Kinetics of antioxidant action of α‐ and γ‐toco‐pherols in sunflower and soybean triacylglycerols

A kinetic analysis was performed to evaluate the antioxidant behavior of α‐ and γ‐to‐copherols (5—2000 ppm) in purified triacylglycerols obtained from sunflower oil (TGSO) and soybean oil (TGSBO) at 100 °C. Different kinetic parameters were determined, viz. the stabilization factor as a measure of effectiveness, the oxidation rate ratio as a measure of strength, and the antioxidant activity which combines the other two parameters. In the low concentration range (up to 400 ppm in TGSBO and up to 700 ppm in TGSO) α‐tocopherol was a more active antioxidant than γ‐tocopherol whereas the latter was more active at higher concentrations. It has been found that the different activity of the tocopherols is not due to their participation in chain initiation reactions, but that the loss of antioxidant activity at high tocopherol concentrations is due to their consumption in side reactions. The rates of these reactions are higher in TGSBO than in TGSO. Both α‐tocopherol itself and its radicals participated more readily in side reactions than γ‐tocopherol and its radicals. Both α‐ and γ‐tocopherol reduce lipid hydroperoxides, thus generating alkoxyl radicals which are able to amplify the rate of lipid oxidation by participating in chain propagation reactions.     

Addition of α‐tocopherol on poly(lactic acid): Thermal,mechanical, and sorption properties

This work investigates the effect of the addition of a well‐known antioxidant, α‐tocopherol in poly (lactic acid) flexural and barrier properties. For that purpose, films of poly(lactic acid) enriched with 0, 2.2, and 4.4% of α‐tocopherol were prepared. Differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis were used to characterize the changes in the mechanical and thermal properties. The sorption of oxygen and carbon dioxide in the prepared enriched films of poly(lactic acid) was measured at different temperatures between 283 and 313 K and pressures up to atmospheric pressure using a Quartz Crystal Microbalance. Although no significant changes were found in the mechanical and thermal properties, the addition of α‐tocopherol promotes an increasing in the oxygen sorption and the convex shape of the isotherms indicate a strong interaction gas‐polymer. Regarding the sorption of carbon dioxide, no pronounced effect was found. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(L‐lactic acid) with added α‐tocopherol and resveratrol: optical,physical, thermal and mechanical properties

Poly(L ‐lactic acid) (PLLA) films containing various concentrations of two natural antioxidants, α‐tocopherol and resveratrol, were fabricated by a melt compounding and compression molding process. The influence of the antioxidants on the optical properties such as color and UV‐visible light transmission was analyzed. The thermal, mechanical, rheological and physical properties of PLLA films with added antioxidants were assessed. PLLA films with added α‐tocopherol and resveratrol showed a yellowish brown color and the lightness was influenced by the presence of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. PLLA films with added antioxidants were slightly more hydrophobic than neat PLLA. The combination effect of plasticizing and enhancement of the elastic modulus with differing concentrations of two antioxidants played a critical role in the mechanical and thermomechanical properties of PLLA films. The melt viscosity of the PLLA films with added antioxidants was substantially higher than that of neat PLLA. The higher melt viscosity and G′(ω) could be an indication of formation of entanglement between PLLA and the two antioxidants. Copyright © 2012 Society of Chemical Industry     

Two approaches in preparation for cogeneration α‐tocopherol and biodiesel from cottonseed

A two‐step process and a direct alkaline transesterification process in preparation for cogeneration α‐tocopherol and biodiesel (fatty acid methyl esters, FAME) from cottonseeds were studied in this article. The effects of some factors on recovery of α‐tocopherol and conversion of cottonseed oil (triacylglycerols, TAGs) to biodiesel in the two processes were systematically studied by single factor experiments and orthogonal design method. In the two‐step process, α‐tocopherol and biodiesel were produced from extraction with two‐phase solvent followed by base‐catalysed transesterification. Approximately 95.5% TAGs was converted into biodiesel, and 1.008 mg/g (wet basis) α‐tocopherol was detected on the condition: 1:3 petroleum ether/methanol volume rate, 40°C extraction temperature; 7:1 methanol/cottonseed oil molar ratio, 1.1% KOH (w/v) concentration in methanol and 60°C esterification temperature. And in the direct alkaline transesterification reaction, 98.3% conversion of TAGs and 0.986 mg/g content of α‐tocopherol could be achieved at 60°C in 2 h. Both of the two processes were feasible from the economic point of view for further utilisation of cottonseed. © 2011 Canadian Society for Chemical Engineering     

Cationic copolymers of α,β‐poly‐(N‐2‐hydroxyethyl)‐DL‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy): synthesis and characterization

In the present study the derivatization of two water‐soluble synthetic polymers, α,β‐poly(N‐2‐hydroxyethyl)‐DL ‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introduce positive groups in their chains and it permits the preparation of interpolyelectrolyte complexes with DNA. © 2000 Society of Chemical Industry     

Highly Enantioselective Phase‐Transfer Catalytic α‐Alkylation of α‐tert‐Butoxycarbonyllactams: Construction of β‐Quaternary Chiral Pyrrolidine and Piperidine Systems

