N—芳基马来酰亚胺与硫化硫酸钠的电荷转移络合物研究

本文以硫代硫酸根离子作为电荷给体（Ｄ），系列Ｎ－芳基取代马来酰亚胺（ＲＰｈＭＩ）作为电荷受体（Ａ），用含水５％的二甲基亚砚（９５％ＤＭＳＯ）为溶剂，以紫外可见分光光度法研究了ＲＰｈＭＩ与Ｓ２Ｏ３作用生成的电荷转移（ＣＴ）络合物，以其ＣＴ光谱计算了ＲＰｈＭＩ的电子亲合能（ＥＡ），测定了ＣＴ络合物的生成常数Ｋ。结果显示，弱的受体Ｎ－马来酰亚胺与强的本硫代硫酸根负离子可以生成稳定的ＣＴ络合物，文章还讨论     

一种新型不对称马来酰亚胺单体的合成

以马来酸酐（ＭＡ）,Ｄ,Ｌ－氨基丙酸（Ａｌｎ）为原料合成了一种既含不对称碳原子又含官能团（羧基）的新型马来酰亚胺单体Ｎ－（异丙酸基）－马来酰亚胺（ＡＭＩ）。考察了溶剂、原料配比、催化剂用量、反应时间对产率的影响,确定了最佳反应条件。所得Ｎ－（Ｄ,Ｌ－异丙酸基）马来酰业胺的产率达５２％。并用ＰＥＲＫＩＮ－ＥＬＭＥＲＦＴＩＲ－１７１０红外光谱仪、ＰＥ－２４００有机元素分析仪对产品进行了检测。本实验具有     

氯乙烯／N—苯基马来酰亚胺／乙烯基单体悬浮共聚速率

根据氯乙烯（ＶＣ）／Ｎ－苯基马来酰亚胺（ＰＭＩ）／乙烯基单体悬浮共聚合工艺的特点，确定了倒加料的聚合工艺，比较了丙烯腈（ＡＮ），甲基丙烯酸甲酯（ＭＭＡ）对ＶＣ／ＰＭＩ聚合速率的影响，研究了ＡＮ的用量和聚合温度对ＶＣ／ＰＭＩ／ＡＮ三元悬浮共聚合速率的影响。     

无皂乳液聚合制备阳离子功能性微示研究

苯乙烯（Ｓｔ）／丙烯酸丁酯（ＢＡ）体系在无乳化剂的条件下分别与少量的自制的Ｎ，Ｎ－二甲基，Ｎ－丁基，Ｎ－甲基丙烯酰氧乙基溴化铵（ＤＢＭＥＡ）、Ｎ，Ｎ－二甲基，Ｎ－丁基，Ｎ－（３－甲基丙烯酰胺基）丙基溴化铵（ＤＢＭＰＡ）进行共聚，难过离子交换－－电导滴定确定了两体系微球表面基团及粒子表面电荷密度，认为微球大小及表面电荷密度主要由引发剂浓度、共聚单体浓度、离子强度、Ｓｔ／ＢＡ主单体比及单体加料方式决定     

松香马来酰亚胺聚酯合成

松香与马来酐反应加合物的产率为７９％。在ＤＭＦ中加合物与氨基苯甲酸反应的产物，Ｎ－羧苯基松香马来酰亚胺的产率大于９０．４％。在Ｈ＿３ＢＯ＿３－ＺｎＯ催化下３种松香马来酰亚胺聚酯的产率为８０％，８０％，７２％。ＴＧＡ测定表明，它们的ＯＮＳＥＴ温度超过４９０℃。应用试验表明，添加１５％松香马来酰亚胺聚酯，不但提高不饱和聚酯固化膜的热稳定性能．而且保持不饱和聚酯膜的气干性能。     

N—（D,L—异丙酸基）—马来酰亚胺的合成

研究Ｎ－（Ｄ,Ｌ－异丙酸基）－马来酰胺酸闭环合成Ｎ－（Ｄ,－异丙酸基）－马来酰亚胺,考察了溶剂、催化剂用量、反应时间对产率的影响,同时也考察了混合剂对粗产物重结晶的影响,确定了最佳反应条件。所得Ｎ－（Ｄ,Ｌ－异丙酸基－）民来酰亚胺的产率达５２％。本实验具有产率高、溶剂容易回收、ＡＭＡ不需纯化等优点。     

N—（取代苯基）马来酰亚胺的合成及表征

合成了８种Ｎ－（取代苯基）马来酰亚胺。研究了主、副反应机理及合成条件的控制,并采用＾１ＨＮＭＲ、ＴＧ－ＤＴＡ对中间产物和最终产物进行了表征。     

N—苯基马来酰亚胺的合成

以顺丁烯二酸酐和苯胺为原料，选择二步法合成了Ｎ－苯基马来酰亚胺，无需使用ＤＭＦ溶剂。用正交法优化了工艺条件，产品收率为９２％，质量分数为９７％，溶点８６．８￣８８．０℃。应用试验表明Ｎ－苯基马来酰亚胺是ＰＶＣ塑料有效的热稳定剂。     

N－苯基取代2，3双－［3－（1－乙基－2－甲基－吲哚）］－马来酰亚胺的合成和光致变色性能研究

Ｎ－苯基取代２，３双－［３－（１－乙基－２－甲基－吲哚）］－马来酰亚胺的合成和光致变色性能研究于联合，赵伟利，樊美公（中国科学院感光化学研究所，北京１００１０１）朱自强（河南大学物理系，开封４７５００１）关键词合成，马来酰亚胺，光致变色，瞬态吸收光谱...     

