Surface active sites present in the orthorhombic M1 phases: low energy ion scattering study of methanol and allyl alcohol chemisorption over Mo–V–Te–Nb–O and Mo–V–O catalysts

The outermost surface compositions and chemical nature of active surface sites present on the orthorhombic (M1) Mo–V–O and Mo–V–Te–Nb–O phases were determined employing methanol and allyl alcohol chemisorption and surface reaction in combination with low energy ion scattering (LEIS). These orthorhombic phases exhibited vastly different behavior in propane (amm)oxidation reactions and, therefore, represented highly promising model systems for the study of the surface active sites. The LEIS data for the Mo–V–Te–Nb–O catalyst indicated surface depletion for V (−23%) and Mo (−27%), and enrichments for Nb (+55%) and Te (+165%) with respect to its bulk composition. Only minor changes in the topmost surface composition were observed for this catalyst under the conditions of the LEIS experiments at 400 °C, which is a typical temperature employed in these propane transformation reactions. These findings strongly suggested that the bulk orthorhombic Mo–V–Te–Nb–O structure is terminated by a unique active and selective surface layer in propane (amm)oxidation. Moreover, direct evidence was obtained that the topmost surface VO _x sites in the orthorhombic Mo–V–Te–Nb–O catalyst were preferentially covered by chemisorbed allyloxy species, whereas methanol was a significantly less discriminating probe molecule. The surface TeO _x and NbO _x sites on the Mo–V–Te–Nb–O catalyst were unable to chemisorb these probe molecules to the same extent as the VO _x and MoO _x sites. These findings suggested that vastly different catalytic behavior exhibited by the Mo–V–O and Mo–V–Te–Nb–O phases is related to different surface locations of V⁵⁺ ions in the orthorhombic Mo–V–O and Mo–V–Te–Nb–O catalysts. Although the proposed isolated V⁵⁺ pentagonal bipyramidal sites in the orthorhombic Mo–V–O phase may be capable of converting propane to propylene with modest selectivity, the selective 8-electron transformation of propane to acrylic acid and acrylonitrile may require the presence of several surface VO _x redox sites lining the entrances to the hexagonal and heptagonal channels of the orthorhombic Mo–V–Te–Nb–O phase. Finally, the present study strongly indicated that chemical probe chemisorption combined with low energy ion scattering (LEIS) is a novel and highly promising surface characterization technique for the investigation of the active surface sites present in the bulk mixed metal oxides.     

Quantitation of volatile compounds in heated trilinolein by static headspace-capillary gas chromatography/infrared spectroscopy-mass spectrometry

Static headspace and capillary gas chromatography/infrared spectroscopy-mass spectrometry were used to collect, separate, detect and quantitate the oxidative and thermal decomposition products in heated trilinolein. Trilinolein without added antioxidants was heated in a deep-fat fryer at 190°C for 12 h each day for a total of 24 h until the amount of polymeric material in the oil exceeded 20%. The concentration of the volatile compounds in trilinolein, as well as thep-anisidine values and polymer content, increased with an increase in heating time. After 24 h of heating, the concentrations of the major volatile compounds (>10 ppm) had increased as follows: pentane (33.4–398.7 ppm), pentanal (11.7–73.5 ppm), 1-pentanol (5.2–46.7 ppm), hexanal (67.6–346.1 ppm), (E)-2-hexenal (12.9–87.6 ppm), (E)-2-heptenal (309.6–894.1 ppm), 1-octen-3-ol (35.2–150.2 ppm), formic acid (0–18.7 ppm), hexanoic acid (0–83.8 ppm), heptanal (2.5–29.5 ppm), 2-pentylfuran (29.2–146.9 ppm), (E)-2-octenal (26.4–347.2 ppm), (E)-2-octenal (26.4–347.2 ppm), (E)-2-nonenal (31.6–163.2 ppm), (E,Z)-2,4-decadienal (15.0–320 ppm) and (E,E)-2,4-decadienal (43.1–1137.5 ppm).     

