Mono-thioesters and di-thioesters by lipase-catalyzed reactions of a,?-alkanedithiols with palmitic acid or its methyl ester

Weber, Nikolaus; Klein, Emily J.; Vosmann, Klaus; Mukherjee, Kumar D.

doi:10.1007/s00253-004-1604-8

Cited by 14 publications

(7 citation statements)

References 18 publications

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“…In analogy, bacterial PHA synthases catalyzing the biosynthesis of PHA are also capable of utilizing the sulfur analogues of their natural substrates, which are short-and medium-chain-length 3-hydroxyacyl-CoAs, resulting in polythioester biosynthesis (15). Furthermore, it was recently shown that lipases are able to biosynthesize thio wax esters (28) and polythioesters, respectively (8).…”

Section: Discussionmentioning

confidence: 99%

“…Hexadecyl thioesters of palmitic and oleic acids were prepared in vacuo by solvent-free, lipasecatalyzed esterification of the corresponding fatty acid with 1-hexadecanethiol as described previously (25,27). 1-S-Monopalmitoyloctanedithiol and 1,8-S-dipalmitoyloctanedithiol, respectively, were synthesized and purified as described by Weber et al (28).…”

Section: Methodsmentioning

confidence: 99%

“…Injector and detector temperatures were maintained at 380°C. Peaks in GC were assigned by comparison of their retention times with those of known standards (25,28). Peak areas and percentages were calculated using Hewlett-Packard 3365 series GC ChemStation software.…”

Section: Methodsmentioning

confidence: 99%

“…2C). Acylation of the free thiol group of 1-S-monopalmitoyloctanedithiol, which is synthesized in vitro by lipase catalysis (28), by palmitoyl-CoA should result in the formation of 1,8-S-dipalmitoyloctanedithiol. By comparison with synthetic reference substances, all of the putative reaction products mentioned above were identified by autoradiography following TLC separation.…”

Section: Purification Of N-terminal Hismentioning

confidence: 99%

“…Response factors of evaporative light scattering detection were determined for 1-S-monopalmitoyloctanedithiol and 1,8-S-dipalmitoyloctanedithiol by using purified compounds as internal standards, which were prepared as described previously (28). 6 -tagged WS/DGAT.…”

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confidence: 99%

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Thio Wax Ester Biosynthesis Utilizing the Unspecific Bifunctional Wax Ester Synthase/Acyl Coenzyme A:Diacylglycerol Acyltransferase of Acinetobacter sp. Strain ADP1

Uthoff

Stöveken

Weber

et al. 2005

Appl Environ Microbiol

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The bifunctional wax ester synthase/acyl coenzyme A (acyl-CoA):diacylglycerol acyltransferase (WS/DGAT) from Acinetobacter sp. strain ADP1 (formerly Acinetobacter calcoaceticus ADP1) mediating the biosyntheses of wax esters and triacylglycerols was used for the in vivo and in vitro biosynthesis of thio wax esters and dithio wax esters. For in vitro biosynthesis, 5His 6 WS/DGAT comprising an N-terminal His 6 tag was purified from the soluble protein fraction of Escherichia coli Rosetta(DE3)pLysS (pET23a::5His 6 atf). By employing SP-Sepharose high-pressure and Ni-nitrilotriacetic acid fast-protein liquid chromatographies, a 19-fold enrichment with a final specific activity of 165.2 nmol mg of protein ؊1 min ؊1 was achieved by using 1-hexadecanol and palmitoyl-CoA as substrates. Incubation of purified 5His 6 WS/DGAT with 1-hexadecanethiol and palmitoylCoA as substrates resulted in the formation of palmitic acid hexadecyl thio ester (10.4% relative specific activity of a 1-hexadecanol control). Utilization of 1,8-octanedithiol and palmitoyl-CoA as substrates led to the formation of 1-S-monopalmitoyloctanedithiol and minor amounts of 1,8-S-dipalmitoyloctanedithiol (59.3% relative specific activity of a 1-hexadecanol control). The latter dithio wax ester was efficiently produced when 1-S-monopalmitoyloctanedithiol and palmitoyl-CoA were used as substrates (13.4% specific activity relative to that of a 1-hexadecanol control). For the in vivo biosynthesis of thio wax esters, the knockout mutant Acinetobacter sp. strain ADP1acr1⍀Km, which is unable to produce fatty alcohols, was used. Cultivation of Acinetobacter sp. strain ADP1acr1⍀Km in the presence of gluconate, 1-hexadecanethiol, and oleic acid in nitrogen-limited mineral salts medium resulted in the accumulation of unusual thio wax esters that accounted for around 1.19% (wt/wt) of the cellular dry weight and consisted mainly of oleic acid hexadecyl thioester as revealed by gas chromatography-mass spectrometry.Polyhydroxyalkanoic acids (PHA) in bacteria represent the most abundant group of neutral storage lipids, which serve as intracellular carbon and energy storage compounds (23). In addition, triacylglycerols (TAGs) and wax esters also occur as bacterial storage lipids, though at a much lower frequency than in eukaryotic microorganisms (22). Significant TAG accumulation was found, particularly in species belonging to the class Actinomycetes (1), as was reported for the genera Mycobacterium (3), Nocardia, and Streptomyces (2). TAGs are synthesized by the acyl coenzyme A (acyl-CoA):diacylglycerol acyltransferase (DGAT) (13), which catalyzes the esterification of diacylglycerol with long-chain acyl-CoA. Wax esters are oxoesters of primary long-chain fatty alcohols and long-chain fatty acids. Occurrence of wax esters has been frequently reported for various Acinetobacter species (6). Under growthlimiting conditions, Acinetobacter calcoaceticus accumulates wax esters intracellularly as insoluble inclusions. The chemical structure of the wax esters synthesized by A. ca...

