by homogenization of paraffin oil/water (5:5 volume ratio) and 2%-by-weight relative to the water phase.
  • FIG. 20 shows viscosity of emulsions prepared from paraffin oil/water 7:3 v/v stabilized by 1 %-by-weight MSL or SDS as a function of aging time at room temperature (25°C).
  • FIG. 21 shows viscosity of emulsions prepared from paraffin oil/water 7:3 v/v, aged for 24 hours at room temperature (25°C), as a function of MSL or SDS concentration (weight-%-relative to the oil phase).
  • FIG. 23A shows a microscopic image of sample A in FIG. 1 diluted in paraffin oil that contained sudan red. The image shows that a water-in-oil emulsion formed (scale bar: 100 ⁇ ).
  • FIG. 23B shows a microscopic image of sample B in FIG. 23 diluted in paraffin oil. The water-in-oil emulsion was confirmed by dilution experiment, as dye experiment gave poor resolution (scale bar: 10 ⁇ ).
  • FIG. 24 shows a microscopic image of water-in-oil emulsion formed with rapeseeds oil using compound 40; picture was taken after 6 weeks and studies of the emulsion phase and emulsion droplet size shows the emulsion remained stable.
  • FIG. 25 MSL combinations. Emulsions were processed with a high shear homogenizer at 13,500 rpm.
  • One example of this MSL combination formulation included 5 weight% surfactant, 1 weight% lemon oil, and 94% D.I. H 2 O.
  • solubilizing means obtaining a transparent or semitransparent homogenous solution when a substance to be solubilized is dissolved in a solvent.
  • emulsifying means obtaining a homogenous emulsion when a substance to be emulsified is dispersed when a liquid substance and a solvent are emulsified.
  • dispersing means obtaining a homogenous dispersion when a solid substance is dispersed in a solvent.
  • the solubilizer, emulsifier or dispersing agent is an agent that improves solubility, emulsifying capacity or dispersion capacity of a solvent, compared to the inherent capacity of the solvent in which materials such as oils, cosmetics, pesticides, antimicrobials, hydrocarbons and drugs are dissolved, emulsified or dispersed alone.
  • the present solubilizer, emulsifier or dispersing agent contains as an effective ingredient, MSL or ingredients, MSLs or combination of effective ingredients, MSLs with natural sophorolipids as solubilizers, emulsifiers, and dispersants.
  • FIGs. 1 to 1 1 MSLs and natural SLs that are useful in this invention and thereby incorporated herein are shown in FIGs. 1 to 1 1 , Scheme 1 and 2, and Table 1 .
  • FIGs. 1 to 1 1 MSLs and natural SLs that are useful in this invention and thereby incorporated herein are shown in FIGs. 1 to 1 1 , Scheme 1 and 2, and Table 1 .
  • Table 1 MSLs and natural SLs that are useful in this invention and thereby incorporated herein are shown in FIGs. 1 to 1 1 , Scheme 1 and 2, and Table 1 .
  • FIG. 2 shows the general formulas for sophorolipids and sophorolipid analogs of the present invention.
  • FIG. 5 shows representative ester derivatives of the open chain form:
  • FIG. 6 shows amide and related derivatives of the open chain form:
  • R 3 CH 2 CH 2 OH
  • R 3 CH 2 CH 2 NMe 2
  • R 3 CH 2 CH 2 -(1 -Imidazole)
  • FIG. 9 shows peptide derivatives of the open chain form.
  • R 3 H, alkyl, aryl, heterocyclic, cationic, anionic groups.
  • MSLs and combinations of MSLs described in this disclosure also include other MSL compositions that would be obvious to one skilled in the art based on review of this application or those encompassed within prior art.
  • Natural SLs and MSLs suitable for use in this invention include the following chemical compositions.
  • a second class of MSLs includes esterified ring-opened sophorolipids. Esterification of sophorolipids is achieved by alcoholysis of natural sophorolipid mixtures. Esters of varying chain lengths and with varying degrees of branching and containing a variety of heteroatoms are included in this invention (FIG. 5). Moreover, methods are already disclosed in the literature that describes selective acetylation of SLs at the 6'- and/or 6"-hydroxy sophorose groups. Therefore one skilled in the art will recognize that many variants may be generated by permutations of the ester functional group and sophorose acetyl groups.