Interprovenance variation in the composition of <Emphasis Type="Italic">Moringa oleifera</Emphasis> oilseeds from Pakistan

Interprovenance variation was examined in the composition of Moringa oleifera oilseeds from Pakistan. The hexane-extracted oil content of M. oleifera seeds harvested in the vicinity of the University of Agriculture, Faisalabad (Punjab, Pakistan), Bahauddin Zakariya University (Multan, Pakistan), and the University of Sindh, Jamshoro (Sindh, Pakistan), ranged from 33.23 to 40.90%. Protein, fiber, moisture, and ash contents were found to be 28.52–34.00, 6.52–7.50, 5.90–7.00, and 6.52–7.50%, respectively. The physical and chemical parameters of the extracted M. oleifera oils were as follows: iodine value, 67.20–71.00; refractive index (40°C), 1.4570–1.4637; density (24°C), 0.9012–0.9052 mg/mL; saponification value, 177.29–184.10; unsaponifiable matter, 0.60–0.83%; color (1-in. cell), 1.00–1.50 R+20.00–30.00Y; smoke point, 198–202°C; and acidity (% as oleic acid), 0.50–0.74. Tocopherols (α, γ, and δ) accounted for 114.50–140.42, 58.05–86.70, and 54.20–75.16 mg/kg, respectively, of the oils. The induction periods (Rancimat, 20 L/h, 120°C) of the crude oils were 9.64–10.66 h and were reduced to 8.29–9.10 h after degumming. Specific extinctions at 232 and 270 nm were 1.80–2.50 and 0.54–1.00, respectively. The major sterol fractions of the oils were campesterol (14.13–17.00%), stigmasterol (15.88–19.00%), β-sitosterol (45.30–53.20%), and ͤ⁵-avenasterol (8.84, 11.05%). The Moringa oils were found to contain high levels of oleic acid (up to 76.00%), followed by palmitic, stearic, behenic, and arachidic acids up to levels of 6.54, 6.00, 7.00, and 4.00%, respectively. Most of the parameters of M. oleifera oils indigenous to different agroclimatic regions of Pakistan were comparable to those of typical Moringa seed oils reported in the literature. The results of the present analytical study, compared with those for different vegetable oils, showed M. oleifera to be a potentially valuable oilseed crop.     

Physico-Chemical Characteristics of Citrus Seeds and Seed Oils from Pakistan

The physico-chemical characteristics of the seeds and seed oils of four citrus species, Mitha (Citrus limetta), Grapefruit (Citrus paradisi), Mussami (Citrus sinensis), and Kinnow (Citrus reticulata) were investigated. The hexane-extracted oil content of citrus seeds ranged from 27.0 to 36.5%. The protein, fiber and ash contents were found to be 3.9–9.6%, 5.0–8.5%, and 4.6–5.6%, respectively. The extracted oils exhibited an iodine value of 99.9–110.0; refractive index (40 °C), 1.4639–1.4670; density (24 °C), 0.920–0.941 mg/mL; saponification value, 180.9–198.9; unsaponifiable matter, 0.3–0.5%; acid value (mg KOH/g of oil), 0.5–2.2 and color (1-in. cell) 1.4–3.0R + 15.0–30.0Y. The oils revealed a good oxidative stability as indicated by the determinations of specific extinctions at 232 and 270 nm (2.3–4.4 and 0.6–0.9, respectively), p-anisidine value (2.2–3.2) and peroxide value (1.6–2.4 mequiv/kg of oil). The citrus seed oils mainly consisted of linoleic acid (36.1–39.8%). Other prominent fatty acids were palmitic acid (25.8–32.2%), oleic acid (21.9–24.1%), linolenic acid (3.4–4.4%), and stearic acid (2.8–4.4%). The contents of tocopherols (α, γ, and δ) in the oil were 26.4–557.8, 27.7–84.1, and 9.1–20.0 mg/kg, respectively. The results of the present study demonstrated that the seeds of citrus species investigated are a potential source of valuable oil which might be utilized for edible and other industrial applications.     

