烷基聚葡糖苷溶液的表面吸附平衡与动力学

用吊片法和气泡最大压力法分别测定了烷基聚葡糖苷(APG)C₉.₆G_1.3水溶液的平衡和动态表面张力,研究了APG水溶液表面的吸附平衡、动力学及其影响因素.测得其cmc(临界胶束浓度)为0.032g/L.吸附过程由初始的扩散控制转变到势垒控制,吸附势垒为4～7kJ/mol.温度升高,平衡和动态表面张力均减小,吸附量增加;加入无机盐,平衡和动态表面张力增大,吸附量亦增加;醇类的吸附使动态表面张力下降速率加快,表明APG与醇分子间有协同吸附作用.     

Isocratic Separation of Dansylated Biogenic Amines on a C8‐Bonded Silica Column under the LC Elution of Methanol‐Based Mobile Phase

Under the elution of methanol‐based mobile phase, the isocratic resolution of 12 biogenic amines, including 1 aromatic, 2 heterocyclic and 9 aliphatic amines, as the dansylated derivatives has been accomplished in less than 25 minutes on a 15 cm C₈‐bonded column. The resolution can not be reproduced on other examined alkyl‐bonded phases (e.g., C₄ and C₁₈) under the same chromatographic conditions, or in the reversed‐phase mode. The retention, mainly as a result of hydrophobic interaction between analyte and stationary phase, can be adjusted by varying the percentage of methanol in the mobile phase. Also, incorporating acetic acid as additive to the mobile phase to protonate the analyte and silanol groups that are little shielding on the surface of silica gel reduces the dipole‐dipole interaction, and thus the retention scale, which in turn deteriorates the resolution. Furthermore, the elution reversal is plausible for some of analytes as a greater percent of acetic acid is used in the elution. Values of correlation coefficients (R²) range between 0.9995 and 0.9996, indicating good linearity.     

Synthesis and the effect of alkyl chain length on photochromic properties of diarylethene derivatives

A new class of photochromic diarylethenes bearing pyrrole and thiophene units with different length of alkyl chains at 2-position of thiophene rings have been synthesized. Their characteristics, including photochromism and fatigue resistance were investigated systematically, and each diarylethene derivative showed good photochromic properties whether in solution or in PMMA films. The alkyl group moiety was connected directly to the central cyclopentene ring as a heteroaryl unit and availably participated in photoisomerization reaction. And some properties, for example, the conversion ratio in the photostationary state(PSS) and the absorption coefficient of the ring-closed isomers in acetonitrile were significantly affected by the alkyl chain length. The results revealed that substituents of alkyl chain played an important role in the photoisomerization process of diarylethenes.     

十四烷基芳基磺酸盐形成的分子有序组合体

以表面张力法、碘光谱法、水增溶法和相态图法研究了自制的三种十四烷基芳基磺酸盐在不同条件下形成的分子有序组合体(胶束、反胶束和微乳液),并考察了分子结构、溶剂、无机盐和短链醇等对其的影响.结果表明:增加十四烷基芳基磺酸盐分子亲油基支化度,不利于其在水溶液或混合极性溶剂(乙二醇-水)中形成胶束而有利于其在非极性溶剂正庚烷中形成反胶束;溶剂极性的降低,促使表面活性剂溶液由胶束溶液→单体溶液→反胶束溶液转变;无机盐或短链醇的加入促进了水溶液中胶束的形成,且反离子价态数或醇烷基碳原子数越大,越有利于胶束形成;无机盐浓度的增加导致表面活性剂/正丁醇/正辛烷/NaCl/水形成的微乳液体系在一定温度下发生由WinsorI→WinsorIII→WinsorII型的转变.     

A molecular mechanics (MM3) study of fluorinated hydrocarbons

A molecular mechanics study of small saturated hydrocarbons (up to C-6), substituted by up to six fluorines was carried out with the MM3 force field. Perfluorobutane and Teflon were also studied. A parameter set was developed for use in the calculation of bond lengths, bond angles, torsion angles, conformational energies, barriers to rotation, dipole moments, moments of inertia and vibrational frequencies for these compounds. The results are in good agreement with experiment when only one or two fluorines are present, but some rather large discrepancies were noted when the F/H ratio becomes high. These can be taken into account only by using a force field more complicated than MM3. Some of the requirements of such a force field are delineated. Some pertinent ab initio results are also reported in this article.     

