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    • 专利摘要:
    MIXTURE COMPOSITION UNDERSTANDING RHAMNOLIPIDS The invention relates to a mixing composition comprising rhamnolipids, a process for its preparation, its use to produce formulations and formulations comprising that mixing composition.
    公开号:BR102014007948B1
    申请号:R102014007948-3
    申请日:2014-04-02
    公开日:2020-11-03
    发明作者:Martin Schilling；Christian Hartung；Fabien Cabirol；Steffen Schaffer；Petra Allef
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The invention relates to a mixture composition comprising rhamnolipids, a process for its preparation, its use for the production of formulations and formulations comprising that mixture composition. PREVIOUS TECHNIQUE
    [002] Rhamnolipids are glycolipids that are produced in the free nature from bacteria, for example, Pseudomonas aeruginosa. Microorganisms usually produce mixtures of rhamnolipids that comprise mono- and di-rhamnolipids that have one or two units of rhamnose per molecule and may contain lipid chains of different length.
    [003] EP 153,634 describes a mixing composition with an almost balanced weight ratio of mono - to dihamnolipids.
    [004] Likewise, EP 0.499.434 describes, in Example 3, compositions of rhamnolipids with a balanced weight ratio of the two components.
    [005] EP 2,410,039 describes cleaning compositions comprising mono- and di-rhamnolipids with a weight ratio of 95: 5 to 45:55.
    [006] The characterization of the surface activities of pure dhamnolipids, pure mono-rhamnolipids and mixtures thereof are described, for example, in Chen et al., Solution self-assembly and adsorption at the airwater interface of the monorhamnose and dirhamnose rhamnolipids and their mixtures, Langmuir. 2010 December 7; 26 (23: 18281-92.
    [007] A disadvantage of rhamnolipids hitherto known that can be prepared by simple fermentative processes is their relatively small fraction of rhamnolipids.
    [008] In addition to this, these rhamnolipid compositions often comprise rhamnolipids with only one acyl chain as an undesirable by-product.
    [009] Compositions of pure di-rhamnolipids purified by fractionation are characterized under use as cosmetic by a dry, rough skin feeling.
    [0010] It was an object of the invention to provide compositions that have good foam properties and, in addition, have a light feeling on the skin when used in skin care compositions or skin cleansing compositions. Description of the invention
    [0011] Surprisingly, it was revealed that the mixture composition described below is capable of achieving the objective addressed by the invention.
    [0012] Therefore, the present invention provides mixing compositions that comprise certain rhamnolipids in defined weight ratios.
    [0013] The invention further provides a process for preparing the mixing compositions according to the invention using genetically modified cells.
    [0014] The present invention further provides formulations that comprise the compositions of the mixture according to the invention.
    [0015] An advantage of the compositions of the mixture according to the invention is their excellent foam stability under aqueous conditions.
    [0016] Another advantage of the compositions of the mixture according to the invention is its excellent volume of the foam in aqueous conditions-
    [0017] Another advantage of the mix compositions according to the invention is their exceptional foaming behavior.
    [0018] Another advantage of the mix compositions according to the invention is their simple ability to formulate in all the desired aqueous surfactant systems.
    [0019] Another advantage of the mix compositions according to the invention is their good ability to thicken with conventional thickeners in the formulations.
    [0020] Another advantage is its good ability to wash skin and hair.
    [0021] Another advantage of the compositions of the mixture according to the invention is its softness and good physiological compatibility, in particular characterized by a high value in the hemolysis test (RBC).
    [0022] Another advantage is your good skin feeling during and after washing.
    [0023] Another advantage of the mix compositions according to the invention is that they leave behind a soft touch of the skin after washing.
    [0024] Another advantage of the mix compositions according to the invention is that they leave a feeling of smoothness of the skin after washing.
    [0025] Another advantage of the mix compositions according to the invention is that they have an over-greasy effect on the skin.
    [0026] Another advantage of the mix compositions according to the invention is that they can be synthesized essentially free of oil.
    fórmula (I) onde m = 2, 1 ou 0, n = 1 ou 0, R1 e R2 = radical orgânico idêntico independentemente um do outro ou diferente tendo 2 a 24, de preferência 5 a 13 átomos de carbono, em particular, radical alquila opcionalmente ramificado, opcionalmente substituído, em particular hidróxi-substituido, opcionalmente insaturado, em particular, opcionalmente mono-, di- ou tri-insaturado, preferivelmente aquele selecionado de um grupo consistindo de pentenila, heptenila, nonenila, undecenila e tridecenila e (CH2)O-CH3 em que o = 1 a 23, de preferência de 4 a 12.[0027] In context with the present invention, the term "rhamnolipid" is understood to mean in particular compounds of the general formula (I) or their salts, formula (I) where m = 2, 1 or 0, n = 1 or 0, R1 and R2 = identical organic radical independently of each other or different having 2 to 24, preferably 5 to 13 carbon atoms, in particular, radical optionally branched, optionally substituted alkyl, in particular hydroxy-substituted, optionally unsaturated, in particular, optionally mono-, di- or tri-unsaturated, preferably that selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and (CH2 ) O-CH3 where o = 1 to 23, preferably 4 to 12.