Metabolism in humans ofcis-12,rans-15-octadecadienoic acid relative to palmitic,stearic, oleic and linoleic acids

Mixtures of triglycerides containing deuterium-labeled hexadecanoic acid (16∶0), octadecanoic acid (18∶0),cis-9-octadecenoic acid (9c–18∶1),cis-9,cis-12-octadecadienoic acid (9c, 12c–18∶2) andcis-12,trans-15-octadecadienoic acid (12c,15t–18∶2) were fed to two young-adult males. Plasma lipid classes were isolated from samples collected periodically over 48 hr. Incorporation and turnover of the deuterium-labeled fats in plasma lipids were followed by gas chromatography-mass spectrometry (GC-MS) analysis of the methyl ester derivatives. Absorption of the deuterated fats was followed by GC-MS analysis of chylomicron triglycerides isolated by ultracentrifugation. Results were the following: (i) endogenous fat contributed about 40% of the total fat incorporated into chylomicron triglycerides; (ii) elongation, desaturation and chain-shortened products from the deuterated fats were not detected; (iii) the polyunsaturated isomer 12c,15t–18∶2 was metabolically more similar to saturated and 9c–18∶1 fatty acids than to 9c,12c–18∶2 (iv) relative incorporation of 9c,12c–18∶2 into phospholipids did not increase proportionally with an increase of 9c,12c–18∶2 in the mixture of deuterated fats fed; (v) absorption of 16∶0, 18∶0, 9c–18∶1, 9c,12c–18∶2 and 12c,15t–18∶2 were similar; and (vi) data for the 1- and 2-acyl positions of phosphatidylcholine and for cholesteryl ester fractions reflected the known high specificity of phosphatidylcholine acyltransferase and lecithin:cholesteryl acyltransferase for 9c,12c–18∶2. These results illustrate that incorporation of dietary fatty acids into human plasma lipid classes is selectively controlled and that incorporation of dietary 9c,12c–18∶2 is limited. These results suggest that nutritional benefits of diets high in 9c,12c–18∶2 may be of little value to normal subjects and that the 12c,15t–18∶2 isomer in hydrogenated fat is not a nutritional liability at the present dietary level.     

Incorporation oftrans-8- andcis-8-octadecenoic acid isomers in human plasma and lipoprotein lipids

Mixtures of deuterium-labeledtrans-8-,cis-8- andcis-9-octadecenoic acids (8t–18∶1, 8c–18∶1, 9c–18∶1) were fed as triglycerides (TG) to two adult male subjects. Blood samples were collected sequentially over a 48-hour period. Plasma and lipoprotein lipids were separated by thin layer chromatography and analyzed by gas chromatography-mass spectroscopy. Results indicate (i) absorption of the 8t- and 8c–18∶1 isomers were similar to 9c–18∶1; (ii) the 8t–18∶1 isomer was cleared approximately 30% faster than 9c–18∶1 from plasma TG; (iii) cholesterol ester samples contained 8.4 times less 8t–18∶1 than 9c–18∶1; (iv) incorporation at the 1-acyl phosphatidylcholine (PC) position was higher for 8t–18∶1 and 8c–18∶1 (2.2 and 1.7 times) than for 9c–18∶1; and (v) discrimination at the 2-acyl PC position was 4.6-fold against 8t–18∶1 and 1.3-fold against 8c–18∶1 compared with 9c–18∶1. Discrimination against uptake of the Δ-8 isomers in both neutral and phospholipid classes suggests that both 8t- and 8c–18∶1 may be preferentially oxidized relative to 9c–18∶1. Except for triglycerides, data for each of the lipid classes from total plasma and individual lipoprotein samples were similar. These data indicate that differences for incorporation and turnover of the 8t- and 8c–18∶1 isomers relative to 9c–18∶1 are not substantially influenced by the lipoprotein classes. The maximum isotopic enrichment detected in the chylomicron triglycerides fractions was 60%, which indicates that a substantial amount of endogenous triglycerides was mobilized during absorption of the deuterated fats.     

