New phospholipid fatty acids from the marine spongeCinachyrella alloclada uliczka

The fatty acid composition of phospholipids from the Senegalese spongeCinachyrella alloclada was examined. Two new fatty acids not hitherto found in nature, namely 10,13-octadecadienoic acid and 16-tricosenoic acid, were identified. 8-Hexadecenoic, 13-nonadecenoic and 5,9,13-trimethyltretradecanoic fatty acids were also found for the first time in sponges. The latter compound (1.4% of the total fatty acid mixture), an isoprenoid fatty acid, accompanies the major fatty acid 4,8,12-trimethyltridecanoic acid (19.7%). The monomethyl branched fatty acids (22%) identified include 23-methylpentacosanoic acid (anteiso-26∶0), not previously observed in sponged. The major long-chain fatty acids encountered were the known 17-tetracosenoic 19-heptacosadienoic and 5,9,23-tricontatrienoic acid. Some sixty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry.     

Dendritic polymers from vinyl ether

1-[(2-Vinyloxy)ethoxy]ethyl acetate (1) was prepared by the addition reaction between ethylene glycol divinyl ether and acetic acid. 1 contains both a cationically polymerizable C=C double bond and a dormant initiating moiety for cationic polymerization. It can, therefore, undergo self condensing cationic polymerization in the presence of a Lewis acid activator, such as zinc chloride. Using this procedure, a novel dendritic polymer consisting of vinyl ether was prepared and its hyperbranched molecular structure confirmed by FT-IR and ¹H NMR spectra. Received: 22 May 1997/Revised: 17 July 1997/Accepted: 6 August 1997     

Action of 1-(11-selenadodecyl)-glycerol and 1-(11-selenadodecyl)-3-trolox-glycerol against lipid peroxidation

The antioxidant action on lipid peroxidation of the synthesized selenium compounds 1-(11-selenadodecyl)-glycerol (SeG) and 1-(11-selenadodecyl)-3-Trolox-glycerol (SeIrG, where Trolox=6-hydroxyl-2,5,7,8-tetramethylchroman-2-carboxylic acid) was investigated. We compared the reactivity of the selenium compounds toward peroxyl radicals and their inhibitory effect on lipid peroxidation, induced by several kinds of initiating species such as azo compounds, metal ions, and superoxide/nitric oxide in solution, micelles, membranes, and rat plasma. SeTrG, but not SeG, scavenged peroxyl radicals. SeG reduced methyl linoleate hydroperoxides in organic solution and in methyl linoleate micelles oxidized by ferrous ion (Fe²⁺)/ascorbic acid. In rat plasma SeG and SeTrG decreased the formation of lipid hydroperoxides generated by hydrophilic azo compounds. SeG and SeTrG spared α-tocopherol (α-TOH) consumption in multilamellar vesicle membranes oxidized by hydrophilic or lipophilic initiators, and only SeTrG spared α-TOH in superoxide/nitric oxide oxidized membranes. In rat plasma oxidized by radical initiators (either hydrophilic or lipophilic) or superoxide/nitric oxide, SeTrG suppressed α-TOH consumption, but SeG had no effect. The two selenium-containing compounds showed inhibitory effects on lipid peroxidation that depended on their structure, the medium where they acted, and the oxidant used.     

Biphasic compatible blends from injection-molded poly(ether ether ketone)/polysulfone

Poly(ether ether ketone)/polysulfone blends were obtained by direct injection molding throughout the composition range. The almost full immiscibility and biphasic nature of these blends was seen by differential scanning calorimetry and dynamic-mechanical thermal analysis and their homogeneously dispersed phase by scanning electron microscopy. The elastic modulus showed an usual behavior slightly below additivity. However, the strain-related break properties such as ductility or impact strength showed a surprising and positive, for an immiscible blend, behavior close to additivity both in as-molded and in annealed blends. Some possibilities, such as fast cooling, the largely aromatic nature, similar solubility parameters, different dilatation or Poisson coefficients, and the inherent chemical structure of the blends are discussed as reasons for the observed behavior. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1503–1510, 1997     