Gas chromatographic retention of alkyl phosphates on ionic liquid stationary phases

Retention behaviors of alkyl phosophates were studied on a series of ionic liquid gas chromatography columns. The selectivity of the IL columns for alkyl phosphates were compared with a 5% phenyl column as a route to evaluating the potential use of IL columns in the analysis of alkyl phosphates in petroleum samples in both one- and multi-dimensional GC. Most interestingly, we demonstrate for the first time the dependence of elution order on separation temperature for members of a homologous series of compounds. At low temperatures it was found that trihexyl phosphate eluted before trioctyl phosphate, while at higher temperatures this pattern was reversed.     

高分子造纸助剂的设计及作用机理研究Ⅱ.用XPS解析N-氯代聚丙烯酰胺与水和醇的反应

用X 射线光电子能谱仪 (XPS)对聚丙烯酰胺的部分N 氯代衍生物 (简称N 氯代聚丙烯酰胺 )与水、1 丙醇的反应产物进行了表征 .实验结果表明 ,在弱碱性水溶液中N 氯代聚丙烯酰胺 (N Cl PAM)的N 氯代酰胺基的 93%转化成—CONHCONH—结构 ,而在 1 丙醇水溶液中 ,91 8%的N 氯代酰胺基转化为—CONHCONH—和—NHCOO—结构 ,二者比例为 78 0∶13 8.可以推论N Cl PAM在中性造纸条件下 ,可通过自身结合形成网络结构或与纤维羟基反应形成共价键 ,从而达到增强纸的干、湿强度效果     

Effective electrodeposition of Co-Ni-Cu alloys nanoparticles in the presence of alkyl polyglucoside surfactant

The effect of alkyl polyglucoside (APG) surfactant on the electrodeposition Co-Ni-Cu alloys nanoparticles has been investigated. In a typical electrodeposition experiment, it was found that as prepared Co-Ni-Cu alloys nanoparticles characteristics, such as size homogeneity, density, dispersion on the electrode substrate and the chemicals composition, depended strongly on the concentration of APG used in the reaction as well as the applied deposition potential. For the case of chemicals composition, low APG concentration (below CMC) was found to be effective for the preparation of excellent composition of the nanoalloys. Meanwhile, for the case of size homogeneity, density, and dispersion on the surface, high APG concentration (above CMC) and high deposition potential were preferred. It was also found that, at concentration above the CMC, the APG surfactant showed a metals ions deposition inhibition characteristic that caused increasing in the electrodeposition overpotential of the entire metals ions, namely cobalt, nickel and copper. As the result the copper was found to place a high percentage in the nanoalloys deposits. Owing to its simple procedure in controlling the composition and the nanoalloys growth characteristic, present approach should find a potential application in preparing Co-Ni-Cu magnetic nanoparticles for used in currently existing applications.     

One‐Pot Synthesis of Pentaalkyl 7‐[(Alkylamino)carbonyl]‐2‐oxa‐1‐azabicyclo[3.2.0]hept‐3‐ene‐3,4,5,6,7‐pentacarboxylate

Dialkyl acetylenedicarboxylates react with alkyl 2‐nitroethanoates in the presence of alkyl isocyanides in a one‐pot reaction to afford the title compounds in 78–90% yield.     

On the Reaction between Alkyl Isocyanides and Ethynyl Phenyl Ketone in the Presence of N,N′-Dimethylbarbituric Acid

Summary.  The reactive 1:1 intermediate produced in the reaction between alkyl isocyanides and ethynyl phenyl ketone was trapped with N,N ′-dimethylbarbituric acid to produce alkyl 1,3-dimethyl-2,4-dioxo-7-phenyl-1,3,4,5-tetrahydro-2H-pyrano[2,3-d]pyrimidine-5-carboxamides in good yields. Corresponding author. E-mail: isayavar@yahoo.com Received January 8, 2002. Accepted January 14, 2002