Modeling Study on Effects of Liquid Propylene in Horizontally Stirred Gas-Phase Reactors for Polypropylene

Modeling study was carried out for JPP-HORIZONE, which has horizontally stirred gas reactors in which the heat of polymerization is removed by vaporization of liquid propylene (LPP). The effects of LPP were estimated by the model which has a couple of continuous stirred bed reactors different in propylene form, gas of liquid, combined with a less stereospecific catalyst as a probe. LPP affects isotacticity further than catalyst efficiency in the developed model. Observed isotacticity was lower than that estimated by the model without LPP, which can be explained only by the presence of LPP.     

SYNERGISTIC INTERACTIONS ON PHENOL ADSORPTION FROM AQUEOUS SOLUTIONS BY POLYMERIC ADSORBENTS

In this paper, the adsorption behaviors of phenol on polymeric adsorbents (Amberlite XAD4, NDA101, and D301)were investigated in batch system at 293, 303, and 313K, respectively. As the results shown, the adsorption isotherms of phenol on all adsorbents can be well fitted by Langmuir and Freundlich equations, which indicate a favorable and exothermic process. The adsorption capacity on a newly developed aminated adsorbent, NDA101, on which adsorption could be achieved by both hydrogen bonding interaction and π-π interaction, are higher than that on a weak base adsorbent, D301, on which adsorption could be achieved by hydrogen bonding interaction only, and on a nonpolar adsorbent, XAD4, on which adsorption could be achieved by π-π interaction only. The results of this paper indicate that the synergistic effect of some weak interactions, which occur simultaneously would contribute more to the adsorption than that occur individually.     

C. A. Coulson and the surface energy of metals: A further comment

The role of the boundary conditions is emphasized in determining the relation between the counting problem, posed by Coulson and solved by the number theorists, and the physical problem from which it arises. The surface energy term, which Coulson sought, does exist, but only when the periodic boundary conditions, which he used, are replaced by the finite box conditions.     

西红花有效成分合成研究进展

西红花主要有效成分为西红花酸和西红花糖苷,论文综述西红花酸和西红花糖苷生物合成和化学合成方法.在生物合成中最关键的是用葡萄糖糖基转移酶作催化剂将西红花酸转化为西红花糖苷;共轭多烯链化合物是合成西红花有效成分的起始物,在论文中概述了几种通过Wittig和Wittig-Horner 反应合成共轭多烯链化合物的路线.     

In between worlds: G.N. Lewis, the shared pair bond and its multifarious contexts

In this paper, I will look at the rather convoluted discovery process which gave birth to the concept of the shared electron pair bond as developed by G.N. Lewis, to be subsequently appropriated by the American founders of quantum chemistry, and highlight the complex relations between conceptual development and the different contexts in which ideas are created and presented. I will show how the successive installments of Lewis's model of the chemical bond were supported by and gained credence from an epistemological background in which Lewis explored the relations of chemistry to physics. Furthermore, they were shaped by the changing public contexts in which the successive metamorphoses of the ideas took place and their epistemological background was outlined and explored. The complexities which are always associated with a discovery process can therefore be illuminated if one pays attention to different interactive realms-the conceptual, epistemological, and the presentational one.     

Preparative Solid State Chemistry: The Present Position

Two types of reaction are distinguished in solid state chemistry: those in which high mobility of the reactants is aimed at (which can be achieved by the use of high temperatures, by the introduction of defects, by the promotion of surface diffusion, or by means of chemical transport phenomena), and those reactions in which the nature of the products is determined by existing structural elements or lattice defects of the reactants. The importance of paying more attention than hitherto to reaction pathways in preparative solid state chemistry is pointed out.     