N—取代马来酰亚胺在开发新材料中的应用

本文着重介绍了Ｎ－取代马来酰亚胺与异丁烯交替共聚合成新型透明材料、用Ｎ－取代马来酰亚胺改性有玻璃、聚苯乙烯、聚酰亚胺树脂、ＡＢＳ树脂，不饱和聚酯等的研究情况，Ｎ－取代马来酰亚胺可以显著提高上述材料的耐热性，又保持它们优异的力学性能和工艺性。     

Shewanella sp. O23S as a Driving Agent of a System Utilizing Dissimilatory Arsenate-Reducing Bacteria Responsible for Self-Cleaning of Water Contaminated with Arsenic

The purpose of this study was a detailed characterization of Shewanella sp. O23S, a strain involved in arsenic transformation in ancient gold mine waters contaminated with arsenic and other heavy metals. Physiological analysis of Shewanella sp. O23S showed that it is a facultative anaerobe, capable of growth using arsenate, thiosulfate, nitrate, iron or manganite as a terminal electron acceptor, and lactate or citrate as an electron donor. The strain can grow under anaerobic conditions and utilize arsenate in the respiratory process in a broad range of temperatures (10–37 °C), pH (4–8), salinity (0%–2%), and the presence of heavy metals (Cd, Co, Cr, Cu, Mn, Mo, Se, V and Zn). Under reductive conditions this strain can simultaneously use arsenate and thiosulfate as electron acceptors and produce yellow arsenic (III) sulfide (As₂S₃) precipitate. Simulation of As-removal from water containing arsenate (2.5 mM) and thiosulfate (5 mM) showed 82.5% efficiency after 21 days of incubation at room temperature. Based on the obtained results, we have proposed a model of a microbially mediated system for self-cleaning of mine waters contaminated with arsenic, in which Shewanella sp. O23S is the main driving agent.     

Electroless versus electrodriven deposition of silver crystals in polyaniline: Role of silver anion complexes

Electrocrystallization of silver is studied at polyaniline-coated electrodes using silver cations and two silver anion complexes (silver thiosulfate and silver–EDTA) as reducing species. Use of the silver thiosulfate complex results in a significant shift of the silver deposition potential window in the negative direction and highly impeded metal crystallization. The silver cation and silver–EDTA plating solutions allow to perform both electrodriven and electroless metal deposition. Number and size of silver crystals obtained by the two deposition methods in the different plating solutions are compared. Electroless precipitation in the silver–EDTA solution results in the highest number (10⁸ cm⁻²) of small-sized crystals. This result is discussed in terms of the special role of the EDTA anions for the redox state of the polyaniline layers. It is demonstrated that factors such as polyaniline redox charge, concentration of reducing ions and dipping time allow effective control over the amount of electroless deposited metal.     

Electroless versus electrodriven deposition of silver crystals in polyaniline: Role of silver anion complexes

Electrocrystallization of silver is studied at polyaniline-coated electrodes using silver cations and two silver anion complexes (silver thiosulfate and silver-EDTA) as reducing species. Use of the silver thiosulfate complex results in a significant shift of the silver deposition potential window in the negative direction and highly impeded metal crystallization. The silver cation and silver-EDTA plating solutions allow to perform both electrodriven and electroless metal deposition. Number and size of silver crystals obtained by the two deposition methods in the different plating solutions are compared. Electroless precipitation in the silver-EDTA solution results in the highest number (∼10⁸ cm⁻²) of small-sized crystals. This result is discussed in terms of the special role of the EDTA anions for the redox state of the polyaniline layers. It is demonstrated that factors such as polyaniline redox charge, concentration of reducing ions and dipping time allow effective control over the amount of electroless deposited metal.     

The synthesis,photophysical properties and fluoride anion recognition of a novel branched organoboron compound

A novel two-branched organoboron compound, N,N-bis(7-dimesitylboryl-9,9-diethyl-9H-fluorene-2-yl)aniline, containing a phenylamino group as a π-electron donor, fluorene groups as π-bridges and dimesitylboryl groups as electron acceptors, was synthesized and its photophysical properties in various solvents as well as its fluoride anion recognition properties were investigated. The synthesised compound exhibited strong fluorescence in all solvents with the fluorescence changing from blue to orange on going from solvents of low polarity to those of high polarity. The compound was able to recognize fluoride anions in high sensitivity owing to strong interactions between boron atoms and fluoride anions.     

