一维链状有机锡配位聚合物[(PhCH2)3Sn·(O2CC5H4N)·(H2O)]n的合成及晶体结构

[(PhCH₂)₃Sn·(O₂CC₅H₄N)·(H₂O)]_n was synthesized by the reaction of 4-pyridine car-boxylic acid with the tribenzyltin oxide and was characterized by IR,¹H NMR and MS.Its crystal structure was determined by X-ray single crystal diffraction.The crystal belongs to monoclinic.The space group P2₁/c with unit cell parameters a=1.2241(8)nm,b=0.9660(6)nm,c=2.3708(15)nm,β=102.722(12)°,V=2.734(3)nm³,Z =4,D_c=1.298g·cm^-3.In crystal,the tin atom rendered five-coordinate in a trigo nal bipyramidal structure which is bridged by 4-pyridine carboxy-late into one-dimensional chain polymers.     

2-十四烷基-DTPA及其钆(Ⅲ)螯合物的合成与表征(英)

Synthesis and characterization of the ligand, [2-tetradecyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid, H₅L] and its Gd(Ⅲ) chelate are described. Protonation constants for H₅L (lgK_i^H = 10.80, 8.40, 4.30, 2.80, 2.15) and the stability constant for GdL^2- (lgK_GdL^2-= 22.75) were determined by potentiometric titration and are similar with the related values of DTPA and Gd-DTPA respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after introduction of a linear chain tetradecyl group at the terminal acetic acid residue of DTPA.     

α-十四烷基-DOTA及其钆(Ⅲ)螯合物的合成与表征(英)

Synthesis and characterization of the ligand, [10-(α-tetradecylcarboxymethyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid, H₄L] and its Gd(Ⅲ) chelate are described. Protonation constants for H₄L(lgK_i^H = 10.62, 9.50, 4.74, 4.12) and the stability constant for GdL^-(lgK_GdL^-= 24.60) were determined by potentiometric titrations. The results obtained show that the basicity of the ligand is not significantly altered and the ligand still maintains the strong chelating properties of the parent DOTA after introduction of a linear chain tetradecyl group at the acetic side chain of DOTA.     

N-(p-乙烯氧基苯基)咔唑的合成和聚合

N-(p-Ethenyloxyphenyl) carbazole (NEOPC) has been synthesized by etherification of p-bromophenol with vinyl acetate, then p-bromophenyl vinyl ether reacting with carbaxole in the presence of brass power and potassium carbonate at 200℃. The product was identified by elemental analysis, ¹H NMR, ¹³C NMR and IR spectra. NEOPC is readily polymerized by conventional catalysts of cationic polymerization, such as BF₃OEt₂, I₂, TiCl₄, AlCl₃, etc. But no polymer was obtained when free radical initiators were used. The rearrangement products and/or the solvent-insoluble products in cationic polymerization of NEOPC. which may be produced by the crosslinking have been discussed.     

非离子型L-赖氨酸长链酯-双EDTA酰胺钆配合物的合成与弛豫效能

Four novel ester-amino ligands were synthesized by bis-acylation of octadecanyl, hexadecanyl, tetradecanyl and dedecanyl L-lysinate with ethylenediaminetetraacetic acid mono-anhydride (EDTA-MA), respectively. The corresponding neutral dimeric Gd(Ⅲ) complexes were gained by reacting these ligands with GdCl₃·6H₂O. All ligands and complexes were characterized by FTIR, ¹H NMR and elemental analysis. The longitunal relaxation time (T₁) was measured, and their stability were investigated by competition with Ca²⁺ and EDTA. The results indicate that the relaxivity of these netral binuclear Gd(Ⅲ) complexes are higher than that of Gd-DTPA.     

[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).     