Preparation of Mesoporous Ni–alumina Catalyst by One-step Sol–gel Method: Control of Textural Properties and Catalytic Application to the Hydrodechlorination of o-dichlorobenzene

Mesoporous Ni–alumina catalysts (Ni–alumina-pre and Ni–alumina-post) were synthesized by one-step sol–gel method using micelle complex comprising lauric acid and nickel ion as a template with metal source and using aluminum sec-butoxide as an aluminum source. The Ni–alumina catalysts showed relatively high surface areas (303 m²/g for Ni–alumina-pre and 331 m²/g for Ni–alumina-post) and narrow pore size distributions centered at ca. 4 nm. Highly dispersed Ni particles were observed in the Ni–alumina catalysts (ca. 5.2 nm for Ni–alumina-pre and ca. 6.8 nm for Ni–alumina-post) after reduction at 550 °C, while a catalyst prepared without a template (NiAl-comp) exhibited inferior porosity with large metal particles (ca. 12.3 nm). Mesoporous Ni–alumina catalysts with different porosity were obtained by employing different hydrolysis step of aluminum source. When aluminum source was hydrolyzed under the presence of micelle complex, a supported Ni catalyst with highly developed framework mesoporosity was obtained (Ni–alumina-post). On the other hand, when aluminum source was pre-hydrolyzed followed by mixing with micelle solution, the resulting catalyst (Ni–alumina-pre) retained high portion of textural porosity. It was revealed that the hydrolysis method employed in this research affected not only textural properties but also metal-support interaction in the Ni–alumina catalysts. It was also found that the Ni–alumina-pre catalyst exhibited weaker interaction between nickel and alumina than the Ni–alumina-post, leading to higher degree of reduction in the Ni–alumina-pre catalyst. In the hydrodechlorination of o-dichlorobenzene, the Ni–alumina catalysts exhibited better catalytic performance than the NiAl-comp catalyst, which was attributed to higher metal dispersion in the Ni–alumina catalysts. In particular, the Ni–alumina-pre catalyst showing 1.5 times higher degree of reduction and larger amounts of o-dichlorobenzene adsorption exhibited better catalytic performance than the Ni–alumina-post catalyst.     

Swelling Characteristics of pH- and Thermo-Sensitive Crosslinked Poly(Vinyl Alcohol) Grafts

Grafting of N-isopropylacrylamide, NIPAAm, onto partially and fully hydrolyzed poly(vinyl alcohol–g-maleic anhydride), PVA–MA, was carried out in presence of ammonium persulfate as initiator. The crosslinked PVA–MA–NIPAAm copolymers were prepared in presence of different weight percentages of methylene bisacrylamide, MBA, as crosslinker and N,N,N,N′-tetramethylethylenediamine, TMEA, as accelerator. Crosslinked PVA–MA–NIPAAm copolymers were prepared at two different temperatures 5 and 55 °C. The structural features of these grafts were confirmed by ¹H NMR analysis. Solution behaviors of both PVA–MA and PVA–MA–NIPAAm were evaluated from viscosity measurements. The swelling ratios of the crosslinked polymers were measured at different temperatures and pH values. The phase transition of the crosslinked gels was measured from DSC analysis. Crosslinked PVA–MA–NIPAAm grafts show different pH and temperature sensitivity. The swelling behaviors of PVA–MA–NIPAAm were referred to formation of hydrogen bonding between amide and carboxylic groups and also to hydrophobic aggregation of NIPAAm grafts.     