Thermal degradation of fire retardant chloroparaffin-metal compound mixtures: Part II—Bismuth compounds

The mechanisms of reactions which occur on heating mixtures of Bi compounds and a chloroparaffin, which are suitable fire retardant additives for polymers, have been studied.BiCl₃, which is evolved at a high initial rate by reaction of Bi compounds with HCl eliminated by the chloroparaffin, has a strong catalytic effect on the dehydrochlorination process of the chloroparaffin itself. BiCl₃ evolution occurs in a two-stage process: a fast step characterised by a maximum rate at 300°C followed by a slower step which occurs between 300 and 500°C.     

新型硫鎓盐产酸剂的合成及其产酸效率研究

本文合成了六种适用于248nm光致抗蚀剂的产酸剂,其中吩噻口恶 体系的产酸剂由本研究室自主设计合成。六种产酸剂均通过IR,HNMR,UV等进行了结构表征,并利用酸敏染料遇酸异构变色的特点定量检测了六种产酸剂的产酸效率,同时使用荧光追踪法研究了溶剂极性对产酸效率的影响,优选出了硫杂蒽酮系列的产酸剂,为进一步用于248nm光致抗蚀剂提供参考。     

Synthesis and solid-state organization of coil-ring-coil block copolymers

Shape-persistent macrocycles based on the phenyl-ethynyl-butadienyl backbone containing two extraannular hydroxyl groups were prepared by the oxidative coupling of the appropriate phenylethynyl oligomers. Carbodiimide-directed coupling with independently synthesized polystyrene carboxylic acid oligomers led to ABA coil-ring-coil block copolymers in which the central macrocycle serves as rigid and the polystyrene oligomers as flexible elements. Depending on the size of the coil blocks, these structures aggregate in cyclohexane into supramolecular hollow cylindrical brushes in which the rigid core is surrounded by the flexible matrix. However, in the solid state it is not possible to identify a morphology in which isolated channels based on aggregated macrocycles are embedded in a matrix of polystyrene. Detailed X-ray and electron diffraction studies on samples prepared from a solution in cyclohexane under equilibrium conditions show that the material adopts a lamellar morphology in the solid state in which columns of macrocycles are aggregated into layers which are separated by polystyrene.     

直立碳纳米管超级电容器的研究

在石英玻璃基底上,以酞菁裂解法低压气相沉积制备大面积管径均匀、长度一致的直立碳纳米管.分别应用电解质溶液浸润、酸处理和循环伏安扫描等3种不同方法纯化活化该直立碳纳米管,并以活化后的碳纳米管作为原型超级电容器的电极.循环伏安扫描和交流阻抗测试表明,CV曲线呈近似矩形,交流阻抗最大相位角超过80°,该直立碳纳米管的比电容为16~32F/g,乃超级电容器理想的电极材料.     

Carbon layer open tubular capillary columns

Capillary columns coated with Carbopack materials, which provide separation by a mixed partition/adsorption mechanism or by adsorption alone, have recently been developed. The reproducibility of the columns is demonstrated and applications shown in which they provide separations which are either unique or are faster than can be achieved with the wall coated open tubular capillary columns currently available.     

In vivo transformations of artemisinic acid in Artemisia annua plants

Artemisinic acid labeled with both ¹³C and ²H at the 15-position has been fed to intact plants of Artemisia annua via the cut stem, and its in vivo transformations studied by 1D- and 2D-NMR spectroscopy. Seven labeled metabolites have been isolated, all of which are known as natural products from this species. The transformations of artemisinic acid—as observed both for a group of plants, which was kept alive by hydroponic administration of water and for a group, which was allowed to die by desiccation—closely paralleled those, which have been recently described for its 11,13-dihydro analog, dihydroartemisinic acid. It seems likely therefore that similar mechanisms, involving spontaneous autoxidation of the Δ^4,5 double bond in both artemisinic acid and dihydroartemisinic acid and subsequent rearrangements of the resultant allylic hydroperoxides, may be involved in the biological transformations, which are undergone by both compounds. All of the sesquiterpene metabolites, which were obtained from in vivo transformations of artemisinic acid retained their unsaturation at the 11,13-position, and there was no evidence for conversion into any 11,13-dihydro metabolite, including artemisinin, the antimalarial drug, which is produced by A. annua. This observation led to the proposal of a unified biosynthetic scheme, which accounts for the biogenesis of many of the amorphane and cadinane sesquiterpenes that have been isolated as natural products from A. annua. In this scheme, there is a bifurcation in the biosynthetic pathway starting from amorpha-4,11-diene leading to either artemisinic acid or dihydroartemisinic acid; these two committed precursors are then, respectively, the parents for the two large families of highly oxygenated 11,13-dehydro and 11,13-dihydro sesquiterpene metabolites, which are known from this species.     

