双膦胺配体氮原子上取代基的空间和电子效应对于乙烯四聚催化体系的影响

在乙酰丙酮铬、甲基铝氧烷（MAO）、配体三元催化体系中,以乙烯为原料在高压下齐聚生成1-辛烯．主要考察N原子上取代基不同的PNP配体对催化荆活性及1-辛烯选择性的影响结果表明．苯环取代基为3．5-二甲基的配体效果较为理想,其活性达到4990kg／（mol·h）．对1-辛烯选择性为72．31％。PNP配体中苯环取代基上间、对位给电子基团有助于提高催化活性和1-辛烯选择性．而空间位阻较大的基团和吸电子基团则不利于催化反应。     

Steric and Electronic Effects in Basic Dyes. II—Electronic Absorption Spectra of Derivatives of Malachite Green Containing Electron-withdrawing Substituents in the Phenyl Ring

Absorption spectra of several derivatives of Malachite Green containing electron-withdrawing groups in the phenyl ring have been examined. Substituents in the 3- or 4-position modify the position of the first-frequency band to an extent approximately linearly related to the appropriate Hammett substituent constant. Although substituents in the 2-position show an ortho effect, the intensities of the first bands are generally lower than those of derivatives containing electron-donating groups.     

Steric requirements for the stimulation of glycosyltransferase activity by lysophosphatidylcholine

1-Palmitoyl-sn-glycerol-3-phosphocholine and 3-palmitoyl-sn-glycerol-1-phosphocholine have been found to be equipotent in the stimulation of membrane-bound glycosyltransferases in microsomes of rat intestinal villus cells. This indicates that the stimulatory effect of lysophosphatidylcholine is not stereospecific, but that it may be related to a specific detergent property dependent upon the peculiar balance of hydrophilic and hydrophobic components in the molecule.     

烷基糖苷合成工艺中催化剂体系的研究

利用转糖苷化法合成烷基糖苷,对合成烷基糖苷的催化剂体系做了一定改进,并对催化剂的用量做了研究,确定了合成烷基糖苷的最优催化剂体系。     

葡萄糖酶法生物合成烷基糖苷工艺

采用葡萄糖酶法生物合成烷基糖苷,考察了工艺条件对合成烷基糖苷的影响.结果表明m(水)m(乙醇)=37,反应温度为42℃,反应体系pH=5.8;用此法,葡萄糖苷酶活力最高可达75.2×10-3(mg/mL2.min),产品聚合度d.p.=1.43.探讨了该产品的表面性能.     

高活性酯化催化剂烷基锡酸的研究

以松香树脂酸的酯化反应为例,研究了烷基锡酸对酯化反应的催化作用,系统的探讨了影响反应的各种因素。     

Studies on the Decomposition of Alkyl Hydroperoxides by different catalysts

The catalytic decomposition of cumene, 1-methylcyclohexyl and cyclohexyl hydroperoxides was studied in cyclohexane, cis- and trans-1,4-dimethylcyclohexane and cis-pinane as the solvents. The stearates and the acetylacetonates of manganese, cobalt and chromium, the acetylacetonates of molybdenum and vanadium, n-butyl orthoborate and n-butyl metaborate were used as the catalysts. The chromium-, vanadium-, molybdenum- and boron-containing catalysts brought about some Hock-type decomposition of cumene hydroperoxide and thus proved to be acidic. Of these more of less acidic catalysts only molybdenyl acetylacetonate effected a partially stereospecific hydroxylation of the tertiary C H-bonds in cis- and trans-1,4-dimethylcyclohexane. The well-known selectivity of chromium catalysts for the ketone formation during the decomposition of secondary hydroperoxides is caused by the catalytic oxidatio of secondary alcohols by hydroperoxides in the presence of chromium compounds. In the presence of all the catalysts used the free-radical pathways of the hydroperoxide decomposition predominated, and the attack of the intermediate radicals on the starting hydroperoxide was more important than the attack on the solvent molecules.     

