Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Dynamic Strategic Pricing and Speed of Diffusion

Defining speed of diffusion as the amount of time it takes to get from one penetration level to a higher one, we introduce a dynamic model in which we study the link between pricing policy, speed of diffusion, and number of competitors in the market. Our analysis shows that, in the case of strategic (oligopolistic) competition, the speed of diffusion has an important influence on the optimal pricing policy. In particular, we find that higher speeds of diffusion create an incentive to strategically interacting firms to lower their prices.     

电镀污水净化新工艺--电浮选方法简介

综述了电浮选方法处理电镀污水的基本原理和提高电浮选净水技术的途径。重点介绍了俄罗斯门捷列夫化工大学的电浮选两种新工艺方法。     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003     

A new type of two-dimensional packed + capillary column GC system. I. Theory

Summary To match the need of high efficiency capillary column (plate number N₂, Plate height H₂ and carrier gas linear velocity U₂), a new high efficiency packed column (N₁, H₁ and U₁) at high carrier gas velocity with small capacity factor has been developed in the light of theoretical discussion of factors effecting the column efficiency utilization ratio.     

Synthesis of calixarene-cyclodextrin coupling products

The coupling of two or four mono-6-amino β-cyclodextrin (amino-CD) units, (unprotected or permethylated hydroxyls), to diisopropoxycalix[4]arene crown-6 (CAL) was realised using the N,N′-succinyldiamide linker. The resulting molecules in two series were characterised with the help of mass and NMR spectroscopies. The yields of all coupling products were improved for permethylated sugar series compared to the hydroxylated CD series or to our previous studies. The two β-cyclodextrin (β-CD) residues coupled to disubstituted CAL were orientated from the same side of the crown ether.     

关于气相渗透法仪器常数问题——一个新模式

气相渗透法广泛用于测定齐聚物和低分子量聚合物的数均分子量(M_n)。分析文献数据和本文的实验证明,仪器常数K值随溶质的分子量而变化。本文提出了一种新的说明 VPO法 K值依赖于溶质分子量的模式,根据此模式,可清楚地说明这种依赖关系。     

Preparation of apolar glass capillary columns by the barium carbonate procedure

As an extension of previous reports, the barium carbonate procedure has been optimized in detail for the preparation of apolar columns. The aim was to produce optimum overall column characteristics, and to maintain them unchanged under the prolonged influence of the highest possible temperature. The main parameters under optimization were glass variety, leaching of glass surface with aqueous HCl, and amount of barium carbonate deposited, while deactivation and coating were kept constant. The basic column characteristics were adsorption properties and thermostability of deactivation, acid/base behaviour and separation efficiency. They were determined by a new, quantitative testing procedure. Intense leaching was able to eliminate almost totally the differences between glass varieties and to create a well-defined glass surface. While untreated glass, leached glass, and barium carbonate treated glass showed specific weak points in the respective column quality, the combination of leaching and barium carbonate treatment yielded the highest and most stable quality. Some technical modifications of the preparation procedure are described, including deactivation in the gas phase, and use of pentane as a solvent for static coating.     

Interaction between Metal in Metallo Enzyme and Small Biological Molecules

ＩｎｔｅｒａｃｔｉｏｎｂｅｔｗｅｅｎＭｅｔａｌｉｎＭｅｔａｌｌｏＥｎｚｙｍｅａｎｄＳｍａｌｌＢｉｏｌｏｇｉｃａｌＭｏｌｅｃｕｌｅｓ￥ＨｕＪｉｅ－Ｈａｎ；ＳｈｕＺａｎ－Ｙｏｎｇ；ＴａｏＬｉ－Ｍｅｉ；ＣｈｅｎｇＧｕｏ－Ｂａｏ（ＤａｌｉａｎＩｎｓｔｉｔｕｔ...     

Neosappanone A, a xanthine oxidase (XO) inhibitory dimeric methanodibenzoxocinone with a new carbon skeleton from Caesalpinia sappan

A novel dimeric methanodibenzoxocinone, named neosappanone A (1), possessing a unique unprecedented novel carbon framework, has been isolated from the heartwood of Caesalpinia sappan L. of Vietnam, and its structure was elucidated on the basis of spectroscopic analysis. Neosappanone A (1) competitively inhibited xanthine oxidase in a concentration-dependent manner (IC₅₀, 29.7 μM; K_i, 16.3 μM).