- P450Jα: A New, Robust and α-Selective Fatty Acid Hydroxylase Displaying Unexpected 1-Alkene Formation
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Oxyfunctionalization of fatty acids (FAs) is a key step in the design of novel synthetic pathways for biobased/biodegradable polymers, surfactants and fuels. Here, we show the isolation and characterization of a robust FA α-hydroxylase (P450Jα) which catalyses the selective conversion of a broad range of FAs (C6:0-C16:0) and oleic acid (C18:1) with H2O2 as oxidant. Under optimized reaction conditions P450Jα yields α-hydroxy acids all with >95 % regioselectivity, high specific activity (up to 15.2 U mg?1) and efficient coupling of oxidant to product (up to 85 %). Lauric acid (C12:0) turned out to be an excellent substrate with respect to productivity (TON=394 min?1). On preparative scale, conversion of C12:0 reached 83 % (0.9 g L?1) when supplementing H2O2 in fed-batch mode. Under similar conditions P450Jα allowed further the first biocatalytic α-hydroxylation of oleic acid (88 % conversion on 100 mL scale) at high selectivity and in good yields (1.1 g L?1; 79 % isolated yield). Unexpectedly, P450Jα displayed also 1-alkene formation from shorter chain FAs (≤C10:0) showing that oxidative decarboxylation is more widely distributed across this enzyme family than reported previously.
- Armbruster, Julia,Steinmassl, Mathilde,Müller Bogotá, Christina A.,Berg, Gabriele,Nidetzky, Bernd,Dennig, Alexander
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p. 15910 - 15921
(2020/10/29)
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- Preparative Asymmetric Synthesis of Canonical and Non-canonical α-amino Acids Through Formal Enantioselective Biocatalytic Amination of Carboxylic Acids
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Chemical and biocatalytic synthesis of non-canonical α-amino acids (ncAAs) from renewable feedstocks and using mild reaction conditions has not efficiently been solved. Here, we show the development of a three-step, scalable and modular one-pot biocascade for linear conversion of renewable fatty acids (FAs) into enantiopure l-α-amino acids. In module 1, selective α-hydroxylation of FAs is catalyzed by the P450 peroxygenase P450CLA. By using an automated H2O2 supplementation system, efficient conversion (46 to >99%; TTN>3300) of a broad range of FAs (C6:0 to C16:0) into valuable α-hydroxy acids (α-HAs; >90% α-selective) is shown on preparative scale (up to 2.3 g L?1 isolated product). In module 2, a redox-neutral hydrogen borrowing cascade (alcohol dehydrogenase/amino acid dehydrogenase) allowed further conversion of α-HAs into l-α-AAs (20 to 99%). Enantiopure l-α-AAs (e.e. >99%) including the pharma synthon l-homo-phenylalanine can be obtained at product titers of up to 2.5 g L?1. Based on renewables and excellent atom economy, this biocascade is among the shortest and greenest synthetic routes to structurally diverse and industrially relevant ncAAs. (Figure presented.).
- Dennig, Alexander,Blaschke, Fabio,Gandomkar, Somayyeh,Tassano, Erika,Nidetzky, Bernd
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supporting information
(2019/02/09)
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- Preparative Asymmetric Synthesis of Canonical and Non-canonical a-amino Acids through Formal Enantioselective Biocatalytic Amination of Carboxylic Acids
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Chemical and biocatalytic synthesis of non-canonical a-amino acids (ncAAs) from renewable feedstocks and using mild reaction conditions has not efficiently been solved. Here, we show the development of a three-step, scalable and modular one-pot biocascade for linear conversion of renewable fatty acids (FAs) into enantiopure l-a-amino acids. In module 1, selective a-hydroxylation of FAs is catalyzed by the P450 peroxygenase P450CLA. By using an automated H2O2 supplementation system, efficient conversion (46 to >99%; TTN>3300) of a broad range of FAs (C6:0 to C16:0) into valuable a-hydroxy acids (a-HAs; >90% a-selective) is shown on preparative scale (up to 2.3 gL1 isolated product). In module 2, a redox-neutral hydrogen borrowing cascade (alcohol dehydrogenase/amino acid dehydrogenase) allowed further conversion of a-HAs into l-a-AAs (20 to 99%). Enantiopure l-a-AAs (e.e. >99%) including the pharma synthon l-homo-phenylalanine can be obtained at product titers of up to 2.5 gL1. Based on renewables and excellent atom economy, this biocascade is among the shortest and greenest synthetic routes to structurally diverse and industrially relevant ncAAs.