A new enantioselective α‐alkylation of α‐tert‐butoxycarbonyllactams for the construction of β‐quaternary chiral pyrrolidine and piperidine core systems is reported. α‐Alkylations of N‐methyl‐α‐tert‐butoxycarbonylbutyrolactam and N‐diphenylmethyl‐α‐tert‐butoxycarbonylvalerolactam under phase‐transfer catalytic conditions (solid potassium hydroxide, toluene, −40 °C) in the presence of (S,S)‐3,4,5‐trifluorophenyl‐3,3′,5,5′‐tetrahydro‐2,6‐bis(3,4,5‐trifluorophenyl)‐4,4′‐spirobi[4H‐dinaphth[2,1‐c:1′,2′‐e]azepinium] bromide [(S,S)‐NAS Br] (5 mol%) afforded the corresponding α‐alkyl‐α‐tert‐butoxycarbonyllactams in very high chemical (up to 99%) and optical yields (up to 98% ee). Our new catalytic systems provide attractive synthetic methods for pyrrolidine‐ and piperidine‐based alkaloids and chiral intermediates with β‐quaternary carbon centers.     

Direct Decarboxylative Alkynylation of α,α‐Difluoroarylacetic Acids under Transition Metal‐Free Conditions

An efficient and generally applicable protocol for decarboxylative coupling of α,α‐difluoroarylacetic acids with ethynylbenziodoxolone (EBX) reagents has been developed, affording α,α‐difluoromethylated alkynes bearing various functional groups in moderate to excellent yields. Remarkably, this potassium persulfate (K₂S₂O₈)‐promoted reaction employs water as solvent under transition metal‐free conditions, thus providing a green synthetic approach to α,α‐difluoromethylated alkynes.

     

Influence of milling conditions on the α‐tocopherol content of Picual olive oil

The aim of this study was to estimate the α‐tocopherol content in Picual extra‐virgin olive oils obtained from the 2004/2005 harvesting season and to evaluate the influence that different extraction processes and sample handling had on the final vitamin E content in the oils. A new experimental oil extraction carried out at 9 °C enabled us to obtain encouragingly high quantities of α‐tocopherol with an average quantity reaching 341.34 ± 50.17 mg/L (n = 13), with significant differences among the same oil types produced from the traditional two‐phase system at low (9 °C, p <0.01) and moderate (21.5 °C, p <0.001; 33 °C, p <0.0001) temperatures. The temperature at which extraction was carried out should be considered as a major factor to be taken into account. Additionally, we also developed a precise method for the extraction of α‐tocopherol from olive oil samples, which enables high recovery (96 ± 2%) for use in subsequent HPLC/DAD/fluorescence quantification.     

Oxidation at elevated temperatures: competition between α‐tocopherol and unsaturated triacylglycerols

The competitive oxidation between α‐tocopherol and unsaturated fatty acyls at thermoxidation conditions (180 and 240 °C) was evaluated using purified triacylglycerols from nine fats and oils (refined coconut, palm, tallow, olive, high oleic sunflower, sunflower, corn, soybean, and flaxseed oil). α‐Tocopherol degraded faster in less unsaturated lipids and a linear correlation between the iodine value (x) and the residual tocopherol content (y) was obtained after 2 h of heating at 240 °C (y = 3.72x + 137.5, R² = 0.9463). The formation of polar oxidation products was established and the results were explained by a non‐selective oxidation of unsaturated fatty acyls and α‐tocopherol by highly reactive alkoxyl and hydroxyl radicals generated by decomposition of hydroperoxides.     

Effect of α‐, γ‐, and δ‐tocopherol on the distribution of volatile secondary oxidation products in fish oil

The relative ability of α‐, γ‐ and δ‐tocopherol (TOH) to influence the distribution of volatile secondary oxidation products in fish oil was studied, with particular emphasis on oxidation products expected to be important for adverse flavour formation. Purified fish oil samples with 100 ppm or 1000 ppm of the different tocopherols were analysed by dynamic headspace analysis of the volatiles formed after 2, 5 and 8 d of storage at 30 �C. The tocopherol type and concentration affected not only the overall formation of volatile secondary oxidation products, but also the composition of this group of oxidation products. Principal component analysis of the data obtained suggested that high tocopherol hydrogen‐donating power, i.e. a high tocopherol concentration or the use of αTOH as opposed to γTOH or δTOH, directs the formation of hydrocarbons, unsaturated carbonyl compounds of relatively high molecular weight, as well as the formation of cis, trans isomers of unsaturated aldehydes. Although an active inhibitor of overall volatile formation, αTOH at a high concentration thus appears to direct the formation of the more flavour‐potent aldehydes, such as those linking the carbonyl group with ethylenic conjugated unsaturation.     

Ruthenium(II)‐Catalyzed Protocol for Preparation of Diverse α,β‐ and β,β‐Dihaloenones from Diazodicarbonyls

Efficient one‐step syntheses of α,β‐ and β,β‐dihaloenones were achieved by ruthenium(II)‐catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers several significant advantages, which include ease of handling, mild reaction conditions, one‐step reaction, and the use of an effective and non‐toxic catalyst. The synthesized compounds were further transformed into highly functionalized novel molecules bearing aromatic rings on the enone moiety using the Suzuki reaction.