Hybrid fiber fabric composites from poly ether ether ketone and glass fiber

Poly ether ether ketone (PEEK) polymer was extruded into filaments and cowoven into unidirectional hybrid fabric with glass as reinforcement fiber. The hybrid fabrics were then converted into laminates and their properties with special reference to crystallization behavior has been studied. The composite laminates have been evaluated for mechanical properties, such as tensile strength, interlaminar shear strength (ILSS), and flexural strength. The thermal behavior of the composite laminates were analyzed using differential scanning calorimeter, thermogravimetric analyzer, dynamic mechanical analyzer (DMA), and thermomechanical analyzer (TMA). The exposure of the fabricated composite laminates to high temperature (400 and 500°C) using radiant heat source resulted in an improvement in the crystallanity. The morphological behavior and PEEK resin distribution in the composite laminates were confirmed using scanning electron microscope (SEM) and nondestructive testing (NDT). Although DMA results showed a loss in modulus above glass transition temperature (T_g), a fair retention in properties was noticed up to 300°C. The ability of the composite laminates to undergo positive thermal expansion as confirmed through TMA suggests the potential application of glass–PEEK composites in aerospace sector. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117:1446–1459, 2010     

Diisopropyl ether syntheses from crude acetone

Diisopropyl ether (DIPE) may be generated via a novel, two-step process from crude, by-product, acetone streams through initial acetone hydrogenation over a bulk-metal, nickel-rich catalyst to give isopropanol (IPA), followed by dehydration of said IPA intermediate in the presence of an acidic, large-pore zeolite catalyst. Three classes of acidic zeolite have proven effective for selective DIPE production, including Beta-zeolite, β-zeolites modified with certain transition metals, and dealuminized Y-zeolites. This revised version was published online in July 2006 with corrections to the Cover Date.     

Modeling the low-temperature synthesis of dimethyl ether from methanol

The low-temperature catalytic dehydration of methanol to dimethyl ether (DME) has been analyzed. Efficient sulfocationic catalysts for the liquid-phase dehydration of methanol within a temperature range of 90–150°C and polyoxide catalysts for the gas-phase dehydration of methanol within a temperature range of 130–220°C have been selected. Kinetic models of these reactions are constructed, and their constants are determined from the results of kinetic experiments. The constructed models are shown to be adequate to experiment. The selected catalysts open additional opportunities for intensifying the processes of DME synthesis from methanol and syngas, abruptly reducing the primecost of the target product, dimethyl ether.     

Novel sulfonated poly(ether ether ketone ketone) derived from bisphenol S

A series of sulfonated poly(ether ether ketone ketone)s derived from bisphenol S were prepared by nucleophilic polycondensation. They showed high thermal resistance and good solubility. Most of the polymers were easily cast into tough membranes. The swelling of the membranes (6.02–16.02%) was lower than that of Nafion membranes, and the ion‐exchange capacity of the membranes (0.67–1.44) was higher than that of Nafion membranes. The proton conductivity of the membranes was 0.022–0.125 s/cm. They could be used as proton‐exchange membranes in fuel cells. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1569–1574, 2004     

Poly(ether ether sulfone)s and sulfonated poly(ether ether sulfone)s derived from functionalized 1,1‐diphenylethylene derivatives

Symmetrically disubstituted 1,1‐diphenylethylene derivatives, 1,1‐bis[4‐(t‐butyldimethylsiloxy)phenyl]ethylene and 1,1‐bis(4‐hydroxyphenyl)ethylene, were prepared by new synthesis methods and employed as functionalized monomers in the preparation of new poly(ether ether sulfone) derivatives, with the introduction of the 1,1‐diphenylethylene unit along the polymer backbone. A series of parent 1,1‐diphenylethylene based poly(ether ether sulfone)s were prepared via (a) the cesium fluoride catalysed polycondensation reactions of dihalogenated diaryl sulfones with silylated bisphenols and (b) the base catalysed aromatic nucleophilic substitution polycondensation reaction between aromatic dihalogenated diaryl sulfones with bisphenols. The post‐polymerization sulfonation reaction via the thiol‐ene addition reaction of the poly(ether ether sulfone) precursor containing the 1,1‐diphenylethylene unit along the backbone, with sodium 3‐mercapto‐1‐propane sulfonate, afforded well‐defined sulfonated poly(ether ether sulfone), with the alkyl sulfonate group introduced pendant to the polymer backbone. The organic compounds and different polymer derivatives were characterized by standard chromatography, spectroscopy, spectrometry, thermal analyses, microscopy and X‐ray diffraction measurements. © 2016 Society of Chemical Industry     