- Dennig, Alexander,Blaschke, Fabio,Gandomkar, Somayyeh,Tassano, Erika,Nidetzky, Bernd
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supporting information
p. 1348 - 1358
(2019/10/28)
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- Synthesis of 6-Hydroxysphingosine and α-Hydroxy Ceramide Using a Cross-Metathesis Strategy
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(Chemical Equation Presented) In this paper, a new synthetic route toward 6-hydroxysphingosine and α-hydroxy ceramide is described. The synthesis employs a cross-metathesis to unite a sphingosine head allylic alcohol with a long-chain fatty acid alkene that also bears an allylic alcohol group. To allow for a productive CM coupling, the sphingosine head allylic alcohol was protected with a cyclic carbonate moiety and a reactive CM catalyst system, consisting of Grubbs II catalyst and CuI, was employed.
- Wisse, Patrick,De Geus, Mark A. R.,Cross, Gen,Van Den Nieuwendijk, Adrianus M. C. H.,Van Rooden, Eva J.,Van Den Berg, Richard J. B. H. N.,Aerts, Johannes M. F. G.,Van Der Marel, Gijsbert A.,Codée, Jeroen D. C.,Overkleeft, Herman S.
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p. 7258 - 7265
(2015/07/27)
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- Synthesis of phalluside-1 and Sch II using 1,2-metallate rearrangements
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(4E,8E,10E)-9-Methyl-4,8,10-sphingatrienine, a core component of marine sphingolipids, was synthesised for the first time using a copper(i)-mediated 1,2-metallate rearrangement of a lithiated glycal as a key step. It was converted to phalluside-1, a cereb
- Black, Fiona J.,Kocienski, Philip J.
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supporting information; experimental part
p. 1188 - 1193
(2010/06/15)
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- Personal care compositions comprising solid particles enterapped in a gel network
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The present invention relates to a personal care composition comprising a three dimensional gel polymeric network comprising: a. a polymer; b. one or more solid particles that are entrapped within said polymer during polymerization of said polymer; and c. a solvent in which said polymer is dispersed. Another embodiment further includes at least one second colorant that is substantially similar to an at least one first colorant which is a solid particle and wherein said second colorant is dispersed within said composition but is not entrapped in said polymer and is separate and distinct from said network. In contrast, a third embodiment allows for the at least one second colorant to be substantially different from the at least one first colorant.
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- COSMETIC COMPOSITIONS CONTAINING A SILOXANE ELASTOMER
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A skin treatment composition is provided which includes a crosslinked non-emulsifying siloxane elastomer, a volatile siloxane and at least 50% by weight of water. Inclusion of the elastomer provides a unique liquid/powdery feel when rubbed into the skin.
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- Cosmetic compositions
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The present invention relates to pigmented emulsion cosmetic compositions containing emulsifying silicone elastomers that provide a natural appearance to the skin upon application. In particular, these cosmetic compositions are formulated such that agglomeration of the pigment upon application to the skin is minimized.
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- Cosmetic compositions
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A skin treatment composition is provided which includes a crosslinked siloxane elastomer gel of specific yield point, a skin-conditioning agent, a volatile siloxane and water. Inclusions of the select elastomers provide improved uniform distribution of the pigments.
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- Anhydrous cosmetic compositions
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An anhydrous skin treatment composition is provided which includes a crosslinked emulsifying siloxane elastomer, at least 20% humectant and a volatile siloxane. Inclusion of the elastomer provides a non-traditional smooth/silky feel to the skin upon application with a non-draggy rub in.
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- Cosmetic compositions
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The invention relates to cosmetic compositions comprising a combination of non-emulsifying and emulsifying crosslinked siloxane elastomers.