  • a third class of sophorolipid derivatives includes amides of acidic sophorolipids. Representative examples of sophorolipid amide derivatives are shown in FIG. 6. In the exemplary reaction shown, sophorolipid amides can be synthesized from the sophorolipid methyl ester derivative 6 by treatment with an amine at elevated temperature. It is contemplated that a variety of amines, diamines, triamines of differing chain lengths containing aliphatic, olefinic, acetylenic, and aromatic substituents can be used to synthesize the corresponding amide derivatives.
  • amides derived from biogenic amines including, but not limited to, 4- aminosalicylic acid, 5-aminosalicylic acid, octopamine, 3-hydroxytyramine, phenethylamine, tryptamine, histamine, spermine, spermidine, 1 ,5-diaminopentane.
  • amides bearing at the sophorose head group ionic moieties such as sulfate, sulfonate, phosphate, carboxylate and quarternary ammonium salts that result in cationic or anionic charged head groups.
  • substituted amino-containing compounds can be used as a platform to expand the family of sophorolipid amides and that amino acids and polypeptides of varying chain lengths and composition can be incorporated (FIG. 9).
  • a fourth class of MSL includes ammonium salts derived from SL-amides with ⁇ ', ⁇ '-dimethylamino moieties.
  • An exemplary reaction is conversion of the sophorolipid ⁇ ', ⁇ '-dimethylethylamide derivative into the corresponding ammonium salt by treatment with methyl iodide at elevated temperature.
  • the quaternary ammonium salt may be prepared from alkyl halides of varying chain length as well as ⁇ , ⁇ , ⁇ -diiodoalkanes, leading to the formation of a wide array of sophorolipid structures.
  • a fifth class of MSLs include those modified at the sophorose 6' or 6" positions by, inter alia, an activated acyl molecule such as the vinyl ester or alkyl ester of propionic acid catalyzed by an enzyme catalyst such as a lipase in conjunction with one or more of the modifications described herein.
  • an activated acyl molecule such as the vinyl ester or alkyl ester of propionic acid catalyzed by an enzyme catalyst such as a lipase in conjunction with one or more of the modifications described herein.
  • an enzyme catalyst such as a lipase in conjunction with one or more of the modifications described herein.
  • the unsubstituted open-chain acidic sophorolipid is acetylated at the sophorose 6'-hydroxyl position.
  • carbonyl compounds of varying chain lengths and degrees of branching can be incorporated and that a variety of carbonyl-containing functional groups can be incorporated including succinate, malate and citrate.
  • esters of amino acids and oligopeptides can be incorporated at the 6' and/or 6" positions of the sophorose ring.
  • the 6' and/or 6" positions of the sophorose ring may be alkylated (FIG. 1 1 ) by ethylene oxide or a substituted alkylene oxide such as 2,3-epoxypropyl- 1 ,1 ,1 -trimethylammonium chloride (Quab151 ) or related electrophiles as described by Solarek (1989). Such substitutions will likely occur at the primary ( ) 6' and/or 6" positions but may also occur at the secondary (2 ° ) sophorose ring hydroxy! groups to generate mixtures of sophorolipid derivatives.
  • Novel compounds in this class include alkenes with linear or branched alkyl substituents.
  • combinations of metathesis (performed on either the lactonic or open chain SL) and chemical modification can be anticipated.
  • the cross metathesis of lactonic sophorolipid with vinyl acrylate will produce a diester wherein each of the ester groups can be converted into the corresponding amide derivative (Scheme 2).
  • a seventh class of MSLs includes MSLs synthesized using cross metathesis chemistry as described here.
  • lactonic sophorolipids were dissolved in THF (0.54M) at 60°C, and then 4 mol equivalent of acrylates (with various ester chain lengths) were added along with 5 mol% M2 catalysts (1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1 H-inden-1 - ylidene) (tricyclohexylphosphine)ruthenium(ll)). The reaction was quenched by adding ethyl vinyl ether. The conversion was higher than 90%.
  • CMC critical micelle concentrations
  • Example 1 CMCs of MSL esters and amides.
  • FIG. 12 shows CMC of SL-amides, SL-esters and alkyl glucoside as a function of alkyl chain length.
  • the SL-amide series has higher (5 to 8 times) CMC and higher MST than the corresponding SL-ester series. It appears that compared to the ester bond, the amide bond is more disruptive to organization of the corresponding MSL's.
  • One skilled in the art could not have anticipated that the SL-amide n-alkyl series would have higher (5 to 8 times) CMC and higher MST than the corresponding SL-ester series.