A Comparative Study of the Properties of Six Sudanese Cucurbit Seeds and Seed Oils

The proximate analysis of seeds and physicochemical properties of oils extracted from six Sudanese cucurbit seeds Cucumis mello var. agrestis, Cucumis melo var. flexuosus, Cucumis sativus, Citrullus lanatus var. colocynthoides, Cucumis prophetarum, and Luffa echinata were examined by established methods. For each variety, the proximate analysis showed ranges for moisture, protein, and carbohydrates as 3.70–6.87, 14.50–17.50, and 15.62–28.89% on a dry matter basis, respectively. The oils were extracted by Soxhlet using petroleum ether, with yields that ranged from 10.9 to 27.10% (wt/wt). The obtained extracted oils were subjected to phyiscochemical, fatty acid, and tocopherol analysis. The physicochemical characterization of the oil revealed that the refractive indices and relative densities of the oils fell within the narrow ranges of 1.334–1.442 and 0.874–0.920 g/cm³, respectively. Unsaponifiable matters ranged between 0.8 and 1.2 mg KOH/g, whilst peroxide values (PV) ranged from 2.3 to 4.1 meq/kg. The ranges of the values for free fatty acid (FFA %) were 1.2–4.0%. The predominant fatty acids were 16:0, 18:0, 18:1, and 18:2 with ranges of 8.9–14.2, 6.0–9.4, 14.6–32.1, and 43.6–65.5%, respectively. γ-Tocopherol was the predominant tocopherol in all samples ranging from 0.8 to 43.2% of the total tocopherols, followed by δ-tocopherol and α-tocopherol.     

Fatty acid (FA) composition and contents of <Emphasis Type="Italic">trans</Emphasis> unsaturated FA in hydrogenated vegetable oils and blended fats from Pakistan

This study presents the FA composition and trans FA (TFA) contents of different hydrogenated vegetable oils and blended fats marketed in Pakistan. Thirty-four vanaspati (vegetable ghee), 11 shortenings, and 11 margarines were analyzed. The contents of saturated FA, cis monounsaturated FA, and cis PUFA were in the following ranges: vanaspati 27.8–49.5, 22.2–27.5, 9.3–13.1%; vegetable shortenings 37.1–55.5, 15.8–36.0, 2.7–7.0%; and margarines 44.2–55.8, 21.7–39.9, 2.9–20.5%, respectively. Results showed significantly higher amounts of TFA in vanaspati samples, from 14.2 to 34.3%. Shortenings contained TFA proportions of 7.3–31.7%. The contents of TFA in hard-type margarines were in the range of 1.6–23.1%, whereas soft margarines contained less than 4.1% TFA.     

β-Apo-8′-Carotenoic acid and its esters in sunflower oil oxidation

The oxidation kinetics of sunflower oil (SO) and pure triacylglycerols of sunflower oil (TGSO) in the presence of different concentrations (0.0008–0.02%, 1.9–32.7×10⁻⁵ M) of β-apo-8′-carotenoic acid (CA), ethyl β-apo-8′-carotenoate (EC), and β-apo-8′-carotenoylglycerol (CG) were studied. The process was performed at high (kinetic regime) and low (diffusion regime) oxygen concentrations at room temperature and at 100°C and in the dark and in daylight. CA, EC, and CG were not antioxidants in TGSO systems. However, the carotenoid derivatives, especially CA, increased the stability of tocopherol-containing SO at room temperature and in daylight. The stabilization effect was more evident in a kinetic regime of oxidation. The synergism between the carotenoids and tocopherols was characterized by the increase of the stabilization factor F and activity A. F and A were highest for CA (F=1.2–5.5, A=2.4–78.6), followed by EC (F=1.2–3.5, A=1.7–14.6) and CG (F=1.1–2.1, A=1.6–5.5) in the kinetic regime for SO exposed to daylight at room temperature. Presented at the 91st AOCS Annual Meeting & Expo, April 25–28, 2000, San Diego, California.     

