Re-Evaluation of the Activity Coefficients of Aqueous Hydrochloric Acid Solutions up to a Molality of 2.0 Using Two-Parameter Hückel and Pitzer Equations. Part I. Results at 25°C

Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at 25°C up to a molality of 2.0 mol-kg^–1. The data obtained by Harned and Ehlers^(12,13) from galvanic cells without liquid junction were used in the analysis and the parameters obtained were compared to those obtained from all reliable data presented in the literature for HCl at this temperature. A good agreement between the parameters was always observed. The activity coefficients obtained by the new equations were compared to those suggested by Robinson and Stokes,⁽⁸⁾ Hamer and Wu,⁽¹⁾ and Pitzer and Mayorga,⁽⁹⁾ and good agreement was also found. The data from the most important literature data sets for HCl were also predicted using the new activity coefficient equations, and the magnitude of the resulting errors was close to the precision of the measurements, the errors forming an almost random pattern for all data sets.     

有机光伏器件激活层的微结构有序性与电荷输运

本文在对有机光伏电池载流子产生机理分析的基础上,从有机光伏电池激活层的微观结构对光电转换效率影响的角度,系统介绍了目前该领域的一些重要研究成果,详细分析了影响光电转换效率的主要因素,并提出了一系列改善光伏电池效率的方法,对未来该领域的研究作了展望。     

Synthesis of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (chikusetsusaponin-LT8), a glycoside from Panax japonicus

A method for preparative production of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1), a glycoside from Panax japonicus, chikusetsusaponin-LT₈ was developed. Chemical transformation of betulafolientriol, a component of Betula leaves extract, produced the 12-keto-20S-protopanaxadiol (3β,20S-dihydroxydammar-24-en-12-one) (2), exhaustive glycosylation of which by 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylbromide (3) under Koenigs—Knorr reaction conditions with subsequent removal of protecting groups formed 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1). The principal glycosylation product was 3β,20S-dihydroxydammar-24-en-12-one 3-O-β-D-glucopyranoside if equimolar amounts of (2) and (3) were used. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–48, January–February, 2006.     

Co(III)氮芥配合物的合成、表征及其抗肿瘤活性的初步评价

低氧条件下,钴(Ⅲ)的氮芥配合物具有合适的还原电位,就可能还原得到比较活泼的Ｃｏ(Ⅱ)配合物,在溶液中其活性配体很快被体内的小分子取代,释放出的活性配体可以杀死低氧区内外的癌细胞,因此筛选合适的钴配合物作为低氧选择性抗癌药物的研究很有意义。本文以双 (2 氯乙基)胺(简称ＢＣＡ)为活性配体,取代乙酰丙酮为辅助配体,合成一系列Ｃｏ(Ⅲ)配合物(下图)。初步评估结果表明,其中两个配合物具有一定的低氧选择性,配合物的还原电位对药物的低氧选择性影响很大,合适的还原范围可能比较窄。1　实验部分1.1　试剂与仪器按文献[1]的方法合成…     

Fabrication of Poly(allylamine)ferrocene Monolayer Based on Electrostatic Interaction and Its Electrocatalytic Oxidation of Ascorbic Acid

A poly(allylamine)ferrocene monolayer was built on the surface of gold electrode modified with negatively charged alkanethiol based on electrostatic interaction. The electrochemical behavior of the modified electrode was characterized by cyclic voltammetry in detail. The modified electrode was shown to exhibit excellent electrocatalytic response to the oxidation of ascorbic acid. The anodic overpotential was reduced by about 170 mV compared with that obtained at a bare gold electrode. The modified electrode possesses several attractive features, such as simple preparation, fast response and good chemical and mechanical stability.     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究Ⅱ.焙烧温度的影响

