Effect of α-, β-, γ-, and δ-Tocotrienol on the Oxidative Stability of Lard

Despite the structural similarity of tocopherols, the antioxidative activities of tocotrienol homologues have not been studied often. In this study, the antioxidant activities of α-, β-, γ-, and δ-tocotrienols at various concentrations from 100 to 1,000 ppm in lard were evaluated. Headspace oxygen content of the lard without tocotrienol decreased from 21.1 to 10.7 % and the peroxide value increased from 0.4 to 33.4 mequiv/kg after 7 days of storage at 55 °C in the dark. α-Tocotrienol at 100 ppm and β-tocotrienol at 100 and 200 ppm effectively improved the oxidative stability of lard; however, the antioxidative activities of α- and β-tocotrienol reduced as the concentration increased to 1,000 ppm. The γ- and δ-tocotrienols improved the oxidation stability of lard and the effectiveness was essentially same at all concentrations (p > 0.05). The antioxidative activities of tocotrienols in the autoxidation of lard increased in the order of α-, β-, γ-, and δ-tocotrienols. The activities of tocotrienols in lard were different depending on the type of homologues and concentrations.     

Effect of α-, β-, γ-, and δ-Tocotrienol on the Singlet Oxygen Oxidation of Lard

The impacts of four different types of tocotrienol homologues on the singlet oxygen oxidation of lard were evaluated by measuring the headspace oxygen content and the peroxide value. Singlet oxygen oxidation of lard was induced by chlorophyll photosensitization. Samples of 0.100, 0.250, and 0.400 M lard in methylene chloride containing chlorophyll and α‐, β‐, γ‐, or δ‐tocotrienol were prepared and stored under light at 3,000 lux for 4 h. All tocotrienol homologues at 1.20 mM significantly prevented the singlet oxygen oxidation of lard. Chlorophyll under light produced singlet oxygen at 1.09 μmol oxygen/mL headspace/h. A steady state kinetic study showed that tocotrienols reduced the singlet oxygen oxidation of lard by quenching the singlet oxygen. Singlet oxygen reacted with lard at 6.50 × 10⁴M^?1 s^?1. α‐, β‐, γ‐, and δ‐tocotrienol quenched singlet oxygen with the rate of 2.16, 1.99, 2.05, and 0.800 × 10⁷M^?1 s^?1, respectively. Among them, α‐tocotrienol significantly prevented singlet oxygen oxidation of lard.     

Properties of α-, γ-, and δ-tocopherol in purified fish oil triacylglycerols

The effect of α-tocopherol (αTOH) (50–2000 ppm), γ-tocopherol (γTOH) (100–2000 ppm), and δ-tocopherol (δTOH) (100–2000 ppm) on the formation and decomposition of hydroperoxides in purified fish oil triacylglycerols (TAG) was studied. The tests were conducted at 30°C in the dark. Purified fish oil TAG oxidized very rapidly with no apparent induction period. The relative ability of the tocopherols to retard the formation of hydroperoxides decreased in the order αTOH> γTOH>δTOH at a low level of addition (100 ppm), but a reverse order of activity was found when the initial tocopherol concentration was 1000 ppm. This dependence of relative antioxidant activity on tocopherol concentration was caused by the existence of concentrations for maximal antioxidant activity for αTOH and for γTOH. An inversion of activity, on the basis of hydroperoxide formation, was observed for αTOH at 100 ppm and for γTOH at 500 ppm, whereas the antioxidant activity of δTOH increased with level of addition up to 1500–2000 ppm. None of the tocopherols displayed any prooxidant activity. All three tocopherols strongly retarded the formation of volatile secondary oxidation products in a concentration-dependent manner. At concentrations above about 250 ppm there appeared to be a linear relationship between rate of consumption of αTOH and initial αTOH concentration, in accordance with the linear relationship observed between the initial rate of formation of hydroperoxides and the initial αTOH concentration. The rate of consumption of γTOH also increased with initial concentration, but to a lesser extent than for αTOH. At high levels of addition the rate of consumption of δTOH was independent of initial concentration, appearing to reflect the greater stability of this tocopherol homolog and participation in reactions with lipid peroxyl radicals only. Presented in part at the AOCS annual meeting in San Diego, California, April 2000.     