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Purification Of N-terminal Hismentioning

confidence: 99%

mentioning

confidence: 99%

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Thio Wax Ester Biosynthesis Utilizing the Unspecific Bifunctional Wax Ester Synthase/Acyl Coenzyme A:Diacylglycerol Acyltransferase of Acinetobacter sp. Strain ADP1

Uthoff

Stöveken

Weber

et al. 2005

Appl Environ Microbiol

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Thioesters as Acyl Donors in Biocatalytic Friedel‐Crafts‐type Acylation Catalyzed by Acyltransferase from Pseudomonas Protegens

2019

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Functionalization of aromatic compounds by acylation has considerable significance in synthetic organic chemistry. As an alternative to chemical Friedel‐Crafts acylation, the C‐acyltransferase from Pseudomonas protegens has been found to catalyze C−C bond formation with non‐natural resorcinol substrates. Extending the scope of acyl donors, it is now shown that the enzyme is also able to catalyze C−S bond cleavage prior to C−C bond formation, thus aliphatic and aromatic thioesters can be used as acyl donors. It is worth to mention that this reaction can be performed in aqueous buffer. Identifying ethyl thioacetate as the most suitable acetyl donor, the products were obtained with up to >99 % conversion and up to 88 % isolated yield without using additional base additives; this represents a significant advancement to prior protocols.

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Enzyme‐Catalyzed Preparation of Aliphatic Polythioester by Direct Polycondensation of Diacid Diester and Dithiol

Katô

Toshima

Matsumura

2006

Macromol. Rapid Commun.

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Summary: Aliphatic dithiol‐diacid type polythioesters were first enzymatically prepared by the direct polycondensation of hexane‐1,6‐dithiol and diacid diesters using the immobilized lipase from Candida antarctica (lipase CA). As a typical example, diethyl sebacate and hexane‐1,6‐dithiol were polymerized using lipase CA in bulk in the presence of molecular sieves 4A to produce the corresponding polythioester with an $\overline M _{\rm w}$ of 10 200 in 90% yield. Both the melting and crystallization temperatures of the produced polythioesters were higher when compared to those of the corresponding polyoxyesters. A higher molecular weight polythioester was produced using lipase in a two‐step procedure, i.e., cyclization with subsequent ring‐opening polymerization.

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Mono-thioesters and di-thioesters by lipase-catalyzed reactions of a,?-alkanedithiols with palmitic acid or its methyl ester

Cited by 14 publications

References 18 publications

Thio Wax Ester Biosynthesis Utilizing the Unspecific Bifunctional Wax Ester Synthase/Acyl Coenzyme A:Diacylglycerol Acyltransferase of Acinetobacter sp. Strain ADP1

Thio Wax Ester Biosynthesis Utilizing the Unspecific Bifunctional Wax Ester Synthase/Acyl Coenzyme A:Diacylglycerol Acyltransferase of Acinetobacter sp. Strain ADP1

Thioesters as Acyl Donors in Biocatalytic Friedel‐Crafts‐type Acylation Catalyzed by Acyltransferase from Pseudomonas Protegens

Enzyme‐Catalyzed Preparation of Aliphatic Polythioester by Direct Polycondensation of Diacid Diester and Dithiol

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