An autocatalytic chromogenic and fluorogenic photochemical reaction controlled by nucleic acids

The autocatalytic photochemical reaction, which is potentially controlled by any selected nucleic acid, is highly sequence specific and not inhibited by its products, was developed. This reaction generates colored and fluorescent products, which can be monitored by the naked eye.     

肝素温度敏感色谱填料的制备与性能研究

利用自由基聚合法制备了含有聚(N-异丙基丙烯酰胺/N-丙烯酰氧琥珀酰亚胺)和肝素共聚物的温度敏感的亲和色谱填料; 通过热失重分析得到该填料表面聚合物的接枝率为9.45%; Elison-Morgan 法测定该填料表面的肝素含量为3.6mg/g. 将其用作HPLC 固定相, 分离苯和氢化可的松, 表明该色谱固定相具有温度敏感特性; 该色谱柱对凝血酶具有较强的亲和作用, 通过控制温度缩短了凝血酶的释放时间, 回收率为81.4%, 这为蛋白质的分离提供了一个快速有效的方法.     

Mannich products of kojic acid and N-heterocycles and their Ru(II)-arene complexes: Synthesis, characterization and stability

Ru(II)-η⁶-p-cymene compounds bearing pyrone-derived ligands, which were obtained by Mannich reaction with piperidine and related analogues, have been synthesized. The compounds were characterized by NMR spectroscopy, mass spectrometry, thermogravimetric analysis and in the case of 2-(2,6-dimethyl-morpholin-4-ylmethyl)-3-hydroxy-6-hydroxymethyl-pyran-4-one by X-ray diffraction analysis. The chlorido complexes are prone to aquation in aqueous solution which results in the formation of dimers. Dimer formation can be inhibited by in situ replacement of the chlorido ligand by imidazole yielding compounds which are significantly more stable in water, as demonstrated by ¹H NMR spectroscopy.     

基于多金属氧簇的手性超分子液晶

以手性诱导为切入点,采用含胆固醇基团的季铵盐表面活性剂静电包覆缺位的Keggin结构多金属氧簇K₇PW₁₁O₃₉·12H₂O,得到了手性介晶阳离子修饰的多金属氧簇杂化超分子复合物。圆二色谱对该复合物光学活性的表征说明外围的手性表面活性剂可以通过静电相互作用诱导复合物显示出手性。利用差示扫描量热曲线法、偏光显微镜观察和变温X射线衍射详细研究了该复合物的热性质和相行为,结果表明该复合物在较宽的温度范围内具有热致液晶性质,是一种典型的手性近晶A相离子液晶材料。     

Retinal photoisomerase: role in invertebrate visual cells.

