Formation of Furan Fatty Alkyl Esters from their Bis‐Epoxide Fatty Esters

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2‐ethylhexanol, benzyl alcohol, in the presence of Brønsted acid catalyst, were investigated. Products, not reported in prior studies of similar reactions, were found. These were furan fatty acid alkyl esters (FFE, mixture of alkyl 8‐(5‐hexyl‐2‐furyl) octanoate and alkyl 9‐(5‐pentyl‐2‐furyl)nonanoate) which were unambiguously identified by means of GC–MS and two‐dimensional NMR. Evidence suggests that the FFE are formed by an acid‐catalyzed rearrangement of the epoxidized linoleates. The FFE were formed in presence of all four alcohols tested and in the presence of either sulfuric acid or Amberlyst 15 catalyst. Yields of up to 13 %, as quantified by GC and NMR spectroscopies, were observed.     

Influence of the calcination treatment on the catalytic properties of hierarchical ZSM-5

The effect of the calcination conditions on the properties and catalytic performance of hierarchical ZSM-5 zeolite has been investigated using different reactions as catalytic tests: acylation of aromatic substrates and rearrangement of linear and cyclic epoxides. The hierarchical h-ZSM-5 material was prepared by crystallization of silanized protozeolitic units. The removal of the organics present in the as-synthesized ZSM-5 samples has been carried out using two different calcination procedures: (i) directly under air atmosphere; (ii) following a two-step (nitrogen-air) treatment.Clear differences are noticed related to the textural properties of the ZSM-5 samples, since the h-ZSM-5 presents higher BET and external surface area than standard ZSM-5 zeolite. Whereas the calcination method does not affect the properties of the reference ZSM-5 sample, noticeable changes were observed over the hierarchical zeolite. The concentration of Brønsted acid sites decreases by half for one-step air calcination, but only a quarter when using a two-step nitrogen/air calcination, showing that the aluminium present in hierarchical ZSM-5 is very sensitive to the calcination conditions as it may undergo framework extraction and dehydroxylation phenomena. For all the studied reactions, the hierarchical sample, calcined by a two-step treatment, presents higher activity than when using direct air calcination.     

Utilization of green seed canola oil for in situ epoxidation

Green seed canola oil is underutilized for edible purposes due to its high chlorophyll content, which makes it more susceptible to photo‐oxidation and ultimately reduces the oxidation stability. The present work is an attempt to compare the kinetics of epoxidation of crude green seed canola oil (CGSCO) and treated green seed canola oil (TGSCO) with peroxyacids generated in situ in presence of an Amberlite IR‐120 acidic ion exchange resin (AIER) as catalyst. Among the two oxygen carrier studied, acetic acid was found to be a better carrier than the formic acid, as it gives 8% more conversion of double bond than the formic acid. A detailed process developmental study was then performed with the acetic acid/AIER combination. For the oils under investigation parameters optimized were temperature (55°C), hydrogen peroxide to double bond molar ratio (2.0), acetic acid to double bond molar ratio (0.5), and AIER loading (15%). An iodine conversion of 90.33, 90.20%, and a relative epoxide yield of 90, 88.8% were obtained at the optimum reaction conditions for CGSCO and TGSCO, respectively. The formation of the epoxide product of CGSCO and TGSCO was confirmed by Fourier Transform IR Spectroscopy (FTIR) and NMR (1H NMR) spectral analysis.     

Catalytic aminolysis of epoxide by alumina prepared from amine-protected Al precursor

The catalytic activities of alumina prepared from an Al alkoxide-amine adduct monomer for the reaction of cyclopentene oxide with piperidine was determined after various pretreatments, including calcination and exposure to moisture. They were compared with the activity of alumina prepared by the conventional hydrolysis method. It was found that the as-prepared sample from the alkoxide-amine monomer preparation was five times more active than a conventional preparation, suggesting that it has a higher density of surface Lewis acid sites. However, its activity was much more severely suppressed by exposure to moisture.     

我国二氧化碳可降解塑料的研究与应用进展

以CO2为原料合成可降解塑料是CO2资源综合利用的一条有效途径。对CO2与环氧化物共聚合成脂肪族聚碳酸酯在我国的研究开发情况进行了综述，并对其在可降解塑料方面的应用前景进行展望。     

Adaptive relationships of epoxide hydrolase in herbivorous arthropods

Epoxide hydrolase catalyzes a simple hydrolysis of reactive cyclic ethers that may otherwise alkylate and impair critical proteins and nucleic acids required for life. Although much less studied than the cytochrome P-450 monooxygenases that produce epoxides, differences in subcellular, tissue, pH, substrate, and inhibitor specificities argue for at least three forms of insect epoxide hydrolase. Increasing numbers of epoxides are being identified as plant allelochemicals, antifeedants, and essential hormones or precursors for herbivorous arthropods, and in many cases an associated alkene to diol pathway of metabolism is found. A role for epoxide hydrolase in arthropod-plant interactions is strongly supported by species comparisons and by age-activity and induction studies. Two major limitations for study in biochemical ecology of epoxide hydrolase are the lack of an effective in vivo inhibitor and a range of commercially available radiolabeled substrates for the enzymes.     

环氧化合物开环聚合催化剂的研究进展

介绍了环氧化物开环聚合用催化剂及聚合机理,并对阳离子、阴离子、配位开环聚合方法的应用及各自的优缺点进行了探讨。介绍了各种催化体系的工艺进展,指出生物酶和磷腈类催化剂具有好的研究前景。     

Syntheses of Ring C Oxysterols: Inhibitors of Sterol Biosynthesis

Oxygenated derivates of cholesterol and lanosterol, known as oxysterols, have consistently displayed significant activity as inhibitors of 3-hydroxy-3-methylglutaryl (HMG) CoA reductase, a key regulatory enzyme in sterol biosynthesis. We have developed the chemical syntheses of ring C oxysterols for evaluation as inhibitors of sterol biosynthesis. A key intermediate in the chemical synthesis was 3beta-benzoyloxy-9alpha, 1alpha-epoxy-5alpha-cholest-7-ene (1), whose structure was confirmed by X-ray crystallographic analysis and is presented herein.     

环氧石墨抗静电涂料在高硫原油中的性能

选用环氧树脂为成膜物质,石墨为导电介质制备抗静电耐蚀涂料,利用失重法研究了温度、石墨及含硫质量分数对涂料耐蚀性的影响,利用电阻法研究了石墨质量分数对涂料导电性的影响及涂料导电的时效性。结果表明,使用环氧树脂填充石墨制备抗静电耐蚀性涂料是可行的,石墨质量分数为35%~50%,其体积电阻率为105.85~105.66Ω.m,满足GB13348-1992《液体石油产品静电安全规程》,温度对涂料电阻影响较小,电阻率随时间变化不大;在含硫质量分数为3%的高硫油介质中,室温时石墨质量分数为35%的涂层耐蚀性较好;温度在50~70℃时,石墨质量分数为45%~55%的涂层耐蚀性较好,原油中含硫质量分数的变化对环氧石墨抗静电涂料的耐蚀性影响较小。