Renewable Fatty Acids Research Articles

Production of ω-hydroxyundec-9-enoic acid and n-heptanoic acid from ricinoleic acid by recombinant Escherichia coli-based biocatalyst

ω-Hydroxyundec-9-enoic acid and n-heptanoic acid are valuable building blocks for the production of flavors and antifungal agents as well as bioplastics such as polyamides and polyesters. However, a biosynthetic process to allow high productivity and product yield has not been reported. In the present study, we engineered an Escherichia coli-based biocatalytic process to efficiently produce ω-hydroxyundec-9-enoic acid and n-heptanoic acid from a renewable fatty acid (i.e., ricinoleic acid). Expression systems for catalytic enzymes (i.e., an alcohol dehydrogenase of Micrococcus luteus, a Baeyer–Villiger monooxygenase of Pseudomonas putida KT2440, an esterase of Pseudomonas fluorescens SIK WI) and biotransformation conditions were investigated. Biotransformation during stationary growth phase of recombinant E. coli in a bioreactor allowed to produce ω-hydroxyundec-9-enoic acid and n-heptanoic acid at a rate of 3.2mM/h resulting in a final product concentration of ca. 20mM. The total amount of ω-hydroxyundec-9-enoic acid and n-heptanoic acid produced reached 6.5g/L (4.0g/L of ω-hydroxyundec-9-enoic acid and 2.5g/L of n-heptanoic acid). These results indicate that the high value carboxylic acids ω-hydroxyundec-9-enoic acid and n-heptanoic acid can be produced from a renewable fatty acid via whole-cell biotransformation.

Hydrothermal Catalytic Cracking of Fatty Acids with HZSM-5

We explored the hydrothermal cracking of palmitic acid by HZSM-5 zeolite in a batch reactor. The major liquid products were aromatic hydrocarbons (e.g., xylenes, toluene) and alkanes (e.g., 2-methyl-pentane, heptane). The major gaseous products were CO and CO2, but appreciable yields of propane and butane were also obtained. The effects of batch holding time, temperature, hydrogen pressure, and water density on product yields were elucidated. Total yields of gas and liquid products exceeding 90 wt % are available at reaction conditions of 400 °C, 180 min, and either with no added H2 and a water density of 0.1 g/mL or less or with added H2 and a water density of 0.15 g/mL. The activation energy for palmitic acid disappearance is 31 ± 1 kJ/mol. The zeolite catalyst undergoes some modest structural changes under the hydrothermal reaction conditions employed, but the catalyst can be regenerated by controlled oxidation to remove coke and calcination to restore the structure. These results demonstrate the technical feasibility of using HZSM-5 under hydrothermal conditions to produce valuable chemicals from renewable fatty acid feedstocks.

Synthesis and antimycobacterial activity of isoniazid derivatives from renewable fatty acids

This work describes the synthesis of a series of fatty acid hydrazide derivatives of isoniazid (INH). The compounds were tested against Mycobacterium tuberculosis H37Rv (ATCC 27294) as well as INH-resistant (ATCC 35822 and 1896 HF) and rifampicin-resistant (ATCC 35338) M. tuberculosis strains. The fatty acid derivatives of INH showed high antimycobacterial potency against the studied strains, which is desirable for a pharmaceutical compound, suggesting that the increased lipophilicity of isoniazid plays an important role in its antimycobacterial activity.

Multistep Enzymatic Synthesis of Long‐Chain α,ω‐Dicarboxylic and ω‐Hydroxycarboxylic Acids from Renewable Fatty Acids and Plant Oils

A multistep enzyme catalysis was successfully implemented to produce long-chain α,ω-dicarboxylic and ω-hydroxycarboxylic acids from renewable fatty acids and plant oils. Sebacic acid as well as ω-hydroxynonanoic acid and ω-hydroxytridec-11-enoic acid were produced from oleic and ricinoleic acid.

Multistep Enzymatic Synthesis of Long‐Chain α,ω‐Dicarboxylic and ω‐Hydroxycarboxylic Acids from Renewable Fatty Acids and Plant Oils

Eine mehrstufige Enzymkatalyse überführt erneuerbare Fettsäuren und pflanzliche Öle in langkettige α,ω-Dicarbonsäuren und ω-Hydroxycarbonsäuren. Sebacinsäure sowie ω-Hydroxynonansäure und ω-Hydroxytridec-11-ensäure werden ausgehend von Öl- und Ricinolsäure erzeugt. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

New N-acylamino acids and derivatives from renewable fatty acids: gelation of hydrocarbons and thermal properties

This work reports the synthesis of new fatty N-acylamino acids and N-acylamino esters from the C16:0, C18:0, C18:1, and C18:1(OH) fatty acid families and demonstrates the activity of these compounds as organogel agents. Compounds were heated and dissolved in various solvents (n-hexane, toluene, and gasoline). Only saturated C16:0 and C18:0 derived from alanine were able to form gels in toluene, and saturated C16:0 derived from phenylalanine showed gelation in n-hexane. This is the first evidence that fatty N-acylamino esters and N-acylamino acid derivatives of l-serine and fatty acids C16:0, C18:0, and C18:1 are able to form gels with hexane. This observation confirms the importance of the hydroxyl group in the segment derivative of l-serine in forming good gels.

