三种马来二腈基二硫烯镍(Ⅲ)离子对配合物的制备和结构表征

合成了3种离子对配合物 [1-benzyl-3-bromopyridium]⁺[Ni(mnt)₂]^- (1)，[1-(4′-flurobenzyl)-3-bromopyridiunm]⁺[Ni(mnt)₂]^- (2)，[1-(4′-cholorobenzyl)-3-bromopyridium]⁺[Ni(mnt)₂]^- (3)，(mnt=马来二腈基二硫烯，maleonitrile dithiolate)获得了单晶并解析了它们的单晶结构。     

BH分子X 1Σ+、A 1Π和B 1Σ+ 态的势能函数

利用SAC/SAC-CI方法，使用D95++、6-311++g及cc-PVTZ等基组，对BH分子的基态(X ¹Σ⁺)、第一简并激发态(A ¹Π)及第二激发态(B ¹Σ⁺)的平衡结构和谐振频率进行了优化计算． 通过对三个基组计算结果的比较，得出了cc-PVTZ基组为三个基组中的最优基组的结论；使用cc-PVTZ基组，利用SAC的GSUM(group sum of operators)方法对基态(X ¹Σ⁺)， SAC-CI的GSUM方法对激发态(A ¹Π 和B ¹Σ⁺)进行单点能扫描计算, 用正规方程组拟合Murrell-Sorbie函数，得到了相应电子态的完整势能函数；从得到的势能函数计算了与基态(X ¹Σ⁺)、第一简并的激发态(A ¹Π)和第二激发态(X ¹Σ⁺)相对应的光谱常数(Be、αe、ωe 和ωeχe)，结果与实验数据较为一致． 其中基态、第一激发态与实验数据吻合得较好．     

二维二氧化硅改性聚环氧乙烷基固态聚合物电解质用于增强锂离子电池性能

通过改性由酸蚀二维蛭石制备的二维二氧化硅,得到带正电荷的二维介孔二氧化硅(PSN⁺)纳米片,并将PSN⁺用作聚环氧乙烷(PEO)基固体聚合物电解质(SPEs)的填料。由于PSN⁺具有丰富的正电荷,PSN⁺与锂盐解离的阴离子能够有效结合,从而促进锂离子的运输,获得较好的锂离子转移数。在50 ℃时,基于PSN⁺的SPEs表现出较高的离子电导率(7.5×10^-5 S·cm^-1),锂离子迁移数为0.30,稳定电压窗为4.41 V。因此,组装后的LiFePO₄锂电池在50 ℃、0.2C下具有优异的初始放电比容量(155.7 mAh·g^-1),在循环100次后容量保持率为97.1%。     

改性硅藻土负载亚铁氰化铜复合物的制备及其对Cs+的吸附性能

采用水热法、以氯化铝为铝源对硅藻土(De)进行改性,通过浸渍法将亚铁氰化铜(KCuHCF)纳米颗粒负载于改性De表面,制备出γ-AlOOH/De-KCuHCF和γ-Al₂O₃/De-KCuHCF两种复合吸附剂,对所制备的吸附剂进行了表征,并研究了其对Cs⁺的吸附性能。结果表明,所制备吸附剂具有优异的Cs⁺吸附性能,γ-AlOOH/De-KCuHCF和γ-Al₂O₃/De-KCuHCF最高吸附容量分别可达75.44、84.02 mg·g^-1,γ-Al₂O₃/De-KCuHCF对模拟卤水中Cs⁺的吸附率高达97.55%;以3 mol·L^-1 NH₄NO₃为脱附剂,经3级连续脱附后,γ-Al₂O₃/De-KCuHCF的Cs⁺脱附率可达81.88%,经过5次吸附-脱附循环后仍保持了较高的吸附量。     

DFT法研究离子液中EMIM+催化丁烯双键异构反应机理(II)

用密度泛函理论(DFT)在B3LYP/6-31G(d, p)的计算水平上研究了离子液中1-乙基-3-甲基咪唑阳离子(EMIM⁺)的4-H和5-H原子催化丁烯双键异构反应的可能途径，优化了反应体系的平衡态和过渡态的几何构型，分析了反应过程中键参数的变化，通过振动分析对平衡态和过渡态进行了验证. 计算结果表明, 离子液中的EMIM⁺首先通过4-H和5-H原子吸附丁烯, 进而催化丁烯的双键异构反应, EMIM⁺的4-H和5-H催化1-丁烯异构为2-丁烯的正反应活化能分别为204.2和207.3 kJ•mol^-1，逆反应活化能约为220.9和223.8 kJ•mol^-1， 反应为基元反应.     