Spectroscopic Studies on Electron Donor-Acceptor Complex between n,2,4,6-tetranitro-N-methylaniline and ethylenediamine

Spectroscopic studies indicate that N,2,4,6-tetranitro-N-methylaniline (tetryl) forms two charges transfer (CT) complexes with ethylenediamine (EDA) and these complexes show absorption maxima at 440 nm and 340 nm respectively. Both the complexes have 1:1 ratio of donor to acceptor. The formation constant and molar extinction coefficient for the complexes have been determined in acetonitrile as well as in ethanol and methanol to evaluate the effect of polarity. The initial complex (λ_max at 440 nm) undergoes transformation to a product complex (λ_max at 340 nm) when the EDA concentration is lowered. The product complex has been isolated and characterized by IR, UV spectroscopy, thermal analysis and X-ray diffraction (XRD). The transformation of the initially formed CT complex to the product complex in solution has been found to obey first order kinetics. The formation of CT complex of tetryl with EDA has been succesfully used to develop a spectrophotometric method for the quantitative determination of tetryl.     

Novel Polymeric Metal Complexes for Dye Sensitizer: Synthesis and Photovoltaic Performances

Four novel polymeric metal complexes with a D–A–π–A motif, BDTT-PY-Cd, BDTT-PY-Zn, BDTT-PY-Cu and BDTT-PY-Ni, were designed, synthesized and characterized. These polymeric metal complexes were made up with Cd(II), Zn(II), Cu(II), Ni(II) complexes, thienylbenzo-[1,2-b:4,5-b'] dithiophene (BDTT) and the 8-quinolinol derivative, which were used severally as dye sensitzers’ auxiliary electron acceptors (A), electron donor (D) and π bridges as well as the acceptors (A). Under AM 1.5 irradiation (100 mW cm^?2), the devices of dye sensitized solar cells (DSSC) based on four polymer complexes exhibited short-circuit photocurrent densities (J_sc) of 17.45 mA cm^?2, 14.75 mA cm^?2, 13.94 mA cm^?2 and 12.00 mA cm^?2, as well as attractive power conversion efficiencies (PCE) of were 9.73%, 8.02%, 6.82% and 6.12%, respectively. The photovoltaic conversion efficiency (PCE) and short-circuit photocurrent density (J_sc) of BDTT-PY-Cd, BDTT-PY-Zn, BDTT-PY-Cu and BDTT-PY-Ni decrease in order because the radius and charge number of the metal ion affect the strength of the coordination bond between the metal ion and the ligand. These results provides a new way of development for efficient and stable dye sensitizers in the future.

     

Theoretical study of interaction of thiazolidine-2-thione as an anti-thyroid agent with iodine

Quantum chemical calculations were used to investigate the interaction of tautomer forms of thiazolidine-2-thione (T2T) with iodine in the gas and solution phases. The calculations show that the planar complexes are more stable than the perpendicular complexes. Also in the perpendicular complexes, the thione form is more stable than the thiol form. The calculated thermodynamic parameters in the solution phase indicate that the stability of the formed complexes increases as the dielectric constant of the solvent is increased. This result is in good agreement with the experimental results. The NBO results predict that the LP(S) → σ*(I─I) and LP(S) → σ*(N─H) charge transfer (CT) interactions are very important in the stabilizing of the planar complexes with respect to the perpendicular complexes. In all complexes, CT takes place from T2T to I₂. Therefore, it is predicted that the donor properties of T2T are the origin of its anti-thyroid action. The atoms in molecule (AIM) analysis shows that the interactions in the planar complexes are stronger than the perpendicular complexes.     

Interaction of aliphatic amines with substituted quinones—a conductometric study

Interactions of aliphatic amines with chloranil and 2,3-dichloro-5,6-dicyano-p-benzoquinone have been examined by employing a conductometric technique. The stoichiometries, σ_M and σ_p values of the complexes are reported. The σ_p values reflect electron affinity of acceptors with a fixed electron donor and the donor strength of donors with a fixed electron acceptor. σ_M values do not exhibit a definite order. Effect of solvent and temperature on the σ_p values of the complexes has been studied.     

熊果苷的合成新方法

首次报道了采用硫代糖法合成熊果苷。葡萄糖经过乙酰化、硫代、脱乙酰基和苯甲酰化反应,转变成供体异丙基-2,3,4,6-四-O-苯甲酰基-1-硫--βD-葡萄糖苷。对苯二酚选择性地酯化成两种受体对苯二酚单乙酸酯、对苯二酚单苯甲酸酯以及相应的对苯二酚双酯副产物。供体分别与两种受体偶联,由于C-2苯甲酰基的强邻基参与效应,立体专一性地合成了两种保护的熊果苷,后者分别脱保护得到熊果苷。所有产品通过熔点和1HNMR等方法进行了结构表征。此外,上述双酯副产物通过选择性地脱酰基,获得了两种可用的受体对苯二酚单酯,有效地得到回收利用。