Acceptorless ruthenium catalyzed dehydrogenation of alcohols to ketones and esters

The ruthenium complex [RuCl2(p-cymene)(IMes)] catalyses the dehydrogenation of alcohols in the presence of K3PO4 as a base and without a hydrogen acceptor. Secondary alcohols are converted to the corresponding ketones whereas primary alcohols are transformed into esters. The dehydrogenation protocol was successfully extended to the dehydrogenation of methyl ricinoleate, a renewable fatty acid methyl ester (FAME), furnishing in high yields the saturated keto-ester methyl 12-oxostearate via a hydrogen borrowing alcohol dehydrogenation–alkene hydrogenation tandem reaction.

Synthesis of polymeric dispersants from renewable DCO fatty acid and their multifunctional behavior in waterborne flat paint

Copolymers containing 50% dehydrated castor oil fatty acids (DCOFA) derived from renewable resources, were synthesized via free radical solvents less polymerization with maleic anhydride, styrene, and butyl acrylate. The copolymer was crosslinked further with polyethylene glycol 400 (PEG 400) to increase its molecular weight. The copolymers with and without crosslinking were then neutralized with sodium hydroxide to prepare polymeric dispersants DFCD1 and DFCD2 respectively in aqueous medium. It was observed via surface-tension measurement that both DFCD1 and DFCD2 transfer to the air–water interface before forming any aggregates, and the ease of forming the aggregates is in the order of DFCD1 > DFCD2. The efficacy of these dispersants was examined in the dispersion of the titanium dioxide pigment and conventional extenders like calcite, talc, and china clay using flow point and zeta potential measurements. The results reveal that DFCD2 improved the dispersing ability for the pigment and extenders studied. The performance of these polymeric dispersants was also studied and compared in waterborne flat paint as a rheology modifier and pigment-dispersing agent. The paint rheology profile and dE data indicate the superior performance of the paint containing dispersant DFCD2. When used in combination with conventional styrene-acrylic latex, DFCD1 and DFCD2 reduced the minimum film-forming temperature (MFFT) of the polymer latex.

Construction of lipoxygenase‐like gene of pseudomonas aeruginosa PA01 into pET‐28A

Naturally occurring renewable fatty acids in vegetable oil and their derivatives are industrial useful compounds. Castor oil contains greater than 85% of its fatty acid component as ricinoleic acid which is an industrial useful compound. Soapstock is a plentiful and inexpensive byproduct of edible oil refining. About 100 million pounds of soapstock are produced in the United States annually. The acidulated soapstock contains about 15% of free fatty acids primarily as oleic and linoleic acids. We are interested in promoting the cash value of soapstock by converting fatty acids in soapstock to value-added hydroxyfatty acid derivatives. We previously reported that Pseudomonas aeruginosa PA01 (PA01) is capable of transforming oleic acid to 10-hydroxy-8(E)-octadecenoic (HOD) and 7, 10-dihydroxy-8(E)- octadecenoic (DOD). The transformation of oleic to HOD and then DOD has been proposed to include lipoxygenase and hydroxylase. Our interest in lipoxygenase-like enzyme stems partly from the fact that HOD is a ricinoleic acid-like compound with potential industrial applications. To search for a putative lipoxygenase gene in PA01, we have previously cloned a lipoxygenase-like gene (accession no. AE004547) by polymerase chain reaction and expressed it in GST expression system. However, the expressed protein was found in insoluble inclusion body. In the present study, we report sucloning of the putative lipoxygenase gene into pET28a. This expression system will result in expression of a His-tagged protein. The protein will be purified and characterized. The research is supported by USDA- CSREES2004-35504-14712 and the University Research Council at Western Illinois University.

Partial purification and characterization of lipoxygenase‐like enzyme from Pseudomonas aeruginosa 2HSP

Naturally occurring renewable fatty acids in vegetable oil and their chemical derivatives are industrial useful compounds. Castor oil contains greater than 85% of its fatty acid component as ricinoleic acid and is an industrial useful compound. About 100 million pounds of soapstock is produced in the United States annually. Soapstock is a plentiful and relatively inexpensive byproduct of edible oil refining. The acidulated soapstock contains about 15% of free fatty acids (primarily as oleic acid and linoleic acid). We are interested in promoting the cash value of soapstock by converting fatty acids in soapstock to value-added hydroxy fatty acid derivatives. We recently isolated a microbe, Pseudomonas aeruginosa 2HSP, which is capable of transforming oleic acid to 10-hydroxy-8 (E)-octadecenoic (HOD) and 7,10-dihydroxy-8 (E)-octadecenoic (DOD). The transformation of oleic acid to HOD and then DOD has been proposed to include lipoxygenase and hydroxylase. However, the enzyme(s) has (have) never been fully explored yet. Our interest in lipoxygenase-like enzyme stems partly from the fact that HOD is a ricinoleic acid-like compound with potential industrial applications. We have partially purified lipoxygenase-like enzyme using ammonium sulfate fractionation and ion exchange chromatography. The enzyme activity was monitored by TLC analysis of the biotransformation products. This work is supported in part from by the grants from USDA CSREES 2004-35504-14712 and the University Research Council from Western Illinois University.