    [0028] In connection with the present invention, the term "di-rhamnolipid" is understood to mean compounds of the general formula (I) or their salts, where n = 1.
    [0029] In context with the present invention, the term "mono-rhamnolipid" is understood to mean the compounds of the general formula (I) or their salts, where n = 0.
    [0030] Different rhamnolipids are abbreviated according to the following nomenclature: "diRL-CXCY" is understood to mean di-rhamnolipids of general formula (I), where one of the radicals R1 and R2 = (CH2) o-CH3, where o = X-4 and the remaining radical R1 or R2 = (CH2) o-CH3, where o = Y-4.
    [0031] "MonoRL-CXCY" is understood to mean mono-rhamnolipids of general formula (I) in which one of the radicals R1 and R2 = (CH2) O-CH3, where o = X-4 and the remaining radicals R1 or R2 = (CH2) o-CH3, where o = Y-4.
    [0032] The nomenclature used, therefore, makes no difference between "CXCY" and "CYCX".
    [0033] For rhamnolipids where m = 0, monoRL-CX or diRL-CX is used accordingly.
    [0034] If one of the above mentioned indices X and / or Y is provided with "Z", then that means that the respective radical R1 and / or R2 = an unsubstituted hydrocarbon radical, not branched with X-3 or Y- 3 carbon atoms, having Z double bonds.
    [0035] In connection with the present invention, "pH" is defined as the value that is measured for a substance corresponding to 25 ° C after stirring for five minutes using a pH electrode calibrated in accordance with ISO 4319 ( 1977).
    [0036] In connection with the present invention, the term "aqueous medium" is understood to mean a composition that comprises at least 5% by weight of water, based on the total composition under consideration.
    [0037] Unless otherwise stated, all percentages mentioned (%) are percentages by mass.
    [0038] The present invention provides a mixture composition comprising rhamnolipids, characterized in that the mixture composition comprises 51% by weight to 95% by weight, preferably 70% by weight to 90% by weight, particularly preferably 75% by weight at 85% by weight, diRL-C10C10 and 0.5% by weight at 9% by weight, preferably 0.5% by weight at 3% by weight, particularly preferably by 0.5% by weight at 2% by weight of monoRL-ClOClO, where the weight percentages refer to the sum of all rhamnolipids present, with the proviso that the weight ratio of di-rhamnolipids to mono-rhamnolipids is greater than 91: 9, from preferably greater than 97: 3, particularly preferably greater than 98: 2.
    A preferred mixing composition according to the invention is characterized in that the mixing composition comprises 0.5% by weight to 15% by weight, preferably 3% by weight to 12% by weight, particularly preferably 5 % by weight to 10% by weight of diRL-C10C12: 1, where the weight percentages refer to the sum of all the rhamnolipids present.
    An even more preferred blend composition according to the invention is characterized in that the blend composition comprises 0.5 to 25% by weight, preferably 5% by weight to 15% by weight, particularly preferably 7% by weight to 12% by weight of diRL-C10C12, where the weight percentages refer to the sum of all the rhamnolipids present.
    [0041] It is also preferable if the composition of the mixture according to the invention comprises 0.1% by weight to 5% by weight, preferably 0.5% by weight to 3% by weight, particularly preferably 0.5 % by weight to 2% by weight of monoRL-C10C12 and / or, preferably, and 0.1% by weight to 5% by weight, preferably 0.5% by weight to 3% by weight, particularly preferably 0.5 wt% to 2 wt% monoRL-C10C12: 1, where the weight percentages refer to the sum of all rhamnolipids present.
    [0042] It can be advantageous and, therefore, it is preferred that the composition of the mixture according to the invention comprises 0.1% by weight to 25% by weight, preferably 2% by weight to 10% by weight, especially of preferably 4% by weight to 8% by weight of diRL-C8C10, where the weight percentages refer to the sum of all rhamnolipids present.
    A particularly preferred mixing composition according to the invention is characterized in that the mixing composition comprises 0.5% by weight to 15% by weight, preferably 3% by weight to 12% by weight, especially preferably from 5% by weight to 10% by weight of diRL-Cl0C12: 1, 0.5 to 25% by weight, preferably 5% by weight to 15% by weight, particularly preferably 7% by weight to 12% by weight diRL-C10C12, 0.1 wt% to 5 wt%, preferably 0.5 wt% to 3 wt%, particularly preferably 0.5 wt% to 2 wt% monoRL-C10C12 and 0.1% by weight to 5% by weight, preferably 0.5% by weight to 3% by weight, particularly preferably 0.5% by weight to 2% by weight, of monoRL-C10C12: 1, where the weight percentages refer to the sum of all rhamnolipids present.