  • Amides could have provided better stabilization of micelles through strong hydrogen bonding interactions. Instead the esters pack more easily into micelles at relatively low concentration and have a lower MST than the corresponding amide analogues.
  • Example 2 Emulsification activity of MSLs with paraffin oil. [0091] Emulsion type
  • Dilution test In this test the emulsion is diluted either with oil (O) or water (W). If the emulsion is O/W type and it is diluted with water, it will remain stable as water is the dispersion medium. However, if the emulsion is O/W type and it is diluted with oil, the emulsion will break as oil and water are not miscible with each other. Oil-in- water emulsions can easily be diluted with an aqueous solvent whereas water-in-oil emulsions can be diluted with an oily liquid. Emulsions of the O/W type have separated layers after dilution with pure oil but form a homogenous phase when diluted by water.
  • FIG. 13 shows dilution tests for O/W type emulsions.
  • FIG. 13A displays two replicate test tubes with an O/W emulsion (1 ml_ total volume with water/oil ratio 5/5) stabilized by 2 weight% SL-hexyl amide (Compound 25, Table 1 ) where the oil phase was paraffin.
  • FIG. 13B the tube on the left was diluted with 1 ml_ of oil whereas the tube on right was diluted with water. Visual observation of the tubes in FIG. 13B supports that the emulsions formed are indeed O/W emulsions.
  • Oil Red O was applied as an oil soluble dye and emerald green as water soluble dye in the process of emulsion preparation. Observations of emulsions were made before and after staining under optical microscope at 400x magnification (FIG. 14).
  • FIG. 14A shows emulsion before dye stained and
  • FIG. 14B shows emulsion after dye stained by Oil Red O. From the microscopic observation, staining of the droplet center red by the oil soluble dye Oil Red O indicates the emulsion type is O/W (see FIG. 14B).
  • Table 3 lists the solubility of these compounds.
  • Direct comparison of SL-amides and SL-esters having identical alkyl amide and alkyl ester chain lengths showed the amides have much greater solubility. The greatest difference was for the methyl amide and methyl ester MSLs which have solubilities of >60 and ⁇ 1 mg/mL, respectively.
  • the acidic SL showed good solubility (>50 mg/mL) whereas the solubility of lactonic SL was ⁇ 5 mg/mL.
  • SDS had the highest solubility (>100 mg/mL). It is reasonable to assume that the insoluble fraction of compounds can still participate in the process of emulsion formation by residing at the oil-water interface.
  • the paraffin oil/water volume ratio was 5/5 and the emulsifier content was 2%-by-weight relative to the water phase.
  • the emulsion was obtained by homogenizing the oil and water mixture and was allowed to settle at room temperature for 24 hours. Thereafter, the volumes of the different phases in the emulsion (oil/emulsion/water) were measured (FIG. 15, which shows the results after 24 hours).
  • FIG. 15 shows emulsion phase separation for emulsions prepared using natural and modified sophorolipids by homogenization of paraffin oil/water (5:5 volume ratio) and 2%-by- weight relative to the water phase.
  • MA SL-Methyl Amide (22); EA: SL-Ethyl Amide (23); BA: SL-Butyl Amide (24); HA: SL-Hexyl Amide (25); ME: SL-Methyl Ester (6); EE: SL-Ethyl Ester (7); BE: SL-Butyl Ester (8); HE: SL-Hexyl Ester (16); AC: Acidic SL (3); LA: Lactonic SL (2); NA: Natural SL (1 ); SDS: Sodium dodecyl sulfate.
  • Emulsions were prepared by adding 5 ml_ of paraffin oil into 5 ml_ of water containing 2%-by-weight of the emulsifier. Then, this mixture was homogenized at 13,000 rpm for 2 minutes. Thereafter, the resulting emulsion was left unagitated at 25°C for 24 hours.
  • Surfactants which give a larger emulsion phase are denoted as having higher emulsion effectiveness (Process Safety and Environment protection, 2005, 83, 38-46).
  • the emulsion layer increased with increase of the alkyl chain length.
  • SL-esters having identical alkyl chain length as their corresponding amide derivative were more effective emulsifiers.
  • ester bonds of SL-esters are less disruptive to organization at the oil water interface than amide bonds of SL-amides.
  • the lactonic SL (2) was not effective in emulsification of paraffin oil under the conditions studied herein. This result could not have been anticipated by one skilled in the art.
  • the acidic SL (3) gave an 8% emulsion layer, much lower than the MSL examples given herein.