The Influence of Alkyl Chain Length and Steric Effect on the Stability Constants and Extractability of Co(II) Complexes with 1-Alkyl-2-Methylimidazoles

Using the liquid-liquid partition method, the formation of Co(II) complexes with 1-alkyl-2-methylimidazoles (where alkyl = C₄H₉ trough C₁₂H₂₅) at 25°C and at a fixed ionic strength of the aqueous phase (I = 0.5, (HL)NO₃, KNO₃) were studied. Dichloromethane, trichloromethane, and 2-ethylhexanol were used as diluents. The tetrahedral and octahedral complexes were formed. Stability constants (β_n) of the complexes as well partition ratios (P_n) of the extracted species were determined. It was shown that both β_n and P_n increased with an increasing 1-alkyl chain length. Tetrahedral complexes are more readily extractable by organic solvent. Their P_n values are the highest.     

烷基苯磺酸钠／烷基二苯醚双磺酸盐复配体系的洗涤性能研究

主要考察了烷基苯磺酸钠（LAS）与十六烷基二苯醚双磺酸盐（D8390）复配体系在不同复配比、不同浓度、不同水硬度、不同温度条件下对不同种类污布的洗涤能力。结果表明：（1）对于碳黑、皮脂两种污布,单独D8390的洗涤能力不及LAs,LAS／D8390复配体系在w（LAS）：w（D8390）=8：2—7：3范围内洗涤能力最高;（2）对于蛋白污布,单独D8390的洗涤能力明显高于LAS,且在两者复配体系中,随着D8390含量的增加,洗涤能力先快速增大,在w（LAS）：W（D8390）=3：7时达到最高点,之后略降低。（3）在W（LAS）：W（D8390）=7：3的复配体系中,活性物总质量浓度在0．10％-0．20％范围内,质量浓度对碳黑、皮脂两种污布的洗涤能力影响不明显,但随着浓度的降低,对蛋白污布的洗涤能力明显降低;（4）采用LAS与D8390进行复配,可以明显改善体系在高硬度、低温下的洗涤能力。     

固定床催化合成烷基硫醇

介绍了固定床多相催化合成烷基硫醇的工艺流程。分析了以烷基醇与硫化氢为原料取代反应合成烷基硫醇可能发生的化学反应。采用固定床多相催化方法合成了多种烷基硫醇,其中正丙硫醇收率为92.5%、异丙硫醇收率达到65%、正丁基硫醇收率为76.6%、正十二烷基硫醇收率超过78%。介绍了合成以上烷基硫醇的反应温度、反应压力、原料进料配比等制备条件。     

环己酮生产中烷水分离系统的改造

分析了环己酮生产中烷水分离系统产生腐蚀的原因, 结合实际提出了解决腐蚀的措施, 解决了烷水分离系统的腐蚀问题。     

多聚磷酸法烷基磷酸酯的合成研究

用多聚磷酸与十六醇为原料制备出烷基磷酸酯。结果表明：当磷酸中五氧化二磷含量为７９９８％,十六醇与磷酸摩尔比为０９０,温度为７５℃的条件下反应６ｈ,单酯收率可达９３４％,酯总收率为９４５％。     

烷基季铵盐改性膨润土的研究

考察了系列烷基季铵盐对膨润土有机化的效果和层间距变化,比较了两种钠化剂(Na2CO3和NaF)改性的膨润土对有机化的影响。实验结果表明,以NaF改性的膨润土获得了更佳的有机化效果和更大的层间距。在所考察的系列长链季铵盐有机化结果中,十八烷基二甲基苄基氯化铵(1827)和双十八烷基二甲基氯化铵(D1821)改性得到的层间距最大,分别为3 03nm和2 81nm。     

转糖苷化法合成烷基糖苷工艺研究

采用转糖苷化法合成烷基糖苷,考察了原料配比、催化剂用量和反应温度等因素对产率的影响,得到了最佳反应条件:m(催化剂)∶m(丁醇)=0.011∶1;n(正丁醇)∶n(高碳醇)=1∶1;n(丁醇)∶n(葡萄糖)=3∶1。经过H2O2脱色,反应温度为110℃~115℃,反应时间为4 h,葡萄糖的转化率达到98%。实验结果表明:影响产率的主要因素为催化剂和葡萄糖的配料比。     

