变温红外光谱研究多嵌段聚氨脂脲的微相分离行为

用傅里叶变换红外光谱方法研究了热处理对由聚环氧丙烷聚醚多元醇、３．５－二乙基甲苯二胺和４，４－二苯基甲烷二异氰酸酯组成的多嵌段聚氨酯脲（ＳＰＵＵ）的微相分离行为的影响．从室温逐步升温到３１０℃的过程中，氨基甲酸酯键（ＵＴ）之间形成的氢键大量解离，而脲键（ＵＡ）之间形成的、具有平面状双分叉结构的氢键在１３０～２００℃范围却大量生成；从３１０℃缓慢冷却到室温后，部分游离的ＵＴ重新形成氢键，而硬段之间形成的ＵＡ氢键的含量又有所增加．结果表明：高温热处理可以有效地提高ＳＰＵＵ的微相分离程度．     

Modification of silica gel with diethylamino group by novel reaction and its characterization

1,3,5,7-Tetramethylcyclotetrasiloxane (H₄) was deposited on silica gel at 80°C by utilizing a chemical vapor deposition (CVD) method, where it was catalytically polymerized to form a surface coating of polymethylsiloxane (PMS). Treated silica gel (PMS-Si) increased in weight up to a plateau level, and there was no further increase with increasing reaction time. The film of PMS was partially cross linked; typical values of crosslinking ratio and film thickness were 2% and 0.6 nm, respectively. An anionic ion exchanger containing diethylamino groups was synthesized from PMS-Si by hydrosilylation of allyl glycidyl ether followed by treatment with diethylamine. Its structure was confirmed by¹³C and²⁹Si CP/MAS NMR spectroscopy and FT-IR spectrophotometry. Characterization of silica gel (DEA-Si) modified with diethylamino group was evaluated by a packing of the column for liquid chromatography. As a mixture of five nucleotides was completely separated, it was recognized that DEA-Si was operated by ion exchange action. Because the surface of the silica gel was covered with hydrophobic PMS, the peak heights and retention times did not change after washing of the column with alkaline solution.     

Determination of metoprolol enantiomers in human urine by GC-MS using (−)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride as a chiral derivatizing agent

Summary A method for the assay of R-(+)- and S-(−)- metoprolol in human urine has been developed using gas chromatography-mass spectrometry. The method involved purification by liquid-liquid extraction and derivatization with N-methyl-N-(trimethylsilyl)trifluoroacetamide to form an O-silyl ether, followed by subsequent chiral derivatization with (−)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride to form diastereomeric amide. The reaction was rapid and the diastereomeric derivatives were well resolved. Quantitation was performed by selected-ion monitoring of fragment ions of the diastereomers in electron impact ionization mode. No racemization was found during the reaction. The detection limit was 0.5 ng·mL⁻¹. The intra-day variation ranged between 0.38 and 7.86% in relation to the measured concentration and inter-day variation was 2.26–8.06%. The method has been applied to the determination of R-(+)-and S-(−)- metoprolol in human urine from healthy volunteers dosed with racemic metoprolol tartrate.     

液膜法处理含氟废水

为了防止含氟废水的污染,人们研究了多种除氟方法,液膜技术是一项新的分离工艺,它操作简单,试剂用量少,有机相可重复利用。本文利用伯胺作迁移载体处理高含量的含氟废水,分离效率较好。 伯胺N_(1923)(简写RNH_2)为流动载体,上胺N_(205)(上海石油化工厂)为表面活性剂,煤油为溶剂。将内相CaCl_2,溶液与油相(含N_(1923)、N_(205)和煤油)按一定体积比例混合,高速搅拌,制成W/O     

吸附理论的研究进展及其在吸附分离中的应用

综述了吸附理论的进展及其在吸附分离中的应用,并介绍了对气体分离过程至关重要的混合气的吸附模型或关联式。     

The effects of polymer chain rigidification, zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite A mixed matrix membranes