  • the natural SL (1 ) mixture gave a 10% emulsion layer.
  • Emulsion stability with different oil/water ratio [0100] Emulsion stability with different oil/water ratio. [0101] Based on the effectiveness study, SL-butyl amide (24), hexyl amide (25), butyl ester (8), hexyl ester (16), and SDS as a reference commercial emulsifier were tested as emulsifying compounds for paraffin oil/water emulsions prepared by homogenization having different oil/water ratios. The concentration of MSLs and SDS was kept constant at 2%-by-weight relative to the water phase and the oil/water volume ratios evaluated were 1/9, 5/5 and 7/3.
  • SL-esters were discovered to provide higher stabilization of the emulsification phase as a function of time than corresponding SL-amides with the same alkyl chain length. Furthermore, this invention discloses that SL-butyl ester has a better ability to stabilize the emulsion phase than SL-hexyl amide over a wide range of paraffin oil-to-water volume compositions. For example, at oil/water 5/5 (FIG. 17), using SL-butyl amide, the emulsion layer of was not observed in 3 days.
  • the emulsion layer showed a small decrease in volume-% (65 to 50%) in one month. Also, at oil/water 5/5, using SL-hexyl amide, the emulsion layer decreased from 65% to 10% in one month. Surprisingly, using the SL-hexyl ester at oil/water 5/5, the emulsion layer showed only a small decrease in volume-% (70 to 65%) in one month.
  • FIG. 18 emulsion formation and stability results for paraffin oil/water volume ratios of 7/3 are displayed.
  • SL-butyl ester and hexyl ester formed a 95% emulsion layer, which is higher than that formed using SDS as the emulsion stabilizer (90%).
  • the emulsion phases formed at this oil-to-water ratio show excellent stability.
  • the emulsion phase decreased from 95% to 90 and 85%, respectively, over the one month aging period.
  • Table 4 shows the average droplet size of diluted emulsions after 24 hours of preparation as a function of emulsifier concentration and MSL structure.
  • Emulsified oil droplet size (average and standard deviation) was measured after suitable dilution of the emulsion phase using a Coulter LS 230 analyzer. While the particle sizes of emulsions showed no substantial change by increasing the surfactant concentration from 0.5 to 1 .0%, further increase in the surfactant concentration to 2% did result in significantly smaller emulsion drop sizes. Furthermore, for the same concentration of surfactant, emulsion oil-phase drop sizes showed no significant change for the surfactants studied in Table 4. Therefore, surprisingly, similar size emulsion phase droplets were formed for MSL's in Table 4 and SDS. Relative to natural and lactonic SL, selected MSLs show improved properties as emulsifiers on paraffin oil. These data support our development of effective MSL emulsifiers that are largely bio- based and are biodegradable in bioactive disposal systems such as waste-water treatment plants.
  • emulsified oil droplet size (average and standard deviation) was measured after suitable dilution of the emulsion phase using a Coulter LS 230 analyzer and the results are listed in Table 5. Similar to results for emulsions aged for 24 hours, emulsion phase droplet size after 3-months aging showed no substantial change as the surfactant concentration increased from 0.5 to 1 .0%-by- weight with the possible exception of SL-butyl amide. However, increasing the surfactant concentration from 1 to 2% did result in substantially smaller emulsion-phase droplet sizes. Furthermore, comparing Tables 4 and 5 shows that at 1 % and 2% surfactant droplet sizes are similar for 24 hours and 3 month aging.
  • MSL's can stabilize oil phases greatly decreasing their tendency to undergo coalescence.
  • stabilization against coalescence by selected MSLs in this case SL-butyl ester and SL-hexyl ester, is on par with that attained using the commercial product SDS. It follows that the results of 3-month aging studies support the utility of selected MSLs for formation and stabilization of oil-in-water emulsions of paraffin oil phases.
  • One skilled in the art would expect that the ability of these MSLs to stabilize paraffin oil phases teaches that they would also stabilize oil phases of similar structure.
  • Viscosity was measured at 25°C with increasing shear rate from 1 S "1 to 750 S ⁇ 1 . The viscosity change was monitored for aging times up to 3 months. For all samples, the paraffin oil/water ratio is 7/3 and the surfactant concentrations studied were 0.5%, 1 % to 2%-by-weight relative to the oil phase.
  • FIG. 19 presents the viscosity change with shear rate for different aging times.