电位滴定法测定烷基氧化胺及其游离烷基胺

采用电位滴定法测定十二烷基二甲基氧化胺及其残留十二烷基二甲基胺的含量,同时不介绍计算终点的数学公式。此方法准确性好,简便,易于操作。适用于烷基氧化胺及其游离烷基胺的检测。     

Insights into the Optimization of Alkyl Phenol/Alkyl Halide Ratio in Gemini Surfactant Synthesis

¹H NMR and thin layer chromatography (TLC) were applied to analyze the component of two series of synthesized sulfonated Gemini surfactants with different spacer lengths (2, 4, and 6 carbons) and hydrophobic chain lengths (9, 12 carbons). Gemini surfactants were prepared by reacting alkylphenol with alkyl halide followed by sulfonation with chlorosulfonic acid. The influence of the molar ratio of alkyphenol to alkyl halide on the mono‐ to diether ratio was investigated and the results indicated that the molar ratio is a key factor to minimize impurities in the target material, due to the high reactivity of alkyl halide. In addition, the results showed that alkyl halide with a shorter spacer group length required a higher molar ratio of alkyl halide to alkylphenol. To synthesize the intermediate Gemini product with 80 % diether content, the molar ratios were optimized using n(alkylphenol):n(1,6‐dibromohexane) = 1:0.55, n(alkylphenol):n(1,4‐dibromobutane) = 1:0.7, and n(alkylphenol):n(1,2‐dibromoethane) = 1:2.5, respectively.     

GC-MS测定水中烷基汞的方法研究

烷基汞是汞在自然界中的一种有机物形态。广泛存在于大气环境、水环境及土壤环境中。文章主要介绍了如何使用巯基棉提取水中的烷基汞、并用GC-MS测定烷基汞。在保证测试结果准确的前提下,改进了洗脱速率和洗脱装置,本法的检出限为：甲基汞（MMC）10ng／L,乙基汞（EMC）10ng／L。     

烷基多苷的研究进展

概括了新型表面活性剂——烷基多苷的研究进展 ,对其合成技术、催化剂、后处理、分析测试、应用等方面的研究动态进行了评述 ,提出了当前国内烷基多苷的研究和应用所面临的问题 ,展望了烷基多苷在国内的发展前景。     

Photovoltaic Study of Photoelectrochemical Biofuel Cells Sensitized by Porphyrin Derivatives with Different Substituents

Two porphyrin derivatives with different substituents were investigated as dyes for the titanium dioxide (TiO₂) film electrode to construct new two-compartment photoelectrochemical biofuel cells (PEBFCs). The two porphyrin derivatives were tetrakis(4-carboxyphenyl)porphyrin (TCPP) and meso-tetra(p-hydroxyphenyl)porphine (THPP). To determine how cell performance was affected by the dye with different substituents, we analyzed the photochemical and photoelectrochemical properties of the two dyes by physical characterization and photoelectrochemical experiments. The UV–Vis absorption spectra and X-ray photoelectron spectra indicated that the interactions between the dye and TiO₂ decreased in the order of TCPP > THPP, which was also in accord with the results of Fourier transform infrared. In addition, TCPP and THPP were calculated using the density functional theory and the time-dependent density functional theory, and the calculation result exhibited that the radiative lifetime decreased in the order of TCPP > THPP. Compared with THPP, TCPP with longer excited-state was expected to enhance the performance of a PEBFC. We measured and compared the incident photon-to-collected electron conversion efficiency and the light-to-electrical conversion efficiency (η) of the porphyrin-sensitized photoelectrochemical biofuel cell. The photovoltaic characteristics showed the TCPP was more effective compared to the THPP, which obviously showed that the experimental results were consistent with theoretical expectation. These results revealed that the kind of the substituent for the porphyrin influenced the photovoltaic properties of the PEBFC.