采用XRD、FT-IR和NH3-TPD等方法，研究了载体预焙烧温度和催化剂活化焙烧温度对B2O3/TIO2-ZRO2催化剂的结构、酸性和催化环己酮肟气相Beckmann重排反应性能的影响。结果表明，在383-773K范围内，载体预烧温度对催化剂性能的影响不大，但经973K高温预焙烧后，由于生成了ZrTiO4晶相，使其与H3BO3的相互作用减弱，从而导致催化剂的酸性和反应性能降低，提高催化剂活化焙烧温度，有利于B2O3与TiO2-ZrO2的相互作用，生成更多的Beckmann重排反应所需的中等强度酸中心，使催化剂的活性和选择性提高；但活化焙烧温度过高，会使催化剂中大量的B2O3晶粒析出，引起酸中心数量和催化活性的明显下降。     

卟啉试剂与贵金属高灵敏显色反应的研究 Ⅴ.Ru(Ⅲ)-T(4-AOP)P-TritonX-100体系

本文研究了在Ｃｄ（Ⅱ）和ＴｒｉｔｏｎＸ－１００存在下，ｍｅｓｏ－四（４－乙酰氧基苯）卟啉［Ｔ（４－ＡＯＰ）Ｐ］与钌（Ⅲ）的显色反应。结果表明，在ｐＨ９．７～１０．３介质中，Ｒｕ（Ⅲ）与Ｔ（４－ＡＯＰ）Ｐ形成了灵敏度很高的稳定络合物，其表观摩尔吸光系数为７．０４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。钌浓度在０～１．２μｇ／１０ｍＬ范围内服从比尔定律。络合物的摩尔比为Ｒｕ（Ⅲ）∶Ｔ（４－ＡＯＰ）Ｐ＝１∶１。在掩蔽剂存在下，方法有一定的选择性，应用于合成试样中钌的测定，结果满意。     

Supramolecular structures of macromolecules containing bipyridine–copper(I) complexes as revealed from transmission electron microscopy studies

Transmission electron microscopy (TEM) studies on bipyridine (bpy) containing block copolymer systems showed the formation of nanoscopic polymer–ion complexes through complexation with copper(I) ions which segregated to highly ordered columnar domains of mesoscopic dimensions. The domains, i.e. stacks of [(bpy)₂Cu(I)] complex moieties could be visualized by complementary TEM techniques. First, electron energy loss spectra (EELS) showed the absorption edges of copper and nitrogen, which are specific for the bipyridine copper complexes. The element spectroscopic imaging (ESI) technique allowed the imaging of the net copper and net nitrogen distribution, and the coinciding pictures exhibited a microphase separated system in the case of a 3-block copolymer with complexed end segments. High resolution elastic bright field images showed interference lines with a line to line distance of about 8 A which could be related to the Cu–Cu distance in staggered Cu(I)–bipyridine complexes. Received: 6 August 1997 Accepted: 28 April 1998     

复合Fe2O3纳米粒子的高分子微球的结构表征

近年来，复合有机、无机粒子的高分子微球及其特殊性质越来越引起人们的兴趣与关注［1］．获得有机、无机复合微球的方法很多，如在无机粒子存在下的乳液或无皂乳液聚会[2，3]，通过可聚合的表面活性剂在粒子表面形成胶囊化层[4]以及共沉淀法等[5]．这些无机粒子包括氧化钛、氧化铁、氧化铝及氧化硅等．Haga等[6]增发现包覆在聚合物粒子中的CdS与其本体的光电性质不同；单分散的聚合物微球可以在基片上被组装成二维乃至三维有序的结构[7]．这为信息存储、立体印刷等领域提供了新途径．因此，将无机粒子与聚合物复合成为功能化粒子是一项有…     

New ferrocene-containing structures: Poly(silyl ester)s

Two new polymeric structures containing ferrocene units along the chains, namely poly(silyl ester)s, have been synthesized and characterized: a geminal poly(silyl ester) (g-PSE) and one having a disiloxane spacer between the silyl ester groups (s-PSE). The condensation polymerization of AA/BB monomer systems in solution was used in both cases as preparation method involving a silicon-containing diol, (diphenylsilane diol or 1,3-bis(hydroxy)-tetramethyldisiloxane), and 1,1′-di(chlorocarbonyl)ferrocene. The polymers were investigated by differential pulse voltammetry in order to evaluate the redox behavior. Due to the presence of the silyl ester groups in the chain, these polymers are hydrolytically degradable.