  • FIG. 20 shows plots of emulsion viscosity at low shear viscosity ( ⁇
  • FIG. 20 shows viscosity of emulsions prepared from paraffin oil/water 7:3 stabilized by 1 %-by-weight MSL or SDS as a function of aging time at room temperature (25°C). Values of r
  • the extent of viscosity decrease (from lowest to highest) with storage time was in the following order: SL-hexyl ester ⁇ SDS ⁇ SL-butyl ester ⁇ SL-hexyl amide ⁇ SL-butyl amide.
  • the relative ability of different MSL structures to stabilize emulsions and thereby decrease the extent of decrease in viscosity as a function of aging time would not be predictable by one skilled in the art.
  • the behavior as a function of MSL structure is related to emulsion dispersed phase droplet size. That is, the smaller the change in droplet size, the less decrease in emulsion viscosity occurs with increased aging time.
  • Smaller changes in droplet size reflects the ability of the emulsifier to better stabilize particles.
  • the viscosity of the emulsion stabilized by SL-butyl amide decreased by 65% (from 344 Pas to 120 Pas) whereas the viscosity of the emulsion stabilized by SL-hexyl ester decreased by 20% (from 457 Pas to 459 Pas).
  • This result is consistent with the relatively better ability of SL-hexyl ester to retain a small droplet size compared to SL- butyl amide over the aging period.
  • SL-hexyl ester shows almost identical properties in emulsion stability as SDS. Given the commercial importance of SDS, this shows the utility of the invention described here.
  • FIG. 21 shows viscosity of emulsions prepared from paraffin oil/water 7:3, aged for 24 hours at room temperature (25°C), as a function of MSL or SDS concentration (weight-%-relative to the oil phase). The viscosity was measured 24 hours after emulsion preparation. The viscosity increased with increasing surfactant concentration. Such behavior could not have been predicted by one skilled in the art without the teaching provided in this disclosure.
  • the extent of viscosity change with surfactant concentration is related to the interfacial free energy at the droplet surface that reduces with the increase of surfactant concentration.
  • Example 3 Oil solubilization activity of MSLs on lemon and orange oils.
  • MSL's used in this example are SL-hexyl ester (16), SL- octyl ester SL (17), and SL-dodecyl ester (18).
  • MSL capacity for lemon oil solubilization, the volume ratio of water to lemon oil, the concentration of surfactant, and the homogenization time (using a sonicator as the means of homogenization) were varied. Concentration of surfactant is calculated on a w/w basis relative to the mass of water being used.
  • the MSL or other surfactant is first dissolved in the water, oil is added to the solution, and finally the contents of the water/surfactant + oil system is sonicated. Subsequently, the emulsion is allowed to settle for 24 hours at 25°C before measurements or visual observations are made.
  • MSL combinations were investigated. These emulsions were processed with a high shear homogenizer at 13,500 rpm.
  • One example of this MSL combination formulation included 5 weight% surfactant, 1 weight% lemon oil, and 94% deionized water.
  • the pure form of this formulation included 5 weight% SL-hexyl ester.
  • the combination form of this formulation included 2.5 weight% SL-hexyl ester and 2.5 weight% SL-ethyl ester.
  • the SL-hexyl ester emulsion after having been kept at 25°C for one week, was completely opaque, showed surfactant precipitation and possible gelling.
  • FIG. 25 shows representative results of this testing.
  • FIG. 25 shows MSL combinations in which FIG. 25A is 5 weight% EESL + HESL, 1 weight% Lemon Oil; and FIG. 25B is 5wt% HESL, 1wt% Lemon Oil.
  • Example 4 Oil clearing/displacement activity of MSLs with crude oils.
  • Oil cleaning assays were performed using Louisiana Crude, Arabian Light Crude, and Prudhoe Bay Crude as the oil phase.
  • the oil clearing/displacement activity of MSLs were assessed using a crude oil layer on top of sea water in order to simulate oil spill type conditions. Sea water (20 mL) was transferred to plastic Petri dishes and 20 ⁇ of a crude oil type was added on top of the water to create an oil layer. Subsequently, a 20 ⁇ aliquot of MSL solution (1 mg/mL) was added dropwise to the top of the oil layer. The instantaneous formation of an oil clearing zone as well as the diameter of the clearing zone was determined as a function of the dispersant used.
  • Example 5 Emulsification activity of MSLs with crude oils.