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- Anhydrous cosmetic compositions
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An anhydrous skin treatment composition is provided which includes a crosslinked siloxane elastomer gel of specific yield point, a skin conditioning agent and a volatile siloxane. Inclusions of the select elastomers provide improved uniform distribution of the pigments.
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- Cosmetic compositions
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The invention relates to cosmetic compositions comprising a combination of non-emulsifying and emulsifying crosslinked siloxane elastomers.
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- Powdered cosmetic compositions containing silicone elastomers
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A cosmetic powder is provided which includes a crosslinked non-emulsifying siloxane elastomer, a powdered inorganic material and a skin treatment agent. Inclusion of the elastomer allows for the coupling of water as well as water soluble salts into the cosmetic powder.
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- Role of the hydrophobic moiety of tumor promoters. Synthesis and activity of 2-alkylated benzolactams
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The size and position of a hydrophobic moiety on a benzolactam skeleton, which reproduces the active conformation and biological activity of teleocidins, play an important role in the appearance of the activity. Compounds with alkyl groups of various sizes and shapes at the 2-position of benzolactam were synthesized. Structure-activity results indicate that a hydrophobic substituent at the C-2 position plays a critical role in the appearance of biological activities, as in the case of substitution at C-9.
- Endo, Yasuyuki,Yokoyama, Akihiro
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- Synthesis and study of a lipophilic alpha-keto amide inhibitor of pancreatic lipase.
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[reaction: see text] A lipophilic alpha-keto amide, inhibitor of pancreatic lipase, was synthesized using a lipidic 2-amino alcohol as backbone. The chiral key intermediate 2-(tert-butyloxycarbonylamino)-D-undecen-5-ol was synthesized starting from D-glutamic acid. The inhibitor formed a stable monomolecular film at the air/water interface as shown by a force/area curve. Inhibition studies using the monomolecular film technique with mixed films of 1,2-dicaprin containing variable proportions of the inhibitor showed a 50% decrease in lipase activity at a 0.14 molar fraction.
- Chiou,Markidis,Constantinou-Kokotou,Verger,Kokotos
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p. 347 - 350
(2007/10/03)
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- Enantioselective α-hydroperoxylation of long-chain fatty acids with crude enzyme of marine green alga Ulva pertusa
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When palmitic acid was incubated with crude enzyme of marine green alga Ulva pertusa, (R)-2-hydroperoxyhexadecanoic acid was formed in high enantiomeric purity (>99%ee).
- Akakabe,Matsui,Kajiwara
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p. 1137 - 1140
(2007/10/03)
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- Anhydrous cosmetic compositions
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A skin treatment composition is provided which includes a crosslinked non-emulsifying siloxane elastomer, a skin conditioning agent, a volatile siloxane and no more than 5% water. Hydrocarbons such as petrolatum and polyols such as glycerin are the preferred skin conditioning agents. Inclusion of the elastomer provides a non-traditional smooth/silky feel to the skin upon application with a non-draggy rub in.
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- Anhydrous cosmetic composition with ceramides for firming skin
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A method and cosmetic composition for improving skin firmness are provided through an anhydrous composition including a hydrophobic carrier which may be a silicone or hydrocarbon for delivering an effective amount of a ceramide formed of a sphingoid base linked through an amide to a 2-hydroxycarboxylic C2-C30group.
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- Synthesis of optically active α-hydroxy acids by kinetic resolution through lipase-catalyzed enantioselective acetylation
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The lipase-catalyzed acetylation of a broad spectrum of racemic 2-hydroxy acids 1 to their 2-acetoxy acids 2 was shown to proceed with high enantioselectivity. Thus, the microbial lipases, in particular from Candida antarctica and Burkholderia species, are convenient biocatalysts for the synthesis of optically active 2-hydroxy acids in excellent enantioselectivity (ee values up to 99%). The absolute configurations of the 2-hydroxy acids 1 were assigned by comparison of the gas-chromatographic data with that of literature-known reference compounds, or by means of the exciton-coupled circular dichroism method (ECCD) on their bichromophoric 2-naphthoate 9-anthrylmethyl derivatives 3. These results establish that (S)-2-hydroxy acids 1 were preferentially acetylated by microbial lipases.