     

Catalytic Hydrogenation of α‐Iminophosphonates as a Method for the Synthesis of Racemic and Optically Active α‐Aminophosphonates

It was shown that the catalytic hydrogenation of α‐iminophosphonates by molecular hydrogen can serve as a convenient method for the synthesis of racemic and optically active α‐aminophosphonates. Up to 94% ee was achieved in the rhodium‐catalyzed enantioselective hydrogenation using chiral ligand (R)‐BINAP.     

Organocatalytic Enantioselective Aziridination of α‐Substituted α,β‐Unsaturated Aldehydes: Asymmetric Synthesis of Terminal Aziridines

The first example of a highly enantioselective organocatalytic aziridination of α‐substituted α,β‐unsaturated aldehydes is presented. The reaction is catalyzed by simple chiral amines and gives access to highly functional terminal azirdines containing an α‐tertiary amine stereocenter in high yields and enantiomeric ratios (95.5:4.5–98:2).     

Highly Enantioselective Michael Addition of Cyclic 1,3‐Dicarbonyl Compounds to β,γ‐Unsaturated α‐Keto Esters

A highly enantioselective Michael addition of cyclic 1,3‐dicarbonyl compounds to β,γ‐unsaturated α‐keto esters catalyzed by amino acid‐derived thiourea‐tertiary‐amine catalysts is presented. Using 5 mol% of a novel tyrosine‐derived thiourea catalyst, a series of chiral coumarin derivatives were obtained in excellent yields (up to 99%) and with up to 96% ee under very mild conditions within a short reaction time.     

RuO4 staining and lamellar structure of α‐ and β‐PP

Monoclinic (α) and hexagonal (β) polypropylene (α‐ and β‐PP) were stained in the vapor of a ruthenium tetroxide solution prepared in situ. The effect of staining on the fusion behavior was investigated using a DSC. A staining duration between 10 and 24 h was found suitable for obtaining a good electron contrast between the crystalline and amorphous regions for TEM examination without causing severe damage to the crystals. The spherulites of the water‐quenched α‐PP were found to be composed of very fine cross‐hatched lamellae whose long period was about 10 nm. In comparison, the β‐PP spherulites crystallized isothermally at 130°C had a category 2 morphology and the lamellae have a long period of 20 nm. The morphology of the spherulite boundary varied depending on the contact angle between the lamellae of the neighboring spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1529–1538, 1999     

N‐Heterocyclic Carbene‐Mediated Organocatalytic Transfer of Tin onto Aldehydes: New Access to α‐Silyloxyalkylstannanes and γ‐Silyloxyallylstannanes

A new, highly efficient and mild N‐heterocyclic carbene (NHC)‐mediated organocatalytic procedure for the transfer of tin from tributyl(trimethylsilyl)stannane (Bu₃SnSiMe₃) onto aldehydes for the preparation of α‐silyloxyalkylstannanes and γ‐silyloxyallylstannanes has been developed.     

Efficient Synthesis of β,γ‐Alkynyl α‐Amino Acid Derivatives by Ag(I)‐Catalyzed Alkynylation of α‐Imino Esters

The first catalytic synthesis of β,γ‐alkynyl α‐amino acid derivatives was achieved by direct addition of terminal alkynes to α‐imino esters in the presence of an Ag(I) salt under mild reaction conditions.     

Multi‐Enzymatic Synthesis of Optically Pure β‐Hydroxy α‐Amino Acids

A novel enzymatic production system of optically pure β‐hydroxy α‐amino acids was developed. Two enzymes were used for the system: an N‐succinyl L ‐amino acid β‐hydroxylase (SadA) belonging to the iron(II)/α‐ketoglutarate‐dependent dioxygenase superfamily and an N‐succinyl L ‐amino acid desuccinylase (LasA). The genes encoding the two enzymes are part of a gene set responsible for the biosynthesis of peptidyl compounds found in the Burkholderia ambifaria AMMD genome. SadA stereoselectively hydroxylated several N‐succinyl aliphatic L ‐amino acids and produced N‐succinyl β‐hydroxy L ‐amino acids, such as N‐succinyl‐L ‐β‐hydroxyvaline, N‐succinyl‐L ‐threonine, (2S,3R)‐N‐succinyl‐L ‐β‐hydroxyisoleucine, and N‐succinyl‐L ‐threo‐β‐hydroxyleucine. LasA catalyzed the desuccinylation of various N‐succinyl‐L ‐amino acids. Surprisingly, LasA is the first amide bond‐forming enzyme belonging to the amidohydrolase superfamily, and has succinylation activity towards the amino group of L ‐leucine. By combining SadA and LasA in a preparative scale production using N‐succinyl‐L ‐leucine as substrate, 2.3 mmol of L ‐threo‐β‐hydroxyleucine were successfully produced with 93% conversion and over 99% of diastereomeric excess. Consequently, the new production system described in this study has advantages in optical purity and reaction efficiency for application in the mass production of several β‐hydroxy α‐amino acids.