20221-26-5Relevant academic research and scientific papers
Cis-trans isomerization of polyunsaturated fatty acid residues in phospholipids catalyzed by thiyl radicals
Ferreri,Costantino,Perrotta,Landi,Mulazzani,Chatgilialoglu
, p. 4459 - 4468 (2001)
Phospholipids containing trans-unsaturated fatty acid residues are the major products of the thiyl radical attack on L-α-phosphatidylcholine from soybean lecithin in homogeneous solution or in liposomes (LUVET). Thiyl radicals act as the catalyst for the cis-trans isomerization, and the number of catalytic cycles depends on the reaction conditions. The presence of ～0.2 mM oxygen does not influence the reaction outcome but accelerates the efficiency of cis-trans isomerization in homogeneous solution. Under these conditions, the PUFA peroxidation is found to be unimportant. A detailed study of the isomerization of methyl linoleate including product studies indicates the formation of a small amount of conjugated dienes that act as inhibitors. Indeed, all-trans-retinol substantially retarded the isomerization process.
The Reaction of Thiyl Radical with Methyl Linoleate: Completing the Picture
Chatgilialoglu, Chryssostomos,Ferreri, Carla,Guerra, Maurizio,Samadi, Abdelouahid,Bowry, Vincent W.
, p. 4704 - 4714 (2017)
Cis lipids can be converted by thiols and free radicals into trans lipids, which are therefore a valuable tell-tale for free radical activity in the cell’s lipidome. Our previous studies have shown that polyunsaturated lipids are isomerized by alkanethiyl radicals (S?) in a cycle propagated by reversible double-bond addition and terminated by radical H-abstraction from the lipid. A critical flaw in this picture has long been that the reported lipid abstraction rate from radiolysis studies is faster than addition-isomerization, implying that the “cycle” must be terminating faster than it is propagating! Herein, we resolved this longstanding puzzle by combining a detailed product analysis, with reinvestigation of the time-resolved kinetics, DFT calculations of the indicated pathways, and reformulation of the radical-stasis equations. We have determined thiol-coupled products in dilute solutions arise mainly from addition to the inside position of the bisallylic group, followed by rapid intramolecular H? transfer, yielding allylic radicals (LZZ + S? ? SL? → SL′?) that are slowly reduced by thiol (SL′? + SH → SL′H + S?). The first-order grow-in rate of the L-H? signal (kexp280nm) may therefore be dominated by the addition-H-translocation rather than slower direct H?-abstraction. Steady-state kinetic analysis of the new mechanism is consistent with products and the rates and trends for polyunsaturated fatty acids (PUFAs), monounsaturated fatty acids (MUFAs), and mixtures, with and without physiological [O2]. Implications of this new paradigm for the thiol-ene reactivity fall in an interdisciplinary research area spanning from synthetic applications to metabolomics.
Branched alkyl sulfonate anionic surfactant and preparation process thereof
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Paragraph 0090-0091, (2021/02/10)
The invention discloses a branched alkyl sulfonate anionic surfactant and a preparation process thereof, and belongs to the field of fine chemical surfactants. The method comprises the steps of (1) conducting a esterification carboxyl-terminated reaction, specifically, catalyzing oleic acid or linoleic acid and fatty alcohol to be subjected to esterification reaction by adopting organic acid as acatalyst to prepare an alkyl oleate or alkyl linoleate compound; and (2) conducting a double bond addition sulfonation reaction, specifically, in the presence of the catalyst, carrying out sulfonationreaction with the alkyl oleate compound or the alkyl linoleate compound obtained in the step (1) by taking low-carbon alcohol and deionized water as solvents and sodium hydrogen sulfite as a sulfonation reagent to prepare the branched alkyl sulfonate anionic surfactant. The synthesized branched alkyl sulfonate anionic surfactant product can effectively reduce the surface tension of an aqueous solution, and is good in solubility, large in initial foaming amount, high in defoaming speed and excellent in surfactant performance. The method has the advantages of simple process operation, few sidereactions, energy saving and environmental protection.
Metathesis of renewable polyene feedstocks – Indirect evidences of the formation of catalytically active ruthenium allylidene species
Kovács, Ervin,Sághy, Péter,Turczel, Gábor,Tóth, Imre,Lendvay, Gy?rgy,Domján, Attila,Anastas, Paul T.,Tuba, Róbert
supporting information, p. 213 - 217 (2017/09/12)
Cross-metathesis (CM) of conjugated polyenes, such as 1,6-diphenyl-1,3,5-hexatriene (1) and α-eleostearic acid methyl ester (2) with several olefins, including 1-hexene, dimethyl maleate and cis-stilbene as model compounds has been carried out using (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)-dichloro(o-isopropoxyphenylmethylene)ruthenium (Hoveyda-Grubbs 2nd generation, HG2) catalyst. The feasibility of these reactions is demonstrated by the observed high conversions and reasonable yields. Thus, regardless of the relatively low electron density, =CH–CH= conjugated units of molecules, including compound 2 as a sustainable, non-foodstuff source, can be utilized as building blocks for the synthesis of various value-added chemicals via olefin metathesis. DFT-studies and the product spectrum of the self-metathesis of 1,6-diphenyl-1,3,5-hexatriene suggest that a Ru η1-allylidene complex is the active species in the reaction.