Determination of (+)-, (−)-, and total gossypol in cottonseed by high-performance liquid chromatography

Gossypol, a pigment in cottonseed, is a polyphenolic, binaphthyl dialdehyde. Due to steric hindrance between the functional groups of the molecule at the bond connecting the two naphthyl rings, gossypol exists as (+)- and (−)-isomers. Gossypol is physiologically active with the (−)-isomer appearing to be more active and causing temporary infertility in males. It is thus important to know the amounts of isomers in livestock feeds. A quantitative high-performance liquid chromatography (HPLC) procedure was developed for the separation of (+)- and (−)-gossypol contained in cottonseed. This method involves derivatization of gossypol with (R)-(−)-2-amino-1-propanol followed by HPLC separation employing either a Phenomenex Prodigy (5 μ, ODS-3, 100 × 3.2 mm) or a MetaChem Inertsil (5 μ, ODS-3, 100 × 3.0 mm) reversed-phase column eluted with 80% acetonitrile and 20% 10 mM KH₂PO₄ adjusted to pH 3.0 with H₃PO₄ at 1.0 mL/min. The (+)- and (−)-gossypol-2- amino-1-propanol complexes eluted at roughly 1.4 and 2.6 min, respectively. It was found that gossypol from Upland (Gossypium hirsutum) seed was rich in the (+)-enantiomer, with the (+)- and (−)-enantiomers in a ratio of about 65:35, respectively, while gossypol from the seed of a Pima (G. barbadense) cultivar (S-6) was slightly richer in the (−)-enantiomer (46.8:53.2). Deceased.     

[2, 7, 12, 18-四甲基-3, 8-二(-1-羟基乙基)-13, 17-二羧基乙基]-卟啉的改进合成

在酸性条件下,氯化血红素(Ⅰ)与还原性铁粉作用生成原卟啉(Ⅱ),通过HBr-冰醋酸加成不经提纯直接加入NaOH溶液,OH-取代仲位Br制得[2,7,12,18-四甲基-3,8-二(1-羟基乙基)-13,17-二羧基乙基]-卟啉(血卟啉,Ⅲ),反应总产率达到90.6%。探讨了脱铁过程中反应温度、时间、还原剂用量等因素对原卟啉(Ⅱ)合成的影响,反应时间和pH对血卟啉(Ⅲ)合成的影响。结果表明,当氯化血红素和铁粉的摩尔比为1∶1、反应温度为110℃时,原卟啉的产率最高达98.3%;当pH=10,反应时间为6 h时,血卟啉的产率最高达92.1%。通过IR、MS和1HNMR对产物结构进行了表征。     

2,4,6-三（4,-羧基-1,-羧丙氨基）-1,3,5-三嗪

用三聚氯氰和谷氨酸为原料,合成2,4,6-三（4,-羧基-1,-羧丙氨基）-1,3,5-三嗪（TGAT）。讨论了反应物配比、反应时间、反应温度对产率的影响。FTIR及1HNMR表征了衍生物的结构。通过对产物进行阻垢实验发现,该类型阻垢剂对碳酸钙有良好的阻垢效果。通过扫描电镜考察了阻垢剂碳酸钙垢晶型的变化,结果表明TGAT可使碳酸钙垢晶型完全扭曲,形成球霰石晶体,从而达到阻垢目的。     

顺式-,反式-1, 2-环己二醇热力学性质的研究

测定了不同几何结构的1, 2-环己二醇的熔点、熔化热和燃烧热,并考察了它们的混合物的热力学行为.测定了顺式-,反式-1, 2-环己二醇的混合物的熔融温度随着组成的变化情况,并根据其测定结果做出了两种不同几何结构物质混合后的熔融温度与组成的相图.根据DSC差示扫描量热仪测试结果,顺式-1, 2-环己二醇与反式-1, 2-环己二醇的熔化热分别为20.265kJ( mol(1和16.368kJ( mol(1.用氧弹量热仪测得在 298.15K下不同几何结构的1, 2-环己二醇的标准燃烧热分别为-3507.043kJ@mol-1(顺式)和-3497.800kJ( mol(1 (反式).     