Sex Pheromones and Reproductive Isolation of Three Species in Genus <Emphasis Type="Italic">Adoxophyes</Emphasis>

We tested differences in female pheromone production and male response in three species of the genus Adoxophyes in Korea. Females of all three species produced mixtures of (Z)-9-tetradecenyl acetate (Z9–14:OAc) and (Z)-11-tetradecenyl acetate (Z11–14:OAc) as major components but in quite different ratios. The ratio of Z9–14:OAc and Z11–14:OAc in pheromone gland extracts was estimated to be ca. 100:200 for Adoxophyes honmai, 100:25 for Adoxophyes orana, and 100:4,000 for Adoxophyes sp. Field tests showed that males of each species were preferentially attracted to the two-component blends of Z9–14:OAc and Z11–14:OAc mimicking the blends found in pheromone gland extracts of conspecific females. The effects of minor components identified in gland extracts on trap catches varied with species. Addition of 10-methyldodecyl acetate (10me-12:OAc) or (E)-11-tetradecenyl acetate (E11–14:OAc) to the binary blend of Z9–14:OAc and Z11–14:OAc significantly increased captures of A. honmai males, whereas E11–14:OAc exhibited a strongly antagonistic effect on catches of Adoxophyes sp. males. Moreover, (Z)-9-tetradecen-1-ol (Z9–14:OH) or (Z)-11-tetradecen-1-ol (Z11–14:OH) added to the binary blends increased attraction of male A. orana but not A. honmai and Adoxophyes sp. males, suggesting that these minor components, in addition to the relative ratios of the two major components, play an important role in reproductive isolation between Adoxophyes species in the southern and midwestern Korea where these species occur sympatrically.     

Preparation and physical properties of some C18 unsaturated fatty esters containingL-amino acid residues and methyl esters ofN-stearoylamino acids

A series of five C₁₈ unsaturated fatty esters (1–5) containing anL-amino acid residue (glycine, alanine, valine, leucine, phenylalanine) was prepared from methyl 12-amino-9-cis-octadecenoate and five methylN-stearoyl-amino acid ester derivatives (6–10) from stearoyl chloride and the sameL-amino acids. The infrared analysis of compounds 1–5 showed characteristic absorption bands at 3300 and 1665 cm⁻¹ for the amino and amido functions, while the amido function in compounds 6–10 gave absorption bands at 3300 and 1680 cm⁻¹. The position of the amido group (peptide linkage) in compounds 1–5 was readily determined by mass spectral analysis.¹H nuclear magnetic resonance (NMR) analysis showed a doublet at 7.15 ppm for the amide proton (NHCO) in compounds 1–5, while in compounds 6–10 the amide proton signal appeared at 6.0 ppm. In¹³C NMR, the amido carbonyl resonance appeared at 171–175 ppm. In compounds 1–5 the effect of the amide function on the ethylene carbon (C-9) gave a signal at 124.1–125.3 ppm, while the remaining ethylenic carbon appeared at 131.9–132.5 ppm. The methine carbon (C-12) of the alkenyl chain was shifted to 48.4–49.8 ppm, and the assignment of the various carbon nuclei in the amino acid residue was readily achieved. In the methylN-stearoylamino acid ester derivatives (6–10), the methine carbon adjacent to the amido system and alpha to the carbomethoxy group appeared between 41.2–57.0 ppm depending on the type of alkyl group present in the amino acid moiety. The phenyl system in compounds 5 and 10 was confirmed by the¹³C signals in the 127–136 ppm range and by the proton signals in the 7.0–7.27 ppm region.     

Electrochemical investigation of the passive behaviour of biomaterials based on Ag–Sn and Cu–Zn–Al in carbonate buffer in the absence and presence of chloride

The electrochemical behaviour of biomaterials based on Cu–Zn–Al (cubic Cu₃Zn phase) and Ag–Sn (orthorhombic Ag₃Sn and hexagonal Ag₄Sn phases) alloys was investigated in carbonate buffer solutions (pH 9.66) in the absence and presence of chloride, using different electrochemical techniques. Analyses of the open circuit potential and the potentiodynamic polarisation curves showed that the passivation domain and the corrosion parameters depend on alloy composition and chloride concentration. Chronoamperometric studies showed that passivation kinetics and corrosion of the passive film are both well described by a linear ln(i) versus ln(t) relation. The passive film formed on the Ag–Sn alloy is less susceptible to corrosion when compared to the Cu–Zn–Al system. The impedance data obtained in the passive region for the Cu–Zn–Al alloy showed that the passive layer is compact. In contrast, the impedance data obtained for the Ag–Sn alloy showed that the passive layer is formed by a compact oxide layer covered by a porous oxide gel layer. Mott–Schottky analysis showed that the passive film formed on the Cu–Zn–Al alloy behaves as a p-type semiconductor.     