  • Emulsification activity was assessed using Louisiana Crude, Arabian Light Crude, and Prudhoe Bay Crude as the oil phase. A 2 mL solution with emulsifier concentration of 1 mg/mL was prepared. A crude oil (10 mg) was added to the emulsifier aqueous solution, the mixture was vortexed for one minute and the emulsified mixture was allowed to stand for 20 minutes. Emulsification activity was determined by measuring turbidity of the emulsion mixture in a spectrophotometer at 610 nm.
  • FIG. 23A shows a microscopic image of sample A in FIG. 1 diluted in paraffin oil that contained sudan red. The image shows that a water- in-oil emulsion formed (scale bar: 100 ⁇ ).
  • FIG. 23B shows a microscopic image of sample B in FIG. 23 diluted in paraffin oil. The water-in-oil emulsion was confirmed by dilution experiment, as dye experiment gave poor resolution (scale bar: 10 ⁇ ).
  • FIG. 23A shows a microscopic image of sample A in FIG. 1 diluted in paraffin oil that contained sudan red. The image shows that a water- in-oil emulsion formed (scale bar: 100 ⁇ ).
  • FIG. 23B shows a microscopic image of sample B in FIG. 23 diluted in paraffin oil. The water-in-oil emulsion was confirmed by dilution experiment, as dye experiment gave poor resolution (scale bar: 10 ⁇ ).
  • MSLs Modified Sophorolipids
  • sophorolipid components of the natural mixture incorporated for use in this invention.
  • the hydroxylated fatty acid of the natural mixture is predominantly 17-hydroxyoleic acid.
  • concentration of surfactant is calculated on a w/w basis relative to the mass of water used. b) performed by dynamic light scattering
  • Commonly consumed food commodities, animal feed items, and edible fats and oils as described in C 3 ⁇ 4JJiK ⁇ (a), (b), and (c) may be used as inert ingredients in FIFRA Section 25(b) pesticide products applied to food use sites (e.g., food crops, animals used for food) and in FIFRA Section 25(b) pesticide products applied to nonfood use sites (e.g., ornamental plants, highway right-of- ways, rodent control).
  • Specific chemical substances listed under Q3 ⁇ 4JJCL 50(e) that are also acceptable for use as inert ingredients in FIFRA Section 25(b) pesticide products are included in the table below.
  • inert ingredients are also eligible for inclusion in FIFRA Section 25(b) pesticide products. These ingredients are listed by CAS Registry Number and chemical name (common names are given, with systematic names included as synonyms in brackets where applicable). In addition, this listing has two columns to indicate whether the inert ingredient can be used in FIFRA Section 25(b) products applied to food use and/or nonfood use sites.

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Abstract

La présente invention concerne un procédé de création d'une banque de sophorolipides modifiés faisant appel à un large éventail d'outils de type catalyseurs chimiques et enzymatiques pour identifier des sophorolipides modifiés qui peuvent être utilisés purs, en mélange avec d'autres sophorolipides modifiés, en mélange avec des sophorolipides naturels, en mélange avec des sophorolipides modifiés et naturels et en mélange avec d'autres composés connus de l'homme du métier à des fins de dispersion, de solubilisation ou d'émulsification de divers types d'huiles et de divers alicaments, ainsi que des sophorolipides modifiés utilisables dans le cadre de procédés de dispersion, de solubilisation ou d'émulsification.
EP14803556.1A 2013-05-27 2014-05-27 Sophorolipides modifiés utilisables en tant qu'agents de solubilisation des huiles Withdrawn EP3003044A4 (fr)

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PCT/US2014/039624 WO2014193856A1 (fr) 2013-05-27 2014-05-27 Sophorolipides modifiés utilisables en tant qu'agents de solubilisation des huiles

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CN112442098B (zh) * 2019-09-03 2022-05-17 中国石油化工股份有限公司 一种磺化改性槐糖脂或其盐以及它们的制备方法
CN112742855B (zh) * 2019-10-31 2022-11-15 中国石油化工股份有限公司 一种石油污染后的土壤修复方法
CN111096445A (zh) * 2019-12-04 2020-05-05 江苏省农业科学院 一种基于微生物材料的纳米营养载体及其制备方法
CN114106807B (zh) * 2020-08-27 2023-05-05 中国石油化工股份有限公司 一种改性槐糖脂组合物、其制备方法及应用
CN114479866B (zh) * 2020-10-23 2024-02-09 中国石油化工股份有限公司 一种生物型淋洗剂、其制备方法及应用
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