The polyethersulfone (PES)-zeolite 3A, 4A and 5A mixed matrix membranes (MMMs) were fabricated with a modified solution-casting procedure at high temperatures close to the glass transition temperatures (T_g) of polymer materials. The effects of membrane preparation methodology, zeolite loading and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. SEM results show the interface between polymer and zeolite in MMMs experiencing natural cooling is better (i.e., less defective) than that in MMMs experiencing immediate quenching. The increment of glass transition temperature (T_g) of MMMs with zeolite loading confirms the polymer chain rigidification induced by zeolite. The experimental results indicate that a higher zeolite loading results in a decrease in gas permeability and an increase in gas pair selectivity. The unmodified Maxwell model fails to correctly predict the permeability decrease induced by polymer chain rigidification near the zeolite surface and the partial pore blockage of zeolites by the polymer chains. A new modified Maxwell model is therefore proposed. It takes the combined effects of chain rigidification and partial pore blockage of zeolites into calculation. The new model shows much consistent permeability and selectivity predication with experimental data. Surprisingly, an increase in zeolite pore size from 3 to 5 Å generally not only increase gas permeability, but also gas pair selectivity. The O₂/N₂ selectivity of PES-zeolite 3A and PES-zeolite 4A membranes is very similar, while the O₂/N₂ selectivity of PES-zeolite 5A membranes is much higher. This implies the blockage may narrow a part of zeolite 5A pores to approximately 4 Å, which can discriminate the gas pair of O₂ and N₂, and narrow a part of zeolites 3A and 4A pores to smaller sizes. It is concluded that the partial pore blockage of zeolites by the polymer chains has equivalent or more influence on the separation properties of mixed matrix membranes compared with that of the polymer chain rigidification.     

Data loci in algebraic optimization

We consider parametric optimization problems from an algebraic viewpoint. The idea is to find all of the critical points of an objective function thereby determining a global optimum. For generic parameters (data) in the objective function the number of critical points remains constant. This number is known as the algebraic degree of an optimization problem. In this article, we go further by considering the inverse problem of finding parameters of the objective function so it gives rise to critical points exhibiting a special structure. For example if the critical point is in the singular locus, has some symmetry, or satisfies some other algebraic property. Our main result is a theorem describing such parameters.     

Extragradient and extrapolation methods with generalized Bregman distances for saddle point problems

In this paper, we introduce two Bregman-type algorithmic frameworks to generalize the extragradient and extrapolation methods. With the help of relative Lipschitzness and the Bregman distance tool, the iteration properties of the proposed frameworks are analyzed. As applied to smooth convex-concave saddle point problems, our theory rediscovers the main results in Mokhtari et al. (2020) [14] for wider frameworks under weaker assumptions via a conceptually different approach.     

Enantiomeric resolution of anti-HIV agents on a cellulose derivative chiral stationary phase

Summary Anti-HIV enantiomeric 1H, 3H-thiazolo[3, 4-a] benzimidazoles have been stereospecifically analyzed by elution on a column of cellulose tris-(4-methyl-phenylbenzoate)ester adsorbed on macroporous silica (Chiralcel^R OJ).The enantiomeric resolution of the compounds examined is linked to a complex and competitive contribution of different factors.     

Misclassification minimization

The problem of minimizing the number of misclassified points by a plane, attempting to separate two point sets with intersecting convex hulls inn-dimensional real space, is formulated as a linear program with equilibrium constraints (LPEC). This general LPEC can be converted to an exact penalty problem with a quadratic objective and linear constraints. A Frank-Wolfe-type algorithm is proposed for the penalty problem that terminates at a stationary point or a global solution. Novel aspects of the approach include: (i) A linear complementarity formulation of the step function that counts misclassifications, (ii) Exact penalty formulation without boundedness, nondegeneracy or constraint qualification assumptions, (iii) An exact solution extraction from the sequence of minimizers of the penalty function for a finite value of the penalty parameter for the general LPEC and an explicitly exact solution for the LPEC with uncoupled constraints, and (iv) A parametric quadratic programming formulation of the LPEC associated with the misclassification minimization problem.This material is based on research supported by Air Force Office of Scientific Research Grant F49620-94-1-0036 and National Science Foundation Grants CCR-9101801 and CDA-9024618.