Sterol composition inCoincya (Brassicaceae)

Sterol composition was determined for seed oils and leaf waxes in eleven taxa belonging to the genusCoincya (Brassicaceae) on the Iberian Peninsula (Spain and Portugal). Seed sterols ranged from 1.2 to 6.7%. The major components were sitosterol (42.6–54.6%), campesterol (20.4–33.2%), and brassicasterol (10.8–23.5%). In leaf waxes, the major free sterols were sitosterol (40.9–74.2%), campesterol (9.6–17.0%), and cholesterol (4.6–17.0%). In leaf wax esters, the major sterols were sitosterol (22.2–56.5%), cholesterol (7.3–32.8%), and campesterol (5.8–25.6%). An apparent substitution of brassicasterol in free sterols from the seeds by cholesterol in free sterols from the leaves was observed. There was an increase of cholesterol in sterols from leaf wax esters with respect to free sterols from leaves and seeds. InC. monensis subsp.nevadensis, the composition in sterols from leaf waxes may be an adaptation to low temperatures.     

Rheological properties of liquid-crystalline solutions of poly(p-phenylene terephthalamide) and behavior of the jet in spinning through an air space

LC solutions of PPTA behave like liquids with a power law of flow and n =0.65–0.78 for flow through the channels of standard spinnerets with small diameters and q =0.88–0.95 for longitudinal flow in jets. Spinneret expansion of a freely falling jet in channels with small diameters is equal to 1.70–1.75 and is not a function of the shear rate on the wall. Spinneret expansion is preserved in conditions of repeated drawing of the jets in the air space until very small air spaces at 1.5–2.5 mm are used. In spinning PPTA fibres through an air space with a high jet draw ratio, only a small fraction of this drawing in the spinning bath is possible. Translated from Khimicheskie Volokna, No. 2, pp. 3–7, March–April, 1997.     

In vitro desaturation and elongation of rumenic acid by rat liver microsomes

Various nutritional studies on CLA, a mixture of isomers of linoleic acid, have reported the occurrence of conjugated long-chain PUFA after feeding experimental animals with rumenic acid, 9c,11t–18∶2, the major CLA isomer, probably as a result of successive desaturation and chain elongation. In the present work, in vitro studies were carried out to obtain information on the conversion of rumenic acid. Experiments were first focused on the in vitro Δ6-desaturation of rumenic acid, the regulatory step in the biosynthesis of long-chain n−6 PUFA. The conversion of rumenic acid was compared to that of linoleic acid (9c,12c–18∶2). Isolated rat liver microsomes were incubated with radiolabeled 9c,12c–18∶2 and 9c,11t–18∶2 under desaturation conditions. The data indicated that [1-¹⁴C]9c,11t–18∶2 was a poorer substrate for Δ6-desaturase than [1-¹⁴C]-9c,12c–18∶2. Next, in vitro elongation of 6c,9c,11t–18∶3 and 6c,9c,12c–18∶3 (γ-linolenic acid) was investigated in rat liver microsomes. Under elongation conditions, [1-¹⁴C]6c,9c,11t–18∶3 was 1.5-fold better converted into [3-¹⁴C]8c,11c,13t–20∶3 than [1-¹⁴C]6c,9c,12c–18∶3 into [3-¹⁴C]8c,11c,14c–20∶3. Finally, in vitro Δ5-desaturation of 8c,11c,13t–20∶3 compared to 8c,11c,14c–20∶3 was investigated. The conversion level of [1-¹⁴C]8c,11c,13t–20∶3 into [1-¹⁴C]5c,8c,11c,13t–20∶4 was 10 times lower than that of [1-¹⁴C]8c,11c,14c–20∶3 into [1-¹⁴C]5c,8c,11c,14c–20∶4 at low substrate concentrations and 4 times lower at the saturating substrate level, suggesting that conjugated 20∶3 is a poor substrate for the Δ5-desaturase.     