    [0044] Furthermore and above that, it is preferable that the composition of the mixture according to the invention comprises rhamnolipids of formula monoRL-CX or diRL-CX in small amounts only. In particular, the composition of the mixture according to the invention preferably comprises 0% by weight to 5% by weight, preferably 0% by weight to 3% by weight, particularly preferably 0% by weight to 1% by weight. diRLClO weight, where the weight percentages refer to the sum of all rhamnolipids present, and the term "0% by weight" is to be understood as meaning no detectable amount.
    [0045] The composition of the mixture according to the invention preferably comprises at least 60% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight of rhamnolipids , where the weight percentages refer to the dry substance of the total mixture composition.
    [0046] It is preferable, according to the invention, that the mixing compositions according to the invention are essentially free of fatty oil (liquid acylglycerols at 20 ° C) and therefore comprise, in particular, less than 0, 5% by weight, in particular less than 0.1% by weight, particularly preferably no detectable amount of a fatty oil, based on the total composition of the mixture.
    [0047] The mixing compositions according to the invention can be prepared by mixing the pure substances, in which case the pure substances can be purified from conventionally prepared mixtures of rhamnolipids. Corresponding purification processes are, for example, selective crystallizations and chromatographic methods. Corresponding processes are described in Heyd et al., Development and trends of biosurfactant analysis and purification using rhamnolipids as na example, Anal Bioanal Chem. 2008 Jul; 391 (5): 1579-90.
    [0048] In particular, the processes described below, which are also objects of the present invention, are suitable for the preparation of mixing compositions according to the invention.
    [0049] The process according to the invention comprises the process steps: Ia) to supply a Pseudomonas putida cell that has been genetically modified in such a way that it overexpresses in each case at least one gene of the rhlA, rhlB and rhlC, lia) contacting the cell according to the invention with a medium comprising a carbon source, Illa) cultivating the cell under conditions that allow the cell to form rhamnolipid from a carbon source and IVa) optionally isolating the formed rhamnolipids, characterized in that the rhlC gene is more overexpressed compared to rhlB, in particular at least 1.5 times more, preferably at least twice more, particularly preferably at least 10 times more.
    [0050] The relative intensity of the overexpression described above can be determined, for example, with the help of RT-PCR, in which the amount of mRNA formed is determined for the respective gene.
    [0051] The person skilled in the art can obtain a regulation of the intensity of expression in a targeted way, for example, through the selection of promoters, or through the use of inducible promoters in combination with a quantity of inducer, or else by means of multiplications of genes.
    [0052] An equally preferred alternative process according to the invention comprises the process steps: Ib) providing a Pseudomonas putida cell that has been genetically modified in such a way that in each case it has at least one exogenous rhlA gene, rhlB and rhlC of which at least one is under the control of an inducible promoter, Ilb) contacting the cell according to the invention with and culturing it with a medium comprising at least one carbon source while obtaining a cell density of 1 to 30 g of dry cell mass per L of fermentation broth, preferably 2 to 20 of dry cell mass per L of fermentation broth, particularly preferably 5 to 15 g of dry cell mass per L of fermentation broth, Illb) induce by minus an inducible promoter and culturing the cell under conditions that allow the cell to form a rhamnolipid from the carbon source and IVb) optionally isolating the formed rhamnolipids.
    [0053] In connection with the present invention, the term "inducible promoter" is understood to mean a promoter that changes its activity by changing the medium surrounding the cell. Changes can include changes, for example, in temperature and changes in the concentration of certain substances.
    [0054] In connection with the present invention, the term "induce at least one inducible promoter" is to be understood as meaning that the activity of the inducible promoter is increased by changing the medium surrounding the cell.
    [0055] Suitable inducible promoters in connection with the present invention are, for example, promoters that are induced by the addition of chemical inducers (e.g., lactose, IPTG, dicyclopropyl ketone, tetracycline, doxycycline, propionate, cumate, benzoate, arabinose, rhamnose, nicotinic acid, etc.), which are induced by altered environmental conditions (for example, occurrence of phosphate or sulfur deficiency, altered temperatures or pH, etc.), or which are induced by certain physiological states (for example, certain densities growth rates or phases).
    [0056] Inducible promoters used particularly preferably in the process are selected from the group of promoters inducible by dicyclopropyl ketone, tetracycline, doxycycline, propionate, cumate, benzoate, phosphate deficiency, sulfur deficiency or a reduced growth rate.
    [0057] The rhlA, rhlB and rhlC genes in both processes according to the invention are preferably selected from those of P. aeruginosa.
    [0058] The two processes according to the invention are preferably not carried out like biotransformation; this means that rhamnolipids are not formed from fatty acids or compounds containing fatty acid such as, for example, fats and oils, which are introduced into the process externally, but that the carbon sources specified in the processes are, in particular, for be understood to mean those that contain, predominantly, at least one carbon-containing compound, with the exception of fatty acids or compounds containing fatty acid.