In invertebrate visual cells, the rhodopsin content is maintained at a high level by the fast process of photoregeneration during daylight. Rhodopsin is converted by photoabsorption to metarhodopsin, which is reconverted to rhodopsin by light. In addition, rhodopsin is regenerated by a slow process of renewal which takes days to complete and involves the biosynthesis of opsin. It is well known that rhodopsin can be formed from opsin only when 11-cis-retinal is present; this requires the existence of an isomerizing enzyme which is capable of transforming all-trans-retinal, released from the degradation of metarhodopsin, into the 11-cis-retinal isomer. In some invertebrate visual systems, experiments on rhodopsin regeneration have been interpreted by assuming that the isomerization reaction is a light-dependent process involving a retinal-protein complex. Two retinal photoisomerases which have been well characterized, i.e. bee photoisomerase and cephalopod retinochrome, are reviewed here. Their properties are compared in order to determine their physiological role, which is likely to be in the renewal of visual pigment rhodopsin. To conclude, a visual pigment cycle is proposed in which rhodopsin regeneration follows two light-dependent pathways. This greatly simplifies the rhodopsin regeneration scheme for invertebrate visual systems.     

Controlled Radical Polymerization

Various methods which lead to the control of molecular weight and polydispersities, and which allow for the preparation of block copolymers by radical polymerization are discussed. Thermal polymerizationof styrenes in the presence of stable radicals, polymerization of vinyl acetate and methyl methacrylate in the presence of chromium complexed by macrocyclic ligands polymerization of vinyl acetate initiated by organoaluminum compounds complexed by dipyridyl and activated by stable radicals, as well as in the presence of phosphites, are described in detail.     

The morphology of composite polymer particles produced by multistage soapless seeded emulsion polymerization

 Composite polymer particles which contain poly(methyl methacrylate) (PMMA) and polystyrene (PS) components (PMMA/PS composite particle) were synthesized by the method of multistage soapless seeded emulsion polymerization. In this study, the process of multistage soapless seeded emulsion polymerization included two-stage polymerization, three-stage polymerization or four-stage polymerization. The morphologies of the PMMA/PS composite particles were studied. The kinetic factor was the main force to control the morphology of the linear PMMA–PS composite particles which were synthesized by the method of two-stage reaction. Both the kinetic factor and the thermodynamic factor decide the morphology of the linear composite particles which were synthesized by the method of either three-stage or four-stage reaction. However, the thermodynamic factor cannot influence the morphology of the PMMA/PS composite particles with a cross-linked structure which were synthesized by the method of three-stage reaction. The cross-linked composite polymer particles had the morphology of a multilayer structure, which showed that the polymer layers accumulated in their order of production. Received: 9 January 2001 Accepted: 14 June 2001     

Pulsed Laser Deposition ZnS Buffer Layers for CIGS Solar Cells

Polycrystalline ZnS films were prepared by pulsed laser deposition （PLD） on quartz glass substrates under different growth conditions at different substrate temperatures of 20, 200, 400, and 600 ℃, which is a suitable alternative to chemical bath deposited （CBD） CdS as a buffer layer in Cu（In,Ga）Se2 （CIGS） solar cells. X-ray diffraction studies indicate the films are polycrystalline with zinc-blende structure and they exhibit preferential orientation along the cubic phase β-ZnS （111） direction, which conflicts with the conclusion of wurtzite structure by Murali that the ZnS films deposited by pulse plating technique was polycrystalline with wurtzite structure. The Raman spectra of grown films show Al mode at approximately 350 cm^-1, generally observed in the cubic phase β-ZnS compounds. The planar and the cross-sectional morphology were observed by scanning electron microscopic. The dense, smooth, uniform grains are formed on the quartz glass substrates through PLD technique. The grain size of ZnS deposited by PLD is much smaller than that of CdS by conventional CBD method, which is analyzed as the main reason of detrimental cell performance. The composition of the ZnS films was also measured by X-ray fluorescence. The typical ZnS films obtained in this work are near stoichiometric and only a small amount of S-rich. The energy band gaps at different temperatures were obtained by absorption spectroscopy measurement, which increases from 3.2 eV to 3.7 eV with the increasing of the deposition temperature. ZnS has a wider energy band gap than CdS （2.4 eV）, which can enhance the blue response of the photovoltaic cells. These results show the high-quality of these substitute buffer layer materials are prepared through an all-dry technology, which can be used in the manufacture of CIGS thin film solar cells.