Determination of FA composition and total trans FA of Turkish margarines by capillary GLC

In this research, FA composition and total trans FA contents of 16 different brands of margarine (8 hard-type and 8 soft-type) sold in Turkey were determined by capillary GLC method. According to the results, the contents of saturated FA, monounsaturated FA, and PUFA were within the ranges of 23.9–32.3, 44.0–61.9, and 14.2–24.1%, respectively, in hard-type margarines, and 27.0–39.9, 21.0–40.9, and 32.0–53.7%, respectively, in soft-type margarines. Hard-type margarines contained total trans FA concentrations of 20.1–34.3%, whereas soft-type margarines contained less than 8.9% total trans FA. C_18∶1 trans acid content was within the range of 18.5–29.8% in hard-type margarines, and it was significantly higher than the range in soft margarines (0.7–8.1%). C_18∶1 trans acid was the major trans FA in all margarines, and C_18∶3 trans acid concentrations were less than 0.2%.     

Catalytic Performance of the Sb–V Mixed Oxide on Sb–V–O/SiO2 Catalysts in Methane Selective Oxidation to Formaldehyde

Sb–V–O/SiO₂ catalysts were prepared and investigated in methane selective oxidation with O₂ as oxidant. Sb–V–O/SiO₂ catalysts are active and selective in methane selective oxidation. The formaldehyde yield obtained on Sb–V–O/SiO₂ catalysts is clearly higher than that for VO_X/SiO₂ and SbO_X/SiO₂ catalysts. A one-pass formaldehyde yield up to 3% was obtained on Sb–V–O/SiO₂ catalysts at 650 °C. XRD and UV Raman studies showed that the phase of Sb–V mixed oxide on Sb–V–O/SiO₂ catalysts transformed with decreasing Sb/V ratio from Sb₂VO₅ to SbVO₄/VSb_1-XO_4-1.5X phase. The Sb–V mixed oxide in Sb₂VO₅ phase is more active and selective than that in SbVO₄/VSb_1-XO_4-1.5X phase.     

Variation in fatty acid composition of the different acyl lipids in seed oils from fourSesamum species

Seeds from different collections of cultivatedSesamum indicum Linn. and three related wild species [specifically,S. alatum Thonn.,S. radiatum Schum and Thonn. andS. angustifolium (Oliv.) Engl.] were studied for their oil content and fatty acid composition of the total lipids. The wild seeds contained less oil (ca. 30%) than the cultivated seeds (ca. 50%). Lipids from all four species were comparable in their total fatty acid composition, with palmitic (8.2–12.7%), stearic (5.6–9.1%), oleic (33.4–46.9%) and linoleic acid (33.2–48.4%) as the major acids. The total lipids from selected samples were fractionated by thin-layer chromatography into five fractions: triacylglycerols (TAG; 80.3–88.9%), diacylglycerols (DAG; 6.5–10.4%), free fatty acids (FFA; 1.2–5.1%), polar lipids (PL; 2.3–3.5%) and steryl esters (SE; 0.3–0.6%). Compared to the TAG, the four other fractions (viz, DAG, FFA, PL and SE) were generally characterized by higher percentages of saturated acids, notably palmitic and stearic acids, and lower percentages of linoleic and oleic acids in all species. Slightly higher percentages of long-chain fatty acids (20∶0, 20∶1, 22∶0 and 24∶0) were observed for lipid classes other than TAG in all four species. Based on the fatty acid composition of the total lipids and of the different acyl lipid classes, it seems thatS. radiatum andS. angustifolium are more related to each other than they are to the other two species.