    [0059] The mixing compositions according to the invention can advantageously be incorporated into cosmetic formulations, in particular.
    [0060] Therefore, another claim of the present invention is the use of the compositions of the mixture according to the invention for the production of formulations, in particular cosmetic formulations, and also formulations, in particular, cosmetic formulations comprising the composition of the mixture according to the invention.
    [0061] In addition to the compositions of the mixture according to the invention, the preferred formulations according to the invention comprise at least one other surfactant, being possible to use, for example, anionic, non-ionic, cationic and / or amphoteric surfactants. Preferably, from a point of view of related applications, preference is given to mixtures of anionic and non-ionic surfactants. The total surfactant content of the aqueous formulation is preferably 5 to 60% by weight and particularly preferably 15 to 40% by weight, based on the total formulation.
    [0062] The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in the which alcohol radical can be linear or preferably methyl-branched in position 2 or can contain methyl-branched and linear radicals in a mixture, as are generally present in oxo-alcohol radicals. In particular, however, ethoxylated alcohols with linear radicals of native alcohols having 12 to 18 carbon atoms, for example, coconut, palm, tallow fat or oleyl alcohol and, on average, 2 to 8 EO per mol of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO, 4 EO or 7 EO, Cg-Cu alcohol with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12 alcohols -C18 with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and Ci2-Ci8 alcohol with 7 EO. The declared degrees of ethoxylation are average statistical values that can be an integer or a fraction of a specific product. Preferred ethoxylated alcohols have a narrow homologous distribution.
    [0063] In addition to these non-ionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 or 40 EO. Nonionic surfactants that contain EO and PO (propylene oxide) groups together in the molecule can also be used. In this context, it is possible to use block copolymers with EO-PO block units or PO-EO block units, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
    [0064] It is certainly also possible to use mixed alkoxylated non-ionic surfactants in which the OE and PO units are not distributed in blocks, but randomly. Such products can be obtained as a result of the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
    [0065] In addition, alkylglycosides can also be used as other non-ionic surfactants.
    [0066] Another class, preferably used nonionic surfactants, which are used either as the only nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598, or which are preferably prepared by the process described in international patent application WO-A-90/13533.
    [0067] Nonionic surfactants of the type of amine oxide, for example, N-cocoalkyl-N, N-dimethylamine oxide and N-seboalkyl-N, N-dihydroxyethylamine oxide, and the type of fatty acid alkanolamide can also be adequate. The amount of these non-ionic surfactants is preferably not more than that of ethoxylated fatty alcohols, in particular, not more than half of them.
    [0068] Other suitable surfactants are polyhydroxy fatty acid amides; polyhydroxy fatty acid amides are substances that can generally be obtained by reducing amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
    [0069] The anionic surfactants used are, for example, those of the sulfonate and sulfate type. The appropriate sulfonate type surfactants here are preferably C9-C13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates, and also disulfonates, as are obtained, for example, from C12-C18 mono-olefins with double terminal bond or internal by sulfonation with gaseous sulfur trioxide and subsequent acid or alkaline hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C12-C18 alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, cx-sulfo fatty acid esters (sulfonate ester), for example, α-sulfonated methyl esters of hydrogenated coconut, palm seed or tallow fatty acids, are also suitable.
    [0070] Other suitable anionic surfactants are the sulfated glycerol esters of fatty acid. Fatty acid glycerol esters are to be understood as meaning that mono-, di- and triesters, and also mixtures thereof, as are obtained in the preparation by esterifying a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters here are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, for example, caprylic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
    [0071] Preferred alkyl (en) yl sulphates are the alkali metal and, in particular, the sodium salts of the sulfuric acid semi-esters of the C1-C18 fatty alcohols, for example, coconut fatty alcohol, fatty alcohol tallow, lauryl alcohol, myristic, cetyl or oxo-alcohols C10-C20 and those semi-esters of secondary alcohols with these chain lengths. In addition, preference is given to specific chain-length alkyl (en) yl sulfates which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis, and which have a degradation behavior analogous to suitable compounds based on raw materials fatty chemicals. From the point of view of washing, C12-C16 alkyl sulfates and C12-C18 alkyl sulfates and also C14-C18 alkyl sulfates are preferred. 2,3-alkyl sulphates, which are prepared, for example, according to US patent reports 3,234,258 and 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
    [0072] Sulfuric acid mono esters of C7-C20 straight or branched ethoxylated alcohols with 1 to 6 mol of ethylene oxide, such as C9-Cu 2-methyl branched alcohols having on average 3.5 moles of oxide ethylene (EO) or C12-C18 fatty alcohols with 1 to 4 EO are also suitable. Because of their high foaming behavior, they are used in cleaning compositions only in relatively small amounts, for example, in amounts of 1 to 5% by weight.