One-pot synthesis of ethylene glycol and its mono-methyl ether from ethylene using Al-TS-1 catalyst

Ethylene glycol (EG) and its mono-methyl ether (MME) were synthesized directly from ethylene and hydrogen peroxide under mild conditions using Al–TS-1 as the bifunctional catalyst. The progressive incorporation of Al into the framework increased the catalytic capacity of Al–TS-1 until a maximum was reached (SiO₂/Al₂O₃ molar ratio: 504), whereas further Al incorporation decreased the catalytic activity to even lower values than in TS-1. Under the optimum conditions, the conversion and utilization of H₂O₂ reached 95% and 90%, respectively, while the total concentration of EG and MME reached to above 10 wt.%.     

Hollow fiber microfiltration membranes from poly(ether ether ketone) (PEEK)

A procedure for obtaining high performance large internal diameter (ID; >1 mm) hollow fiber microfiltration membranes from poly(ether ether ketone) (PEEK) is presented. A simple mixture of isomers of diphenylphthalate is a good solvent for employing the thermal‐phase inversion process to obtain PEEK membranes. Obtaining large ID hollow fibers with substantial transmembrane flux requires sufficient melt strength during spinning to prevent excessive draw of the extruding fiber. The use of a second leachable polymer to the blend satisfies the conditions, and polysulphone (PS) is found to provide superior membranes relative to either poly(etherimide) (PEI) or poly(ether sulphone) (PES) as a second polymer. PEEK membranes obtained by this process yield better chemical resistance to a concentrated warm surfactant/oil solution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 175–181, 1999     

回收正丙醚-正丙醇工艺过程研究

采用Sim Sci PRO/II 9. 3软件模拟分析和实验验证,建立以DMAC为溶剂从制药废液中回收正丙醚和正丙醇的萃取精馏分离工艺。采用UNIQUAC模型对工艺参数进行优化与分析,并以实验验证模拟模型的可靠性。结果表明,模拟确定适宜工艺参数为:萃取精馏塔理论板数35块,原料液第24块板进料,溶剂第7块板进料,溶剂比1. 2,回流比3. 2,塔顶回收正丙醚含量为99. 88%;溶剂回收塔理论塔板数25块,原料第6块板进料,回流比0. 7,塔顶回收正丙醇含量为99. 86%。在此优化工艺条件下,二者回收率均在99. 5%以上,达到了在原工艺中循环套用要求。在模拟优化的基础上进行萃取精馏实验,实验结果与模拟结果吻合较好,验证了模拟结果的可靠性。     

油品中硫醚脱除技术的研究进展

综述了目前国内外硫醚脱除技术的研究现状,其中包括固体吸附、溶剂吸收、生物脱硫和催化氧化4种技术,总结了各技术的脱硫机理及其优势与弊端,并对未来油品中硫醚的脱除技术进行展望,指出:传统的单相脱硫工艺及双脱联合脱硫工艺已经无法满足生产的需要,应变双脱为三脱;充分利用各技术的优势,将各脱硫技术有机结合,如吸附脱硫与硫醚的催化氧化技术相结合,生物脱硫与加氢技术相结合等。     

