Enzymatic production of zero-trans plastic fat rich in α-linolenic acid and medium-chain fatty acids from highly hydrogenated soybean oil, Cinnamomum camphora seed oil, and perilla oil by lipozyme TL IM.

In the present study, zero-trans α-linolenic acid (ALA) and medium-chain fatty acids (MCFA)-enriched plastic fats were synthesized through enzymatic interesterification reactions from highly hydrogenated soybean oil (HSO), Cinnamomum camphora seed oil (CCSO), and perilla oil (PO). The reactions were performed by incubating the blending mixtures of HSO, CCSO, and PO at different weight ratios (60:40:100, 70:30:100, 80:20:100) using 10% (total weight of substrate) of Lipozyme TL IM at 65 °C for 8 h. After reaction, the physical properties (fatty acids profile, TAG composition, solid fat content, slip melting point, contents of tocopherol, polymorphic forms, and microstructures) of the interesterified products and their physical blends were determined, respectively. Results showed that the fatty acid compositions of the interesterified products and physical blends had no significant changes, while the content of MCFA in both interesterified products and physical blends increased to 8.58-18.72%. Several new types of TAG species were observed in interesterified products (SSL/SLS, PLO/LLS, and OLLn/LnLO/LOLn). It should be mentioned that no trans fatty acids (TFA) were detected in all products. As the temperature increased, the solid fat content (SFC) of interesterified products was obviously lower than that of physical blends. The SFCs of interesterified products (60:40:100, 70:30:100, and 80:20:100, HSO:CCSO:PO) at 25 °C were 6.5%, 14.6%, and 16.5%, respectively, whereas the counterparts of physical blends were 32.5%, 38.5%, and 43.5%, respectively. Meanwhile, interesterified products showed more ß' polymorphs than physical blends, in which ß' polymorph is a favorite form for production of margarine and shortening. Such zero-trans ALA and MCFA-enriched fats may have desirable physical and nutritional properties for shortenings and margarines.

Structure-activity relationships in toll-like receptor 2-agonists leading to simplified monoacyl lipopeptides.

Toll-like receptor 2-agonistic lipopeptides typified by S-[2,3-bis(palmitoyloxy)-(2RS)-propyl]-R-cysteinyl-S-serine (PAM(2)CS) compounds are potential vaccine adjuvants. In continuation of previously reported structure-activity relationships on this chemotype, we have determined that at least one acyl group of optimal length (C(16)) and an appropriately oriented ester carbonyl group is essential for TLR2-agonistic activity. The spacing between one of the palmitoyl ester carbonyl and the thioether is crucial to allow for an important H-bond, which observed in the crystal structure of the lipopeptide:TLR2 complex; consequently, activity is lost in homologated compounds. Penicillamine-derived analogues are also inactive, likely due to unfavorable steric interactions with the carbonyl of Ser 12 in TLR2. The thioether in this chemotype can be replaced with a selenoether. Importantly, the thioglycerol motif can be dispensed with altogether and can be replaced with a thioethanol bridge. These results have led to a structurally simpler, synthetically more accessible, and water-soluble analogue possessing strong TLR2-agonistic activities in human blood.

Structure and biological activity of novel FN analogs as flowering inducers.

(12Z,15Z)-9-Hydroxy-10-oxooctadeca-12,15-dienoic acid (1) and norepinephrine (2) undergo cycloaddition to afford FN1 (3) and FN2 (4), both of which induce flowering in Lemna paucicostata. Although the derivatives of 1 were suggested to also yield FN-like compounds after reacting with 2, their structures have not been elucidated. In this report, we investigated the structure and stereochemistry of seven novel FN analogs. These analogs were shown to be formed in the same regio- and stereocontrolled manner as FNs. Moreover, the activity of FN analogs on flowering induction was investigated, and we determined that all analogs, except for compound 8, were effective flowering inducers for L. paucicostata.

Synthesis of four isomers of parinaric acid.