    [0073] Other suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as esters of sulfosuccinic acid and constitute the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably alcohols fatty acids and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cg-Cig fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol radical that is derived from ethoxylated fatty alcohols. In this context, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homologous distribution are particularly preferred in turn. It is also possible to use alkyl (en) isuccinic acid preferably having 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.
    [0074] Particularly preferred anionic surfactants are soaps. Also suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, erucic acid (hydrogenated) and behenic acid, and also mixtures derived from soap, in particular, fatty acids natural, eg coconut, palm seed, olive oil or tallow fatty acid.
    [0075] Anionic surfactants, including soaps, can be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of sodium salts.
    [0076] Amphoteric surfactants that can be used according to the invention are surfactant compounds that carry at least one quaternary ammonium group and at least one -COO "- or -SO" 3 group in the molecule. Particularly preferred amphoteric surfactants in this context , are betaine surfactants such as alkyl- or alkylamidopropyl betaines, in particular betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example, cocoalkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example, cocoacylaminopropyldimethylammonium glycinate, alkyldimethylacetobetaine CI2-CI8A to cocoamidopropyldimethylacetobetaine, 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines and sulfobetaines in each case 8 to 18 carbonylethylacetylethylacetylethylacetylacetylacetylacetylacetyl and acyl A particularly preferred zwitterionic surfactant is N, N-dimethyl-N- (lauroylamidopropyl) ammonium acetobetaine with known under the name INCI cocoamidopropyl betaine.
    [0077] Other suitable amphoteric surfactants are formed by the group of amfoacetates and amphodiacetates, in particular, for example, coco- or laurylamfoacetates or - diacetates, the group of amphopropionates and amphodipropionates, and the group of amino acid-based surfactants, such as acylglutamates , in particular, disodium cocoylglutamate and sodium cocoylglutamate, acylglycinates, in particular, cocoylglycinates, and acylsarcosinates, in particular, ammonium lauryl sarcosinate and sodium cocoylsarcosinate.
    [0078] Furthermore, the formulations according to the invention may comprise at least one additional component selected from the group of emollients, emulsifiers, thickeners / viscosity regulators / stabilizers, UV photoprotective filters, antioxidants, hydrotropes (or polyols) , solids and fillers, film-forming, pearly additives, deodorant and antiperspirant active ingredients, insect repellents, self-tanning agents, preservatives, conditioners, perfumes, dyes, odor absorbers, cosmetic active ingredients, care additives, over-greasing agents, solvents.
    [0079] Substances that can be used as exemplary representatives of the individual groups are known to the person skilled in the art and can be found, for example, in the German application DE 102.008.001.788.4. This patent application is incorporated herein by reference and is therefore part of the description.
    [0080] With regard to other optional components and the quantities of these components used, express reference is made to the relevant manuals known to the person skilled in the art, for example, K. Schrader, "Grundlagen und Rezepturen der Kosmetika [Cosmetic foundations and formulations ] ", 2nd edition, page 329-341, Hüthig Buch Verlag Heidelberg.
    [0081] The quantities of the respective additives depend on the intended use.
    [0082] Typical guide formulations for the respective applications are known from the prior art and are contained, for example, in the manufacturers' brochures of the respective basic materials and active ingredients. These existing formulations can generally be adopted unchanged. If necessary, however, the desired modifications can be carried out without complications through simple experiments for the purposes of adaptation and optimization.
    [0083] Mixing compositions according to the invention and formulations according to the invention comprising the mixing composition according to the invention can advantageously be used for cleaning surfaces. In this form of use according to the invention, the surface is preferably the surface of a living being, in particular, of a person, with such surfaces particularly preferably being selected from the skin and hair.
    [0084] The examples listed below describe the present invention by way of example without any intention of limiting the invention, the scope of application of which arises from the entire description and the claims, for the modalities specified in the examples.
    [0085] The following figures are part of the description: Figure 1: Foaming behavior shown with SITA measurement Examples: Example 1: Preparation of diRL-ClOClO and monoRL-ClO-ClO
    [0086] The preparation of the various forms of pure RL occurs by means of preparative column chromatography. For this, 750 g of a silica gel 60 (200-500 pm; 35-70 mesh; Sigma - Aldrich, Germany) are suspended in water-saturated ethyl acetate (acidified with 1% by weight of acetic acid) and poured for a column (diameter = 65 mm, maximum filling level = 600 mm, 1 L of solvent tank). 2 to 3 cm of acid-treated sea sand (Riedel de Haen, Seelze, Germany) were coated as a protective layer over the stationary phase. The eluent used is also water-saturated ethyl acetate which comprises 1% by weight of acetic acid. A commercially available mixture of RL (JBR 505, Jeneil Biosurfactantes, ~ 5% by weight of total rhamnolipid concentration) is lyophilized.