回收正丙醚-正丙醇工艺过程研究

采用Sim Sci PRO/II 9. 3软件模拟分析和实验验证,建立以DMAC为溶剂从制药废液中回收正丙醚和正丙醇的萃取精馏分离工艺。采用UNIQUAC模型对工艺参数进行优化与分析,并以实验验证模拟模型的可靠性。结果表明,模拟确定适宜工艺参数为:萃取精馏塔理论板数35块,原料液第24块板进料,溶剂第7块板进料,溶剂比1. 2,回流比3. 2,塔顶回收正丙醚含量为99. 88%;溶剂回收塔理论塔板数25块,原料第6块板进料,回流比0. 7,塔顶回收正丙醇含量为99. 86%。在此优化工艺条件下,二者回收率均在99. 5%以上,达到了在原工艺中循环套用要求。在模拟优化的基础上进行萃取精馏实验,实验结果与模拟结果吻合较好,验证了模拟结果的可靠性。     

Synthesis and properties of a cellulose exchanger with the crown ether diaminodibenzo-17-crown-5 as anchor group

A new cellulose exchanger was synthesized from “o-aminophenolcellulose” by diazotation and coupling with diaminodibenzo-17-crown-5. The distribution coefficients for Ca²⁺, Sr²⁺, Ba²⁺, Na⁺ and K⁺ were determined in water/methanol mixtures as a function of the water content. Separation of Ca²⁺, Na⁺ and K⁺ and fractionation of the calcium isotopes ⁴⁸Ca and ⁴⁰Ca were investigated. The enrichment factor ε = 4.9 · 10^?3 for ⁴⁸Ca²⁺ is appreciably higher than that found for cation exchange resins with ? SO₃H groups, but lower than that reported for certain cryptands.     

杂多酸盐催化乙二醇合成乙二醇乙醚和乙二醇双乙醚的研究

以磷钨酸、硅钨酸和磷钼酸及硝酸银、硝酸铁、硝酸铯和碳酸铯为原料,通过共沉淀法制备了系列杂多酸盐催化剂,通过X射线衍射仪(XRD)、电子能谱(EDS)、热重/差热分析仪(TG)对催化剂的晶型结构、表面元素及热重性质进行了表征。结果表明,磷钨酸银铯和磷钨酸银具有Keggin型磷钨酸结构,表面元素分布均匀,煅烧温度在20～220℃时会失去结合水,300～450℃时会失去结晶水和结构水,900℃以上则会分解。通过催化乙二醇和乙醇合成乙二醇乙醚和乙二醇双乙醚的反应考察杂多酸及杂多酸盐催化性能。考察了阳离子种类、取代度和不同煅烧温度对杂多酸盐催化性能的影响,结果表明,磷钨酸及其盐系列催化剂效果最好。通过考察阳离子种类和磷钨酸氢离子的取代度,结果表明,Cs_(0.66)Ag_(0.33)H_2PW_(12)O_(40)催化效果最好。在该催化剂存在下,n_(乙二醇)∶n_(乙醇)为1∶4,反应时间4 h,反应温度200℃,乙二醇转化率为98.16%,乙二醇乙醚选择性为49.25%,乙二醇双乙醚选择性为48.59%,乙二醇醚的总产率为96.04%。     

合成气一步法制二甲醚过程的热力学模拟研究

使用Aspen plus软件对合成气一步法制二甲醚过程进行热力学模拟计算。考察了温度、压力、合成气组成及CO2体积分数对CO转化率、二甲醚选择性和产率的影响。模拟结果与文献实验结果相比对,具有较好的一致性。     

Mass spectrometric analysis of long chain alk-1-enyl ether esters and alkyl ether esters of diols

The mass spectra of homologous series of long chain alk-1-enyl ether esters and alkyl ether esters of short chain diols were determined, and general patterns of fragmentation were established. Both types of diol lipids yielded ions characteristic of the alkoxy or alk-1-enyloxy moiety and the acyl moiety, as well as ions indicative of the constituent short chain diol. Prominent ions were formed from both types of ether esters due to the loss of the alkoxy or alk-1-enyloxy moieties giving rise to ions for which cyclic structures are proposed. High resolution mass spectrometry and deuterium labeling techniques were used to verify the composition of ions and to substantiate fragmentation mechanisms. This is part VII in the series “Naturally Occurring Diol Lipids” (part VI is Reference 1) and part VIII in the series “Mass Spectrometry of Lipids” (part VII is Reference 23).