- Adam, Waldemar,Lazarus, Michael,Schmerder, Alexandra,Humpf, Hans-Ulrich,Saha-M?ller, Chantu R.,Schreier, Peter
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p. 2013 - 2018
(2007/10/03)
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- Cosmetic compositions for reducing or preventing signs of cellulite
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The invention is directed to increasing the strength and firmness of the skin and reducing the signs of cellulite. The inventive method includes applying to the skin a composition that includes inositol phosphate, particularly phytic acid and its salts, in a cosmetically acceptable carrier.
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- Enantioselective α hydroxylation of carboxylic acids with molecular oxygen catalyzed by the α oxidation enzyme system of young pea leaves (Pisum sativum): A substrate selectivity study
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The substrate selectivity of the α oxidation of carboxylic acids 1 by crude homogenate of young pea leaves was investigated. Saturated fatty acids with 7 to 16 carbon atoms and oleic acid were transformed to the enantiomerically pure (R)-2-hydroxy acids 2 in the presence of molecular oxygen.
- Adam, Waldemar,Lazarus, Michael,Saha-Moeller, Chantu R.,Schreier, Peter
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p. 2287 - 2292
(2007/10/03)
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- Cerebrosides from Fomitopsis pinicola (Sw. Ex Fr.) Karst.
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A cerebroside fraction was obtained from the bruit bodies of fomitopsis pinicola using column chromatography and then separated into six compounds by reversed-phase HPLC.The sugar component of all cerebrosides was D-glucose.The major fatty acids were 2-hydroxyfatty acids (C14-C18), the long chain base was identified as 9-methyl-C18-4,8-sphingadienine which is widely distributed in fungi and reported to be essential for the fruit-inducing activity of fungi.Based on degradation studies, fast atom bombardment mass spectrometry, and different 1H and 13C NMR investigations, the structure of the main cerebroside (1) was determined to be (4E,8E,2S,3R,2'R)-N-2'-hydroxypalmityl-1-O-β-D-glucopyranosyl-9-methyl-4,8-sphingadienine. - Keywords: Cerebroside; Glycolipid; Fomitopsis pinicola; 1H and 13C NMR
- Striegler, S.,Haslinger, E.
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p. 755 - 762
(2007/10/03)
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- Spicamycin derivatives and their use as anticancer agents
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Spicamycin derivative represented by the formula (I) or a salt thereof: STR1 wherein R represents specific diverse substituents, for example, a linear alkadienyl having from 11 to 13 carbon atoms, and R1 and R2 respectively represent H or OH. Examples of specific compounds are 6-[4'-N-(N'-trans,trans 2,4-tridecadienoylglycyl)spicaminyl-amino]purine, and 6-[4'-N-(N'-trans,trans-2,4 dodecadienyoly glycyl) spicaminyl-amino]purine. Comopunds according to this invention are useful as a pharmaceutical for inhibition of a tumor, for example, human colon cancer.
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- Sphingolipids and glycerolipids. IV. Syntheses and ionophoretic activities of several analogues of soya-cerebroside II, a calcium ionophoretic sphingoglycolipid isolated from soybean
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For examination of the structure-activity relationship five analogues [(2'R)-2'-hydroxypalmitoyl (3), palmitoyl (4), (2'S)-2'-hydroxypalmitoyl (5), β-D-galactosyl (6), and 8,9-dihydro (7) relevancies] of soya-cerebroside II (2), which is a calcium ionopho
- Shibuya,Kurosu,Minagawa,Katayama,Kitagawa
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p. 1534 - 1544
(2007/10/02)
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- ENZYMATIC FORMATION OF (2R)-HYDROXY- AND 2-OXO-HEXADECANOIC ACID IN ULVA PERTUSA AND PORPHYRA SP.
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(2R)-Hydroxy-hexadecanoic acid and 2-oxo-hexadecanoic acid have been isolated for the first time from marine algae (Ulva pertusa and Porphyra sp.).The two acids were shown to be formed enzymatically from palmitic acid (16:0) using palmitic acid.