γ辐照诱导金纳米粒子的形成和形貌重塑

在十六烷基三甲基溴化铵(CTAB)水溶液中，抗坏血酸(AA)将橙黄色的Au³⁺还原为无色的Au⁺,在γ射线产生的水合电子的作用下，Au⁺进一步还被原成Au⁰，并在微量的Ag⁺诱导所产生的CTAB胶束中生长成为Au纳米棒。控制γ辐照的时间，可以实现金纳米粒子的形貌重塑，即由最初的棒状变为立方体，最终变为多面体。     

CoPt纳米空心球甲醇电催化氧化和原位电化学傅里叶变换红外光谱研究

采用化学还原和电位置换法制备了CoPt 纳米空心球, 该催化剂对甲醇氧化表现出较好的电催化活性.透射电镜(TEM)、能量散射光谱(EDS)和电化学循环伏安实验结果表明, 在0.1 mol·L^-1 H₂SO₄+0.1 mol·L^-1CH₃OH中进行测试时, CoPt 纳米空心球发生了去合金化过程, 催化剂表面Co元素溶解, 形成了富Pt 表面, 表现出更好的电催化活性, 同时表现出较好的结构稳定性. 采用原位电化学红外光谱在分子水平研究了CoPt 纳米空心球上甲醇氧化过程, 发现甲醇在CoPt 纳米空心球氧化中间产物主要为CO, 且CO表现出异常红外效应, 与CO为探针分子在CoPt纳米空心球上得到的红外光谱结果一致. 研究结果表明, 去合金化方法是一种有效调节催化剂表面组成和性能的手段, 原位电化学红外光谱是潜在的原位研究有机小分子氧化机理的方法, 在燃料电池中将得到广泛的应用.     

一锅法高效制备橙色荧光氧化石墨烯量子点及其在细胞pH成像中的应用

以价廉、易得的石墨片为原料,采用改进的Hummers法,简单、快速、高效地制备了具有良好生物相容性的橙色荧光氧化石墨烯量子点(GOQDs)。所制备的GOQDs尺寸约7.2 nm,具有尺寸均匀、晶格间距为0.20 nm的高度结晶的核心和氧化的外围结构。与大多数报道的碳点(CDs)、包裹掺杂碳点(掺杂 CDs)、石墨烯量子点(GQDS)和 GOQDs不同,我们的方法制备的 GOQDs显示出橙红色并具有激发波长独立的荧光发射。此外,GOQDs具有pH依赖性荧光发射、强的光漂白抗性、低细胞毒性、良好的水溶性(ρ=10 mg·mL^-1)和优异的生物相容性。这些特性使其成功应用于细胞pH成像。     

基于非手性邻苯酚胺衍生物的半醌Fe(III)络合物的镜面对称性破缺及其绝对构型关联

以2- 苯胺基-4,6- 二叔丁基苯酚(H₂L)和FeCl₂·4H₂O为原料制备了一对手性半醌Fe(III) 络合物Λ-mer-[Fe(L^ISQ)₃]和Δ-mer-[Fe(L^ISQ)₃] (L^ISQ: 2-苯亚胺基-4, 6-二叔丁基苯酚, mer: 经式构型), 通过单晶X射线衍射分析结合单晶压制片膜的固体圆二色(CD)光谱确定了该络合物的绝对构型, 在此基础上建立了此类半醌络合物[M(L^ISQ)₃] (M=Cr, Fe, Co)的惟手性金属中心绝对构型与固体CD光谱之间的关联. 此外, 还对10份合成的[Fe(L^ISQ)₃]的大宗产物粉末与单晶的固体CD谱进行了比对分析, 以及对1 份合成产物进行10 次重结晶的固体CD 光谱表征. 研究表明该化合物在结晶过程中发生了镜面对称性破缺(MSB), 对映体过量(ee) 值在15%-100%之间.     

阳离子(从有机铵到无机阳离子)对fac-[Fe(CO)3I3]-阴离子的稳定性和毒性的调节

通过无机碘盐(MI_n)与 cis-[Fe(CO)₄I₂]反应制备了 5 个盐类化合物 fac-M[Fe(CO)₃I₃]_n (Mⁿ⁺=Na⁺ (1),K⁺ (2),Mg²⁺ (3),Ca²⁺ (4),NH₄⁺ (5)),探讨了阳离子Mⁿ⁺对fac-[Fe(CO)₃I₃]^-阴离子的稳定性和细胞毒性的影响。通过傅里叶变换红外光谱(FTIR)监测,发现盐 1~5在 DMSO、D₂O、生理盐水等介质中均能缓释 CO,其释放动力学符合一级反应动力学模型;还发现溶液中碘离子的浓度和酸度对该阴离子的缓释CO性能也具有调节作用。通过噻唑蓝(MTT)实验评估了盐1~5对膀胱癌细胞的毒性,其24 h半抑制浓度(IC₅₀)在 25~43 μmol·L^-1。与有机铵阳离子类的盐化合物相比,盐1~5在含水介质中的释放 CO速率下降,毒性亦有下调。研究还发现这类fac-[Fe(CO)₃I₃]^-阴离子在缓释CO的同时释放碘自由基,并能导致线粒体活性氧(ROS)水平、Parkin蛋白表达均上调。铁死亡抑制剂(Ferrostatin-1和Liproxstatin-1)试验结果表明这类化合物可能引发铁死亡通路并促进肿瘤细胞死亡。     

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.     

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。     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

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.     

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.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。