MgFe2O4纳米粉体的水热合成及其表征(英)

MgFe₂O₄ nanoparticles were hydrothermally synthesized at 150 ℃ using iron nitrate [Fe(NO₃)₃·9H₂O], magnesium nitrate [Mg(NO₃)₂·6H₂O] and sodium hydroxide (NaOH) as starting materials by carefully controlling the reaction conditions. The influences of several factors such as presence or absence of Na⁺, molar ratio of Fe³⁺ / Mg²⁺, concentration of mental ions, temperature and reaction time on resultant products were investigated in the hydrothermal process. The sample was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and its magnetic properties were measured using vibrating sample magnetometer (VSM).     

九配位钇(Ⅲ)-氨三乙酸配合物K3[Y(NTA)2(H2O)]·6H2O的合成及分子结构

In this paper we describe the molecular and crystal structures of the K₃[Y(NTA)₂(H₂O)]· 6H₂O(H₃NTA=nitrilotriacetic acid). The crystal data are as followsmonoclinic system, C2/c space group, a=1.5268(3)nm,b=1.2833(3)nm,c=2.6079(5)nm,β =96.03(3)°,V=5.0815(18)nm³,Z=8,M=708.68,Dc=1.852gcm^-3,μ =2.875mm^-1,F(000)=2880.The final R1 and wR2 are 0.0636 and 0.1523 for 4264 [I >2.0σ (I)] unique reflections and 0.1178 and 0.1651 for all 4364 reflections,respectively.In the title complex, the anion [Y(NTA)₂(H₂O)]^3- has a nine-coordination structure with distorted monocapped square antiprism. Each group acts as a tetradentate ligand with three Oatoms and one Natom and a H₂O molecule caps a quadrilateral face as a ligand.It can be known that the Y(Ⅲ) ion can form a high-coordinate compound with aminopolycarboxylic acid ligands because it has a larger ionic radius (0.104nm).     

Lu(Et2dtc)3(phen)的生成反应焓变、摩尔热容和恒容燃烧能测定

A ternary solid complex Lu(Et₂dtc)₃(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt₂dtc), and 1,10-phenanthroline (o-phen·H₂O) in absolute ethanol. IR spectrum of the complex indicates that Lu³⁺ binds with sulfur atom in the Na(Et₂dtc)₃ and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, Δ_rH_m^Ө (l), was determined to be (-32.821 ± 0.147 ) kJ·mol^-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, Δ_rH_m^Ө (s), was calculated to be (104.160 ± 0.168) kJ · mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (ΔH_≠^Ө), the activation entropy (ΔS_≠^Ө), the activation free energy (ΔG_≠^Ө), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, c_m, was determined to be (82.23 ± 1.47) J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combustion energy of the complex, Δ_cU, was determined as (-17 898.228 ± 8.59) kJ·mol^-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δ_cH_m^Ө, and standard enthalpy of formation, Δ_fH_m^Ө, were calculated to be (-17 917.43 ± 8.11) kJ·mol^-1 and (-859.95 ±10.12) kJ·mol^-1, respectively.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

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.

     

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。     

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.     

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。     

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.     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.     

NiY分子筛表面酸性影响其选择性吸附脱硫性能的机理研究

采用原位红外光谱技术,以噻吩、环己烯和苯为模型探针分子,分别考察单一烃分子在NiY分子筛上的吸附与反应行为以及噻吩与烯烃、芳烃间的竞争吸附和催化反应行为。单一探针分子吸附研究发现,NiY分子筛中与Ni物种相关的Lewis(L)酸位是噻吩的选择性吸附活性位;噻吩和环己烯在NiY分子筛中Brnsted(B)酸位上发生的质子化和低聚反应明显弱于HY分子筛。双探针分子竞争吸附研究发现,环己烯二聚体在NiY中强B酸位上的强化学吸附与噻吩存在显著的竞争吸附行为。另外,苯和噻吩在NiY上的竞争吸附现象在373K时明显减弱。由此,在选择性吸附脱硫过程中,减少吸附剂表面B酸中心可降低烯烃对噻吩的竞争吸附,另外适当提高吸附体系的温度可以有效避免芳烃对噻吩的竞争吸附。