多核多氧硫钼酸盐化合物的合成及质子传导性能

质子交换膜燃料电池(PEMFC)因能量转化率高、 污染小、 工作温度低、 启动速度快而被广泛应用. Nafion系列膜成本高、 结构特性模糊, 阻碍了质子传导性能的进一步提高和对传导机理的精确理解. 因此开发具有结构明确、 传导路径清晰的高质子传导率的晶态材料对于燃料电池领域具有重要意义. 本文利用有机配体5-羟基间苯二甲酸作为模板诱导[Mo₂S₂O₂]²⁺阳离子, 自组装成一种多核多氧硫钼酸盐簇[N(CH₃)₄]₂H₂· [(Mo₂S₂O₂)₈(OH)₁₆(C₈O₅H₄)₂]·22H₂O(Mo₁₆). 该化合物清晰明确的结构和结构中存在的密集氢键网络可用于进行质子传导性能的研究. 交流阻抗测试结果表明, Mo₁₆在宽温度范围内具有较高的质子传导性能. 在97%湿度(RH), 85 ℃条件下其质子传导率可达1.9×10^-2 S/cm, 表明该化合物具有作为高效质子导体的良好前景.     

聚芳撑乙炔微孔骨架材料的合成及其气体吸附

有机微孔聚合物（MOPs）在气体存储、吸附分离和非均相催化等领域具有优良性质而广受关注.近年来,聚芳撑乙炔微孔骨架材料的研究成为MOPs领域中的热点.分别以三（4-乙炔基）苯胺、甲基三（4-乙炔基苯基）硅烷、苯基三（4-乙炔基苯基）硅烷为基本构筑单元,通过端炔基氧化均聚的方法,制备了三种聚芳撑乙炔微孔骨架材料,研究了结构组成对制备聚合物孔道性能和气体吸附性能的影响.氮气吸附测试结果表明,聚合物的Brunauer-Emmett-Teller （BET）比表面积的范围在602~715 m²·g^-1.由于骨架中含有富氮基团（三苯胺）以及具有较大的比表面积,在1.13 bar/273 K条件下,聚三（4-乙炔基）苯胺（TEPA-MOP）的CO₂吸附能力为1.59 mmol·g^-1.此外,TEPA-MOP和聚苯基三（4-乙炔基苯基）硅烷（TEPP-MOP）具有优良的选择性吸附性能,对CO₂/N₂的选择性吸附分别是69.9和73.2.聚合物TEPA-MOP具有优异的CO₂/N₂的选择吸附性和适中的CO₂吸附能力,因此将在气体吸附与分离方面具有潜在的应用前景.     

理论研究8-氮杂鸟嘌呤自由基阳离子脱质子反应

由于8-氮杂鸟嘌呤（8-AG）的氧化还原电势比鸟嘌呤（G）更低,所以单电子氧化嵌有8-AG的DNA后,空穴最终会被8-AG捕获形成8-氮杂鸟嘌呤自由基阳离子（8-AG^·+）.因为酸性的急剧增强,8-AG^·+一般会发生脱质子反应.在本工作中,在M06-2X/6-31+G（d）理论水平,使用显性水分子和连续溶剂化模型模拟8-AG^·+的溶剂化效应,对其脱亚氨基质子（N（1）-H）反应进行了研究.发现位于8-AG^·+中N（1）-H、O（6）、N（2）-H附近以及在O（6）水分子附近稍微远离8-AG^·+的4个水分子会对8-AG^·+脱质子反应产生重要影响,质子从8-AG^·+传递到溶液中具有方向性;最后,通过进一步在N（2）-H、N（3）、O（6）、N（7）和N（8）等位点附近添加水分子（9H₂O）得到了更加精确的8-AG^·+脱质子反应能垒（19.5 kJ/mol）.     