    [0087] 10 g of the lyophilized RL mixture is dissolved in 5% by weight of concentration in the eluent. The solution is placed in a prepared column. The flow rate of the eluent is adjusted to 15 ml / min. The eluate is collected in 100 ml fractions and analyzed using thin layer chromatography and HPLC. The various forms of RL can be separated in this way. Fractions of identical composition are combined and the solvent is removed on a rotary evaporator. Then, the residue is dissolved in water, lyophilized and used as a powder for application tests. In order to obtain adequate quantities, this procedure is performed several times. The purity of the resulting fractions is determined to be> 99% by weight by means of 1H-NMR and HPLC. Example 2: Preparation of a mixture of diRL-Cl OCl The emonoRL-ClOCl0
    [0088] The pure RL forms described in Example 1 are mixed in powder form in a ratio of 97.5: 2.5 diRL-C10C10 to monoRL-ClOClO. Example 3: Preparation of rhamnolipids with rhlABC from P. aeruginosa PAO1 in P. put ida, where the expression of the gene encoding Rhham rhamnosyltransferase is many times greater than that of the gene encoding rhamnosyltransferase rhlB.
    [0089] In order to prepare rhamnolipids with rhlABC from P. aeruginosaPAO1 in a strain of P. putida in which the expression of the gene encoding Rhham rhamnosyltransferase occurs to a much greater extent than that of the gene encoding Rhham rhamnosyltransferase, the plasmid pBBRlMCS2-Plac-rhlABC-T-Ptac-rhlC-T (SEQ ID NO: 1) is constructed. Therefore, the following DNA fragments were synthesized: P. aeruginosaPAO1 rhlA, rhlB and rhlC genes, followed by a terminator, followed by the synthetic tac promoter, followed by the P. aeruginosaPAO1 rhlC gene and a terminator, flanked by a HindIII restriction (5 'end) or Bsu36I restriction site (3' end) (Seq ID No. 2).
    [0090] The vectors provided by the DNA synthesis supplier and which contain the synthesized DNA fragment are cleaved with JLindIII and Bsu36T and linked to the pBBRlMCS-2 vector (SEQ ID 3), also cleaved with Hindlll and Bsu36l, by means of a Fast Link Connection Kit (Epicenter Technologies; Madison, WI, USA). The resulting target vector pBBRlMCS-2-Plac-rhlABC-T-Ptac-rhlC-T (pBBRlMCS-2 with the synthesized fragment Seq ID No. 2) is 9336 base pairs in size.
    [0091] The transformation of Pseudomonas putida KT2440 with the vector pBBRlMCS2-Plac-rhlABC- T-Ptac-rhlC-T (SEQ ID NO: 1) occurs as described above (Iwasaki et al. Biosci. Biotech. Biochem. 1994 58 (5): 851-854). Plasmid DNA from 10 clones in each case is isolated and analyzed. The resulting strain that carries the plasmid is called P. putida KT2440 pBBRlMCS2-Plac-rhlABC-T-Ptac-rhlC-T.
    [0092] The recombinant strain of P. putida KT2440 pBBR1MCS2-Plac-rhlABC-T-Ptac-rhlC-T is cultured on LB-agar-kanamycin plates (50 pg / ml).
    [0093] For the production of rhamnolipids, the medium referred to below as M9 medium is used. This medium consists of 2% (w / v) glucose, 0.3% (w / v) KH2PO4, 0.679% Na2HPO4, 0.05% (w / v) NaCl, 0.2% (w / v) NH4C1, 0.049% (w / v) MgSO4 x 7 H2O and 0.1% (w / v) of a solution with trace elements. This consists of 1.78% (w / v) FeSO4 x 7 H2O, 0.191% (w / v) MnCl2 x 7 H2O, 3.65% (w / v) HCl, 0.187% (w / v) ZnSO4 x 7 H2O, 0.084% (v / v) Na-EDTA x 2 H2O, 0.03% (v / v) H3BO3, 0.025% (w / v) Na2Mo04 x 2 H2O and 0.47 % (w / v) CaCl2 x 2 H2O. The pH of the medium is adjusted to 7.4 with 2OH and the medium is therefore sterilized by autoclaving (121 ° C, 20 minutes). Adjusting the pH during culture is not necessary.
    [0094] To investigate the production of ramnolipid in the shake flask, first a pre-culture is prepared. For this reason, a colony of a strain recently sown on an LB plate - agar is used and 10 ml of LB medium is inoculated into a 100 ml Erlenmeyer flask. All recombinant P. putida strains are grown in LB medium to which 50 pg / ml kanamycin is added. The strains of P. putidas are grown overnight at 30 ° C and 200 rpm.