- Kajiwara, Tadahiko,Kashibe, Masanori,Matsui, Kenji,Hatanaka, Akikazu
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p. 193 - 195
(2007/10/02)
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- New potential immunoenhancing compounds. Synthesis and pharmacological evaluation of new long-chain 2-amido-2-deoxy-D-glucose derivatives
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A series of long-chain fatty acids and the corresponding 2-hydroxy, 2-oxo, 3-hydroxy acid glucosamides were evaluated as immunomodulating compounds. In a preliminary screening, 2-[(2-ethoxycarbonyloxy)tetradecanoyl-amino]-2-deoxy-D-glucose (2b) and 2-(3-hydroxydodecanoyl-amino)-2-deoxy-D-glucose (5a) resulted to be the most effective in enhancing the glucosamine activity. The findings of in vitro-ex vivo tests (unidirectional mixed lymphocyte culture reaction and primary antibody production) and in vivo tests (delayed type hypersensitivity, protection against bacterial or fungal infection and against Sarcoma 180 or Lewis lung carcinoma transplants) were very encouraging and allowed to assume for the two substances a protective activity, presumably through the ability of activating phagocytic and NK cells.
- Valcavi,Albertoni,Brandt,Corsi,Farina,Foresta,Pascucci,Ramacci
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p. 1190 - 1195
(2007/10/02)
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- Synthesis and Biological Activity of the Isomers and Analogs of (4E,8E,2S,3R,2'R)-N-2'-Hydroxyhexadecanoyl-9-methyl-4,8-sphingadienine, the Ceramide Portion of the Fruiting-inducing Cerebroside in a Basidiomycete Schizophyllum commune
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The title compounds were synthesized by employing 2-aminohexadecanoic acid and serine as the chiral sources, and served for an assay of fruiting-inducing activity on Schizophyllum commune.The structure-bioactivity relationship among closely related synthetic ceramides is discussed.
- Funaki, Yuji,Kawai, Genshiro,Mori, Kenji
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p. 615 - 624
(2007/10/02)
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- SYNTHESIS OF (4E,8E,2S,3R,2'R)-N-2'-HYDROXYHEXADECANOYL-9-METHYL-4,8-SPHINGADIENINE, THE CERAMIDE PORTION OF THE FRUITING-INDUCING CEREBROSIDE IN A BASIDIOMYCETE SCHIZOPHYLLUM COMMUNE, AND ITS (2R,3S)-ISOMER
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A synthesis of the natural enantiomer as well as its diastereomer of the title compound was accomplished, confirming the structure proposed for the fruiting-inducing cerebroside of Schizophyllum commune.
- Mori, Kenji,Funaki, Yuji
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p. 2369 - 2378
(2007/10/02)
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- SYNTHESIS OF (4E,8E,2S,3R,2'R)-N-2'-HYDROXYHEXADECANOYL-1-O-β-D-GLUCOPYRANOSYL-9-METHYL-4,8-SPHINGADIENINE, THE FRUITING-INDUCING CEREBROSIDE IN A BASIDIOMYCETE SCHIZOPHYLLUM COMMUNE
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The title compound was synthesized by employing (R)-2-aminohexadecanoic acid, D-glucose and (S)-serine as the chiral sources, and the synthetic sample was found to be chemically and biologically identical with the fruiting-inducing cerebroside isolated fr
- Mori, Kenji,Funaki, Yuji
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p. 2379 - 2386
(2007/10/02)
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- Synthesis of Long Chain Substituted cis- and trans-2-Trichloromethyldioxolanones.
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Reaction of chloral hydrate with α-hydroxy derivatives of palmitic (Ia), stearic (Ib) and behenic (Ic) acids gave the corresponding cis-2-trichloromethyldioxolanones (IIa,b,c) and trans-2-trichloromethyldioxolanones (IIIa,b,c), yields being ca. 50percent for each reaction product.The structures of the individual reaction products were established clearly by elemental analysis as well as by spectral studies.
- Mukarram, Mohammad,Ahmad, Ishtiaque,Ahmad, Mashood
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p. 1949 - 1962
(2007/10/02)
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