高温质子交换膜燃料电池用聚苯并咪唑/聚乙烯基苄基交联膜的制备与性能研究

为提高聚苯并咪唑（PBI）膜的抗氧化性能,以乙烯苄基氯（PVBC）作为PBI的大分子交联剂,并利用1H-1,2,4-三氮唑取代交联剂中的不稳定端基Cl,制备了交联型高温质子交换膜,考察了交联剂用量对膜的电化学性质的影响. 研究表明,膜中的交联结构有效提高了膜的抗氧化性能,并兼具优异的电导率及力学性能. 采用无增湿H₂和O₂对膜电极性能进行了测试,150 ^oC下电池最大功率密度达到0.82 W•cm^-2.     

含噁二唑大环冠醚的合成、 结构及金属离子识别性能

合成了含有1,3,4-噁二唑基团的大环冠醚: 2,3,11,12-二苯并-4,7,10,16-四氧-14,15-二氮杂双环[11.2.1]-十六烷-13,15-二烯(2)、 2,3,14,15-二苯并-4,7,10,13,19-五氧-17,18-二氮杂双环[14.2.1]-十九烷-16,18-二烯(3)和2,3,17,18-二苯并-4,7,10,13,16,22-六氧-20,21-二氮杂双环[17.2.1]-二十二烷-19,21-二烯(4), 并培养得到其单晶; 通过核磁共振波谱、 高分辨质谱及X射线单晶衍射对其结构进行了表征. 结果表明, 冠醚2属正交晶系, Pna2₁空间群; 冠醚3属于单斜晶系, C2/c空间群; 冠醚4属正交晶系, Pbca空间群. 在3个主体化合物中均存在分子间氢键和π-π相互作用将分子连接成三维空间结构. 采用荧光光谱测定了开链冠醚2,5-二[2-(2-甲氧乙氧基)苯基]-1,3,4-噁二唑(1)和不同环空腔大小的噁二唑冠醚(2~4)对金属离子Li ⁺, Na ⁺, K ⁺, Rb ⁺, Mg ²⁺和Ca ²⁺的键合行为. 研究结果表明, 开链冠醚1和冠醚4对碱土金属Mg ²⁺和Ca ²⁺表现出荧光猝灭行为, 且对Ca ²⁺表现出良好的键合能力和选择性; 而冠醚2对Na ⁺和K ⁺表现出良好的键合能力, 但其Na ⁺/K ⁺的选择性较差.     

硫酸交联壳聚糖膜质子传导行为的研究

制备了硫酸交联壳聚糖膜, 通过研究其质子传导性能、力学性能、化学成分及结构变化, 分析了硫酸与壳聚糖分子间的交联方式, 并对质子传导机理进行了解析. 结果表明, 硫酸交联可显著改善壳聚糖膜的质子传导能力与力学性能, 这种改善作用在交联6 h后趋于稳定, 交联6 h后的壳聚糖湿膜在室温下时质子传导率为0.0472 S• cm^－1, 比未交联的壳聚糖膜提高5倍左右. 硫酸交联壳聚糖膜中的质子传导率与温度的关系符合Arrhenius定律, 质子传导激活能为18 kJ/mol, 其传导机制应属于Grotthus机制. 硫酸对提高壳聚糖膜的质子传导能力主要有两方面的作用: (1) H₂SO₄可使壳聚糖分子中NH₂质子化形成NH₃^＋. (2) 处于两个氨基之间的SO₄^2－在质子传递过程中起离子桥梁作用, 参与以水分子为载体的质子传导过程, 从而减小质子传导的阻力, 提高了质子传导率.     

4-单取代-1,2,3-三氮唑的修饰转化研究进展

1,2,3-三氮唑是一类广泛应用在医药、农药以及材料等领域的五元氮杂环结构.自2002年Sharpless和Meldal等发展了铜催化叠氮-炔偶极环加成反应以来,1,2,3-三唑化学在有机合成和药物化学领域的应用进入了新的发展阶段.4-单取代-1,2,3-三氮唑是该类化合物家族中的重要成员之一,其结构具有易于修饰转化的优点,由此可获得结构新颖、种类多样的衍生物分子.主要综述了4-单取代-1,2,3-三氮唑在结构修饰方面的研究进展,转化情况根据反应位点的不同分别展开,包括N¹、N²以及N³位,并讨论了反应的底物范围、局限性以及代表性反应机理.     

