On-column injection onto capillary columns. Part 2: Study of sampling conditions; practical recommendations

During one year continuous use of on-column injection, the typical advantages described in our first report have fully been confirmed. In addition the analysis of large sample volumes has proved promising. Only minor modifications have been applied to the on-column injector device. Broad evidence has been gathered showing that full separation efficiency of the capillary columns after on-column injection is attained only when cold trapping or the solvent effect, as band shortening mechanisms, are working- While, under the conditions of on-column injection, cold trapping is less efficient than with other injection techniques, the opposite holds true for the solvent effect. Compared with splitless injection, the danger of excessive solvent condensation on the column is increased. A working rule is presented for establishing the optimal chromatographic conditions for handling large sample volumes while ensuring full separation efficiency yet avoiding harm to the column.     

Application of size exclusion chromatography to the structural study of polyorganometallosiloxanes

Size exclusion chromatography was employed to elucidate the structure of the organosiloxane moiety in trimethylsiloxy derivatives of organometallosiloxanes containing Na, K, Ni, Mn, Cu, and Fe. An efficient technique of trimethylsilylation of organometallosiloxanes was developed to minimize alterations in their structure. The TMS derivatives of organometallosiloxanes were found to exist mostly as a more or less polydisperse mixture of cyclic poly[phenyltrimethylsiloxy siloxane]s. The preferred size of the cycles depends primarily on the nature of the metal in organometallosiloxane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1057–1062, June, 1994.This work was performed with the financial support of the Russian Foundation for Basic Research (Grant No. 93-03-18121).     

Influence of particle diameter distribution on protein recovery in the expanded bed adsorption process

The General Rate model has been developed and solved to describe protein adsorption in an expanded bed. The model takes into account axial and local variation of particle size distribution (PSD), external and intra-particle mass transfer resistances, and dispersion in liquid phase. The influence of PSD on breakthrough profiles has been analysed. The simulation results show that for a significantly high expanded bed the lower part of the breakthrough curve profiles, calculated for local particle size distribution (LPSD) and for axial average particle size distribution (APSD) are very similar. However, the upper part of breakthrough profiles calculated for LPSD approaches inlet concentration much more slowly than those calculated for APSD. The retention times of the lower part of uptake curves calculated with average particle diameter are constantly shorter than those obtained from LPSD. For the calculation of the dynamic capacity (DC), the LPSD can be replaced by APSD for large expanded bed heights. Using breakthrough profiles calculated for average particle size, DC values are constantly underestimated.     

不同环大小分子筛对钼基分子筛催化剂上甲烷无氧芳构化反应的影响

 钼基分子筛催化剂，由于不同分子筛的孔道大小及孔道形状不同\r\n，对甲烷芳构化反应表现出不同的催化性能．具有8元环孔道结构的小\r\n孔ERS－7分子筛没有催化活性，说明甲烷的芳构化反应离不开分子筛孔\r\n道的择形作用，较小的孔道中不能生成苯等芳烃．具有10元环孔道结构\r\n的ZSM－5，ZSM－11和ZRP－1三种分子筛具有较好的催化性能，但由于\r\n其孔道大小及孔道形状的差别在催化行为上表现出一定的差异．具有1\r\n0元环和12元环孔道结构的MCM－22分子筛，尤其对苯等轻芳烃而言，催\r\n化性能最佳．具有12元环孔道结构的JQX－1以及中孔分子筛SBA－15，\r\n虽然具有一定的催化性能，但活性较低．研究结果表明，孔道大小与苯\r\n分子动态直径相近或孔道稍大的分子筛是催化甲烷芳构化反应的良好载\r\n体，孔道过大或过小都不利于苯和萘等芳烃的生成．     

通过密度函数理论表征炭质吸附剂的孔径分布

通过密度函数理论（DFT-DensityFunctionalTheory）对炭质吸附剂的孔径分布进行了表征。该法以多孔固体上N2吸附分子模型为依据，用一种方法对多孔固体的孔径分布从微孔到大孔范围进行确定。本文用该法对自制的聚丙烯腈活性炭纤维、国产煤质活性炭及日本产活性炭微球等六种炭质吸附剂的孔径分布进行了表征。     

聚合物共混物脆韧转变性能研究 Ⅱ准韧性聚合物共混物脆韧转变的几何模型

给出了分散相粒间基体层厚度Ｔ与分散相粒径（ｄ）、粒径分散度（σ）和分散相体积分数（）的定量关系式．发现σ对Ｔ的影响与有关，不仅Ｔ随σ的增大而增大，而且越大，这种影响越显著．用计算机图像分析仪直接测定了聚氯乙烯／丁腈橡胶、聚丙烯（ＰＰ）／三元乙丙橡胶、ＰＰ／乙烯 醋酸乙烯酯共聚物共混物的Ｔ，发现这三种共混物的Ｔ近似于对数正态分布．理论预示与实验结果很好符合．     

Nd-Fe-B磁体烧结过程晶粒长大行为的研究

定量描述了Nd-Fe-B磁体烧结过程晶粒长大行为，分析了烧结温度、烧结时间、合金粉末粒度及其分布对烧结过程晶粒长大的影响，讨论了烧结过程晶粒长大机制。在Nd-Fe-B磁体烧结过程开始之后的0—1h时间区段，晶粒长大迅速；随着烧结时间的延长，晶粒长大速度减小。合金粉末平均粒度增大，或者合金粉末粒度分布范围增宽，显著促进Nd-Fe-B磁体烧结过程中晶粒的长大。在Nd-Fe-B磁体的烧结过程中，存在两类晶粒长大机制，即Nd2Fe14B颗粒的溶解与析出、Nd2Fe14B颗粒的并合与长大。Nd2Fe14B颗粒的并合与长大不仅使磁体的平均晶粒尺寸增大，也使晶粒尺寸分布范围增宽，是烧结Nd-Fe-B磁体显微组织中出现异常大晶粒的根本原因。     

Estimation of the size of liposomes by modified HDC

Internal calibration in modified hydrodynamic chromatography has been realized by the approach of Prieve and Hoysan, i.e. the use of polystyrene monodisperse latexes to evaluate the equivalent capillary radius, R. The value obtained has been used to estimate the average sizes of a variety of liposome samples from egg yolk lecithin.     

Preparation of Small Particle Sized ZnAl-Hydrotalcite-Like Compounds by Ultrasonic Crystallization

Ultrasonic technology has been intensively studied recently due to its special features. In this paper, an ultrasonic crystallization method was introduced for the preparation of ZnAl-Hydrotalcite-Like compounds (ZnAl-HTLcs). Samples with high crystallinity, small particle size and narrow particle size distribution were obtained and fully characterized using conventional techniques of XRD, FT-IR and TGDTA. The results prove that both ultrasonic frequency and ultrasonic power have effects on the sizes of the product particles. By varying the ultrasonic power from 250 W to 88 W, with the ultrasonic frequency fixed at 59 kHz, the median particle size of the samples increased from 0.37 μm to 0.82 μm. By altering the hydrothermal treatment time from 1 h to 5 h at 110℃, the median particle size of ZnAl-HTLcs synthesized via ultrasonic crystallization increased from 0.88 μm to 1.11 μm.     

Electrochemistry of capillary systems with narrow pores. IV. Dialysis potentials

The dialysis potentials of different collodion membranes with graded pore sizes and electrochemical activities have been measured in dilute aqueous KCl solutions as functions of concentration. It is possible to predict the value of the diffusion potential within a few millivolts on the basis of electrical conductivity data obtained with the same membranes. In general, the measured values are lower than those calculated. It is assumed that this difference is caused by the membranes having a distribution of pore sizes.