Some lanthanide (III) complexes of (S,S)-(+)-2,3-dimethoxyl-N,N′-dimethyl-1,4-diaminobutane

Four new optically active complexes of the composition LnL₃Cl₃ (where, L=(S,S)-(+)-2,3-dimethoxyl-N,N^′-dimethyl-1,4-diaminobutane, Ln=La³⁺, Sm³⁺, Pr³⁺ and Nd³⁺) were prepared and characterized on the basis of their chemical analyses, molar conductance, magnetic properties, CD, XPS, visible and IR spectra. It is found that the complexes behave as non-electrolytes in DMSO and in methanol solution and possess the stoichiometric ratio of Ln:C:N:O:Cl =1.1:24.0:6.1:6.0:3.1 which is consistent with the analyses data. The magnetic moments of the complexes show little deviation from the Van Vleck values, indicating that 4f electrons do not participate in bond formation in these chelates. The thermal analysis revealed that all the complexes are anhydrous. Their dominant conformers were determined from CD spectra. A nine-coordinated model was proposed for these complexes.     

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Spark plasma sintering behavior of combustion-synthesized (Y,Ca)-α-SiAlON

This paper describes the sintering behavior of combustion-synthesized (Y, Ca)-α-SiAlON powders when using spark plasma sintering (SPS) technology. The effects of sintering temperature, heating rate, and holding time on the densification behavior, α→β phase transformation, and Vickers hardness were investigated in detail. Fully dense Y-α-Si_12−(m+n)Al_m+nO_nN_16−n (m=1.2, n=0.6, Y-α-SiAlON) and Ca-α-Si_12−(m+n)Al_m+nO_nN_16−n (m=1.0, n=0.5, Ca-α-SiAlON) were obtained during sintering for 10 min at final temperatures as low as 1400 °C and 1500 °C, respectively. X-ray diffraction results showed that more than 50 mass% of α-phase transformed to the β-phase for Y-α-SiAlON after SPS, whereas no obvious α→β phase transformation was observed for Ca-α-SiAlON, even after sintering at a high temperature of 1600 °C. A maximum Vickers hardness of 18.56 GPa and 19.95 GPa was reached for Y-α-SiAlON and Ca-α-SiAlON, respectively.     

N2,N2,N6,N6-四乙基-4-醛基吡啶-2,6-二甲酰胺的合成

以2,6-二甲基吡啶为原料,经KMnO4氧化、二乙胺酰胺化、吡啶环自由基亲核取代反应得到N2,N2,N6,N6-四乙基-4-羟甲基吡啶-2,6-二甲酰胺,然后用Sarret试剂氧化得到标题化合物并探讨了氧化反应的最佳条件,产物结构经1HNMR、IR和MS得到表征.该产物是合成新型吡啶类有机配体的重要中间体.     

Stereospecific formation of a ternary complex of (S)-α,β-fluoromethylene-dATP with DNA pol β

The influence of water: crystallization of (R/S)-α,β-CHF-dATP with the preorganized pol β-DNA complex shows that (S)-α,β-CHF-dATP is preferentially bound to the active site with the C=F fluorine proximal to a structural water bound to Asp276.     

Characterization and identification of essential residues of the glycoside hydrolase family 64 laminaripentaose-producing-β-1, 3-glucanase

Laminaripentaose-producing β-1,3-glucanase (LPHase) from Streptomyces matensis DIC-108 uniquely catalyzes the hydrolysis of β-1,3-glucan to release laminaripentaose as the predominant product. For studying this novel enzyme, the gene of LPHase was reconstructed with polymerase chain reaction and over-expressed in Escherichia coli. The recombinant wild-type enzyme and various mutants were further purified to >90% homogeneity on an ion-exchange chromatograph. The catalysis of the recombinant LPHase is confirmed to follow a one-step single-displacement mechanism with (1)H-NMR spectrometry. To determine the amino-acid residues essential for the catalysis, more than ten residues, including five highly conserved residues--Asp(143), Glu(154), Asp(170), Asp(376) and Asp(377), were mutated. Among the mutants, E154Q, E154G, D174N and D174G significantly lost catalytic activity. Further investigation with chemical rescue using sodium azide on E154G and D174G confirmed that Glu(154) functions as the general acid whereas Asp(170) serves as the general base in a catalytic turnover. This work is the first report that provides direct information for the identification of the essential residues of GH-64 through kinetic examination.