    [0095] Pre-cultures are used to inoculate 50 ml of M9 medium (+50 pg / ml kanamycin) in a 250 ml Erlenmeyer flask (starting from ODβOO 0.1). Cultures are grown at 200 rpm and 30 ° C. After 24 h, a 1 ml sample of culture broth is removed from the culture flask. Fermentation and purification
    [0096] A mineral medium (M9) is also used for the main culture. Fermentation following inoculation with 10% by volume of pre-culture and the consumption of glucose initially introduced occurs with carbon limitation through a glucose feed in a 2 liter fermenter with an operational volume of 1.2 1. The feed of glucose occurs by reference to the dissolved oxygen signal. The dissolved oxygen is regulated to a saturation of 20% through the stirring speed. The pH is adjusted to 7 using a pH electrode and the addition of NH4SO4. Fermentation is carried out over 4 days for a dry biomass of 15g / l. The concentration of rhamnolipid was verified by HPLC and is 9.8 g / 1. After separating the cells by centrifugation at 10,000 g, the fermentation broth is adjusted to a pH of 4.0 by the addition of concentrated HCl. The extraction is then carried out with the same volume of ethyl acetate. The organic phase containing the rhamnolipid is separated and processed. The pH of the solution is adjusted to pH 7 by adding 50% KOH by weight (aq). This results in the formation of two liquid phases. The lower phase contains rhamnolipids free of lipophilic and hydrophilic impurities in high purity. The composition of the RL mixture is not influenced as a result. The lower phase is removed and the solvent is largely removed on a rotary evaporator. Water is then added again and the aqueous RL solution is lyophilized. The resulting powder is analyzed using HPLC and characterized as for application. Quantification of rhamnolipids
    [0097] The sample preparation for the next chromatographic analysis takes place as follows. A displacement pipette (Combitip) is used to initially introduce 1 ml of acetone into a 2 ml reaction vessel, and the reaction vessel is closed immediately to minimize evaporation. This is followed by the addition of 1 ml of culture broth. After the vortex, the culture broth / acetone mixture is centrifuged for 3 minutes at 13,000 rpm, and 800 µl of the supernatant is transferred to an HPLC vessel.
    [0098] For the purposes of detection and quantification of rhamnolipids, an evaporative light scattering detector (SEDEX LT-ELSD model 85LT is used. The actual measurement is performed using Agilent Technologies series 1200 (Santa Clara, California) and the Zorbax SB-C8 rapid resolution column (4.6 x 150 mm, 3.5 pm, Agilent). The injection volume is 5 pl and the method execution time is 20 minutes. The mobile phase used is TEA 0.1% aqueous (trifluoroacetic acid, solution A) and methanol (solution B). The column temperature is 40 ° C. Serving as detectors are ELSD (detector temperature 60 ° C) and DAD (diode array, 210 nm) .The gradient used in the method is:
    resultando em uma relação em peso de di-rhamnolipideos de mono-rhamnolipideos de 99:1.[0099] The rhamnolipid composition of P. Putida KT2440 pBBRlMCS2-Plac-rhlABC-T-Ptac-rhlC-T obtained with the process described above comprises: resulting in a 99: 1 weight ratio of mono-rhamnolipid di-rhamnolipids. Example 4: Testing skin care performance and foam properties using a hand wash test
    [00100] To evaluate the skin care performance and foam properties of Product Examples 2 and 3 according to the invention in aqueous surfactant compositions (surfactant formulations), sensory hand washing tests compared to known rhamnolipids were performed.
    [00101] A group of 10 trained evaluators washed their hands in a defined manner during this hand washing test and evaluated the properties of the foam and hand sensation by reference to a rating scale of 1 (bad) to 5 (very good) ). The products used were tested in each case in a standardized surfactant formulation (Table 1).
    [00102] The surfactant formulation without the addition of a secondary surfactant was used as a control formulation of surfactant formulations A. Surfactant formulations B and C are the comparison products not according to the invention and surfactant formulations D and E are the compositions according to the invention (Table 1).
    [00103] Table 1: Test formulations for the hand washing test (data in% by weight).
    [00104] Table 2 shows the results of the hand washing test.
    [00105] It is evident from the results of the measurements in Table 2 that compositions D and E according to the invention using product examples 2 and 3 have a better skin feeling during washing with the formulation and surprisingly also a better behavior foaming and increased creaminess of the foam compared to control A and comparison compositions B and C according to the prior art. In addition, it is evident that the compositions D and E according to the invention were evaluated as being better than the comparison formulations for skin sensation (skin smoothness and skin softness), after washing and drying.
    [00106] Contrary to expectations, a certain low fraction of mono-rhamnolipid in the biotensoactive exhibited a positive influence on the foam behavior and skin sensation in the present formulations. Example 5: Testing foam properties using a SITA foam evaluator
    [00107] The capacity of foam surfactant solutions is an important parameter. Application properties can be inferred from this. Rapid foaming and a large volume of foam are expected in many good surfactant applications. One method for evaluating this parameter is based on a SITA R-2000 foam evaluator from SITA Messtechnik GmbH. Here, air is introduced into a given volume of a surfactant solution through a dispersion disc and the total volume of liquid and resulting foam is measured over the period using probes in the foam.