A simple and reliable method for synthesizing four isomers of parinaric acid from alpha-linolenic acid (ALA) in high yields is described. The methylene-interrupted, cis triene system (1,4,7-octatriene) of ALA and common to other naturally occurring polyunsaturated fatty acids was transformed to a conjugated tetraene system (1,3,5,7-octatetraene). The synthesis involves bromination of ALA using 0.l M Br(2) in a saturated solution of NaBr in methanol, esterification of the fatty acid dibromides, double dehydrobromination by 1,8-diazabicyclo[5.4.0]undec-7-ene and saponification of the conjugated esters to a mixture of free conjugated acids. Addition of one molecule of bromine to the 12,13-double bond of ALA and subsequent dehydrobromination produces alpha-parinaric acid (9Z,11E,13E,15Z-octadecatetraenoic acid); addition of Br(2) to the 9,10-double bond or 15,16-double bond and then dehydrobromination and rearrangement yields 9E,11E,13E,15Z-octadecatetraenoic or 9E,11E,13E,15Z-octadecatetraenoic acids, respectively. The mixture of parinaric acid isomers is obtained in 65% yield, and the isomers can be purified by preparative HPLC; alternatively, the isomers can be converted by base catalyzed cis-trans isomerization (or by treatment with I(2)) to exclusively beta-parinaric acid (9E,11E,13E,15E-octadecatetraenoic acid). The various parinaric acid isomers were characterized by (1)H NMR, (13)C NMR, UV, GLC, HPLC and mass spectrometry.

Microbial synthesis of trans isomer of eicosapentaenoic acid (EPA) from the chemically synthesized trans isomer of linolenic acid by a delta12 desaturase-defective mutant of Mortierella alpina 1S-4.

The mono trans geometrical isomer of eicosapentaenoic acid, 5c,8c,11c,14c,17t-eicosapentaenoic acid (20:5delta5c,8c,11c,14c,17t), was synthesized by fatty acid microbial conversion using a delta12-desaturase defective mutant of an arachidonic acid (AA)-producing fungus, Mortierella alpina 1S-4. The substrate for the bioconversion, a geometrical isomer of linolenic acid, was prepared by isomerization of linseed oil methyl ester by the nitrous acid method, followed by purification on a AgNO3-silica gel column. The structure and double bond geometry were identified after hydrazine reduction followed by permanganate oxidation to 20:5delta5c,8c,11c,14c,17t. The biosynthetic route from 18:3delta6c,9c,12t to 20:5delta5c,8c,11c,14c,17t was presumed to mimic the route from linoleic acid to arachidonic acid.

Synthesis of the (17R)- and (17S)-isomers of volicitin, an elicitor of plant volatiles contained in the oral secretion of the beet armyworm.

Both the (17R)- and (17S)-isomers of volicitin, which is contained in the oral secretion of the beet armyworm and induces corn seedlings to emit a blend of volatile compounds to attract the natural enemy of the herbivore, were synthesized via the semi-hydrogenation of an intermediary diyne and (Z)-selective olefination as the key steps. They were both obtained as crystalline compounds.

Possible anti-Parkinson properties of N-(alpha-linolenoyl) tyrosine: a new molecule.

Tyrosine is unable to cross the blood-brain barrier and is therefore unable to improve the status of brain dopamine (DA) and to provide relief for patients with Parkinson's disease (PD) or other DA-insufficient disorders. We report the creation of an amide bond molecule [N-(alpha-linolenoyl)tyrosine (NLT)] that combines tyrosine with a fatty acid mixture. NLT significantly improves the rotational behavior of rats [following unilateral striatal lesions (as a model for Parkinson's)] and overcomes the exaggerated eye-blinking induced by a potent DA-depleting agent (as a model for essential blepharospasm). These results are supported by the finding that NLT's mode of action, in striatum, is the same as the mode of action of D-amphetamine. They both induce an increase in the DA level, DA turnover and release.

Large-scale preparation of (9Z,12E)-[1-(13)C]-octadeca-9,12-dienoic acid, (9Z,12Z,15E)-[1-(13)C]-octadeca-9,12,15-trienoic acid and their [1-(13)C] all-cis isomers.

Several grams of labelled trans linoleic and linolenic acids with high chemical and isomeric purities (>97%) have been prepared for human metabolism studies. A total of 12.5 g of (9Z, 12E)-[1-(13)C]-octadeca-9,12-dienoic acid and 6.3 g of (9Z,12Z, 15E)-[1-(13)C]-octadeca-9,12,15-trienoic acid were obtained in, respectively, seven steps (7.8% overall yield) and 11 steps (7% overall yield) from 7-bromo-heptan-1-ol. The trans bromo precursors used for the labelling were synthesised by using copper-catalysed couplings. The trans fatty acids were then obtained via the nitrile derivatives. A total of 23.5 g of (9Z,12Z)-[1-(13)C]-octadeca-9, 12-dienoic acid and 10.4 g of (9Z,12Z,15Z)-[1-(13)C]-octadeca-9,12, 15-trienoic acid were prepared in five steps in, respectively, 32 and 18% overall yield. Large quantities of bromo and chloro precursors were synthesised from the commercially available acid according to Barton's procedure. In all cases, the main impurities (>0.5%) of each labelled fatty acid have been characterised.