Antiproliferative activity of synthetic fatty acid amides from renewable resources
Dos Santos, Daiane S.,Piovesan, Luciana A.,D'Oca, Caroline R. Montes,Hack, Carolina R. Lopes,Treptow, Tamara G.M.,Rodrigues, Marieli O.,Vendramini-Costa, Débora B.,Ruiz, Ana Lucia T.G.,De Carvalho, Jo?o Ernesto,D'Oca, Marcelo G. Montes
, p. 340 - 347 (2015/02/02)
In the work, the in vitro antiproliferative activity of a series of synthetic fatty acid amides were investigated in seven cancer cell lines. The study revealed that most of the compounds showed antiproliferative activity against tested tumor cell lines, mainly on human glioma cells (U251) and human ovarian cancer cells with a multiple drug-resistant phenotype (NCI-ADR/RES). In addition, the fatty methyl benzylamide derived from ricinoleic acid (with the fatty acid obtained from castor oil, a renewable resource) showed a high selectivity with potent growth inhibition and cell death for the glioma cell line - the most aggressive CNS cancer.
ADDUCTS OF LEVULINIC DERIVATIVES WITH EPOXIDIZED FATTY ACID ESTERS AND USES THEREOF
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Page/Page column 19-20, (2010/11/27)
The present disclosure relates to methods of preparation of compounds resulting from the reaction of levulinic esters and epoxidized unsaturated fatty acid esters. The compounds are useful as renewable biomass-based plasticizers for a variety of polymers. Mono-, di- and tri-ketal adducts formed in a reaction between alkyl esters of levulinate and epoxidized unsaturated fatty acid esters derived from vegetable oils are also disclosed.
Large-scale synthesis of methyl cis-9, trans-11-octadecadienoate from methyl ricinoleate
Berdeaux,Christie,Gunstone,Sebedio
, p. 1011 - 1015 (2007/10/03)
The conjugated linoleic acid methyl cis-9, trans-11-octadecadienoate has been prepared on a large scale from methyl ricinoleate. Methyl ricinoleate was purified from castor esters by a partition method. It was converted to the mesylate, which was reacted with a base (1,8-diazabicyclo[5.4.0]-undec-7-ene) to give a product that contained 66% of the desired ester. Two urea crystallizations produced a product containing 83% methyl cis-9,trans-11-octadecadienoate, the identity of which was confirmed by gas chromatography linked to mass spectrometry and by Fourier transform infrared spectroscopy. The remaining impurities were methyl cis-9,cis-11- and cis-9-,trans-12-octadecadienoate.
Synthesis, Characterisation, and Transformations of a Lipid Cyclic Peroxide
Bascetta, Emanuele,Gunstone, Frank D.,Scrimgeour, Charles M. S.
, p. 2199 - 2206 (2007/10/02)
Photosensitised oxidation of (9E,11E)-methyl octadeca-9,11-dienoate gave an unsaturated cyclic peroxide (epidioxide) in high yield.This was characterised spectroscopically.The peroxide underwent facile rearrangement to a furanoid ester under a variety of reaction conditions.Catalytic reduction of the unsaturated peroxide cleaved the O-O bond.Bromination and epoxidation gave dibromo and epoxy esters respectively with the peroxide group still intact.
An Electron Spin Resonance Study of Fatty Acids and Esters. Part 1. Hydrogen Abstraction from Olefinic and Acetylenic Long-chain Esters
Bascetta, Emanuele,Gunstone, Frank D.,Walton, John C.
, p. 603 - 614 (2007/10/02)
The radicals generated from unsaturated fatty acid esters by hydrogen abstraction with photochemically formed t-butoxyl radicals have been investigated by e.s.r. spectroscopy.The substituted allyl and pentadienyl radicals generated from monoenoic and dienoic esters were conformationally stable under the conditions of the experiments.The main species observed on hydrogen-abstraction from monoynoic esters were substituted propynyl radicals, and the same radical type was generated from diynoic esters with more than one methylene unit separating the triple bonds.Substituted penta-1,4-diynyl and penta-1,3-diynyl radicals were identified on hydrogen-abstraction from methylene-interrupted and conjugated diynoic esters.Hydrogen abstraction from triacylglycerols containing one or more double bonds was also examined.Most of the unsaturated esters also gave rise to secondary radicals produced by hydrogen-abstraction from the chain methylene groups.From the measured concentrations of the secondary and delocalised radicals the following approximate relative rates of hydrogen-abstraction by t-butoxyl radicals from the different sites were obtained: secondary: propynylic: allylic: bisallylic = 1:18:36:116 at 293 K.