    [00108] Three different rhamnolipid preparations were measured on such an instrument at pH = 6 and a total rhamnolipid concentration 1 of 0.5% by weight. The composition of the rhamnolipid fractions is listed in the following table:
    [00109] A composition according to the invention, E09-S6, which was obtained by fermentation, pure diRL-C10C10 and a commercially available product from Jeneil were investigated.
    [00110] The measurements regarding the foaming capacity were carried out at a temperature of 30 ° C with a liquid volume of 300 ml and a stirring speed of 1500 rpm.
    [00111] Figure 1 shows that the foaming capacity of E09 S6 was considerably better than those of the other samples, that is, the maximum foam volume was obtained more quickly.
    权利要求:
    Claims (11)
    [0001]
    1. Mixture composition comprising rhamnolipids, characterized by the fact that the mixture composition comprises: 51% by weight to 95% by weight of diRL-C10C10 and 0.5% by weight to 9% by weight of monoRL-Cl0C10, where weight percentages refer to the sum of all rhamnolipids present, with the proviso that the weight ratio of dl-rhamnolipids to mono-rhamnolipids is greater than 91: 9, preferably greater than 97: 3, particularly preferably greater than 98: 2.
    [0002]
    2. Mixture composition, according to the claim characterized by the fact that the mixture composition comprises: 0.5% by weight to 15% by weight of diRL-Cl0C12: 1 where the weight percentages refer to the sum of all rhamnolipids present.
    [0003]
    Mixture composition according to either of claims 1 or 2, characterized in that the mixture composition comprises: 0.5 to 25% by weight of diRL-C10C12, where the weight percentages refer to sum of all rhamnolipids present.
    [0004]
    Mixture composition according to any one of claims 1 to 3, characterized in that the mixture composition comprises: 0.1% by weight to 5% by weight of monoRL-Cl0C12 and / or, preferably, and 0.1-10% by weight at 5% by weight of monoRL-Cl0C12: 1, where the weight percentages refer to the sum of all rhamnolipids present.
    [0005]
    5. Composition of the mixture according to claim 1 / characterized by the fact that it comprises: 0.5% by weight to 15% by weight of diRL-Cl0C12: 1, 0.5 to 25% by weight of diRL-C10C12, 0.1-0 by weight to 5% by weight of monoRL-Cl0C12 and 0.1% by weight to 5% by weight of monoRL-Cl0C12: 1, where the weight percentages refer to the sum of all rhamnolipids present .
    [0006]
    Mixture composition according to any one of claims 1 to 5, characterized by the fact that the mixture composition comprises: 0% by weight to 5% by weight of diRLClO, where the weight percentages refer to the sum of all rhamnolipids present.
    [0007]
    Mixture composition according to any one of claims 1 to 6, characterized in that the mixture composition comprises at least 60% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight. weight of rhamnolipids, where the weight percentages refer to the dry substance of the total composition of the mixture.
    [0008]
    8. Process characterized by the fact that it comprises the steps of the process: Ia) to supply a puttified Pseudomonas cell that has been genetically modified in such a way that it overexpresses in each case at least one gene from the rhlA, rhlB and rhlC group, in that the selected genes are those of P. aeruginosa, lia) contacting the cell with a medium comprising a carbon source, Illa) cultivating the cell under conditions that allow the cell to form rhamnolipid from a carbon source and IVa) optionally isolating the formed rhamnolipids, characterized by the fact that the rhlC gene is more overexpressed compared to rhlB.
    [0009]
    9. Process, characterized by the fact that it comprises the steps of the process: Ib) to supply a Pseudomonas putida cell that has been genetically modified in such a way that in each case it has at least one exogenous gene from the rhlA, rhlB and rhlC group of which at least one is under the control of an inducible promoter, Ilb) bringing the cell according to the invention into contact with and culturing it with a medium comprising at least one carbon source while reaching a cell density of 1-30 g of dry cell mass per L of fermentation broth, Illb) to induce at least one inducible promoter and to cultivate the cell under conditions that allow the cell to form a rhamnolipid from the carbon source and IVb) optionally isolate the formed rhamnolipids.
    [0010]
    10. Use of a blend composition as defined in any of claims 1 to 7, characterized by the fact that it is for the production of formulations.
    [0011]
    11. Use of a mixture composition defined in any one of claims 1 to 7, characterized by the fact that it is for cleaning a surface.
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    同族专利:
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    EP2786743B1|2019-05-22|
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    CA2847899A1|2014-10-02|
    CN104095765A|2014-10-15|
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    BR102014007948A2|2015-12-08|
    JP2014201589A|2014-10-27|
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    法律状态:
    2015-12-08| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2017-08-15| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-10| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2020-05-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/04/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE201310205756|DE102013205756A1|2013-04-02|2013-04-02|Mixture composition containing rhamnolipids|
    DE102013205756.3|2013-04-02|
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