基于超分子离子晶体的湿度传感构效关系研究

相对湿度是许多领域的关键参数,环境湿度与人们的生活密切相关,因此对湿度进行测量和控制是各个领域中值得关注的问题之一. 在前期的研究中,作者制备了一种新型的超分子离子材料（SIM）,它是由基于咪唑的双阳离子（如1,10-双（3-甲基咪唑-1-基）癸烷,C₁₀(mim)₂）和电活性二阴离子（如2,2'-连氮基-双（3-乙基苯并噻唑啉-6-磺酸）,ABTS）组成的,发现其对湿度具有敏感且快速的响应. 在此基础上,本文制备了6种不同碳链（C₄,C₆,C₈,C₁₀,C₁₂,C₁₄）的咪唑基化合物,发现其中3种（C₁₀,C₁₂,C₁₄）可与ABTS形成水稳定的SIM. 循环伏安法、计时电流法以及石英晶体微量天平表征了这些超分子离子材料的湿度传感性能,发现基于C12的SIM具有最佳的湿度传感性能. 同时,SEM结果显示随着碳链的增加,离子材料的厚度变薄并且形态变得不规则. 因此,作者认为疏水作用和材料比表面积均会影响湿度传感的灵敏度. 本研究为发展新的湿度响应的离子传感材料奠定了基础.     

含螺环位阻铱(III)配合物的共轭结构调控及其电致发光性能研究

基于螺[芴-9,9'-氧杂蒽]的位阻结构,在其芴端连接苯并噻唑构成共轭扩展的环金属配体,并成功合成了相应的均配、面式构型铱（III）配合物fac-Ir（SFXbtz）₃.配合物的最强发射峰位于587 nm,在635 nm处伴有肩峰发射;其在溶液中的磷光寿命为316 ns,光致发光量子产率达到64.7%.以fac-Ir（SFXbtz）₃为发射材料,在高掺杂浓度下分别制备了橙光电致发光器件及与蓝光材料FIrpic（双（4,6-二氟苯基吡啶-N,C²）吡啶甲酰合铱）组合的二元白光器件.以CBP（4,4'-二（9-咔唑）联苯）为主体材料的橙光器件最高电流效率和功率效率为10.8 cd·A^-1和8.4 lm·W^-1,最大亮度为7217 cd·m^-2.二元白光器件最高电流效率和功率效率为11.6 cd·A^-1和8.0 lm·W^-1,最大亮度为8763 cd·m^-2,在3~9 V操作电压下CIE1931色坐标稳定.结果表明：协同利用螺环芳烃的共轭结构和位阻结构优势,是获得低成本、本征光电性质良好及可高浓度掺杂的磷光铱（III）配合物的便捷方法.     

应用于水相有机液流电池的双电子紫精化合物

由3-氯-1,2-丙二醇与4,4'-联吡啶通过简单的一步反应得到具有双电子特性的1,1'-双(2,3-二羟丙基)-(4,4'-联吡啶)二氯化物(DHPV²⁺Cl^2-), 其理论比容量为142.56 mA·h/g. 电化学测试结果表明, 该材料有利于提升电池容量, 且还原电位低至-0.807 V(vs. Ag/AgCl). 以NaCl为支持电解质、 DHPV²⁺Cl^2-为负极活性物质、 氮氧自由基哌啶醇(4-OH-TEMPO)为正极活性物质的全电池电压高达1.562 V, 且可在10~100 mA/cm²的电流密度下稳定运行. 采用25 mA/cm²的电流密度充放电, 活性物质的有效利用率为70.90%. 循环100次后的放电容量保持率为98.09%, 每次循环的容量平均保持率为99.93%, 表现出较好的循环性能.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。     

Features of the mechanism of oxidative dehydrodimerization of propynol

Analysis of kinetic regularities for the propynol oxidative coupling under the action of cupric salts in pyridine and in the presence of a buffer is undertaken. The reaction mechanism, including the formation of Cu(I) acetylides, is considered.