簇合物Mo_2X_8~(4-)(X=Cl,Br)低能态电子光谱

应用间略微分重叠自洽场和组态作用(INDO/S-CI)方法,计算双核簇合物Mo_2X_8~(4-)(X=Cl,Br)基态~1A_(1g)至不同低能态的d电子自旋允许的跃迁能,得出Mo—Mo四重键均裂时所需的能量大小依次为键σ>π>>δ。对于Mo_2Cl_8~(4-)簇合物态~1A_(1g)→1~1A_(2u)(δ→δ~*)和~1A_(1g)→2~1E_g(π→δ~*)的电子跃迁能,理论值(15584和22587cm~(-1))与低温时测得光谱实验值(18083和22000cm~(-1))较为接近。此外,本文还提出了簇合物Mo_2X_8~(4-)的态相同而X不同时,电子跃迁能变化,主要决定于参与电子转移过程的分子轨道组成成份的看法。     

Eu(Ⅲ)离子光谱探针配合物Eu(DMBM)(TPPO)_2(NO_3)_2中Eu(Ⅲ)的格位

77K下测得的激光激发光谱和发光光谱表明,配合物Eu(DMBM)(TPPO)_2(NO_3)_2(DMBM:二对甲氧基苯甲酰甲烷;TPPO:三苯基氧化膦)中的Eu(Ⅲ)离子具有两种晶格格位。~5D_0→~7F_I(0～2)跃迁光谱说明这两种铕(Ⅲ)格位的点群对称性分别是C_(2v)和C_1(或C_2或C_5)。有较高对称性(C_(2v))的格位在配合物中占优势。     

氯冉酸阴离子桥联双核铜(II)配合物的合成和磁性

本文合成了五种以氯冉酸二价阴离子为桥联配体的Cu(II)单核([CuLCA].H~2O)和双核([Cu~2L~2CA](ClO~4)~2配合物:[Ca(phen)CA].H~2O(1),[Cu~2(phen)~2CA](ClO~4)~2(2),[Cu(NO~2-phen)CA].H~2O(3),[Cu~2(NO~2-phen)~2CA](ClO~4)~2(4)和[Cu~2(bpy)~2CA](ClO~4)~2(5)。经元素分析、红外、固体紫外、顺磁共振、磁化率及变温磁化率的测定对上述各配合物进行了表征。配合物1,3可能是通过水分子中的氢键将两个[CuLCA]单元联接而缔合的假双聚体。配合物2,4,5则由阳[Cu~2L~2CA]^2^+阳离子和弱配位的ClO~4^-阴离子所组成。双核配合物中Cu(II)离子的几何构型可能为畸变的四方锥。所有五种配合物均难溶于水及常见有机溶剂。上述配合物的室温ESR谱呈现ΔM~s=2的从单重态到三重态的半场跃迁。配合物2,5的变温磁化率(4-300K)已测得,利用Heisenberg模型确定交换参数J值为-29.2和-25.7cm^-^1。表明在此类桥联配合物中,两核间存在着反铁磁性交换耦合作用。     

稀土硼氢化物研究——ⅩⅡ.含[B_(12)H_(12)]~(2-)、[B_(10)H_(10)]~(2-)及[B_(10)H_9NH_2COC_3H_7]~-的联吡啶氮氧化物稀土配合物

稀土十二氢十二硼酸与2,2′-联吡啶-N,N′-二氧化物反应,或稀土氯化物与2,2′-联吡啶N,N′-二氧化物及十硼十氢双四乙基铵或Et_4NB_(10)H_9NH_2COC_3H_7反应,制取八个新型稀土配合物。经元素分析、红外光谱、紫外光谱、摩尔电导测定及X射线衍射分析对配合物进行了表征。结果表明,2,2′-联吡啶N,N′-二氧化物以两个氧原子与稀土螯合。含[B_(10)H_9NH_2COC_3H_7]~-配合物中,它通过羰基氧与稀土配位。配合物热稳定次序为:[B_(12)H_(12)]~(2-)>[B_(10)H_9NH_2COC_3H_7]~->[B_(10)H_(10)]~(2-)配合物。     

氯冉酸阴离子桥联双核铜(II)配合物的合成和磁性

本文合成了五种以氯冉酸二价阴离子为桥联配体的Cu(II)单核([CuLCA].H~2O)和双核([Cu~2L~2CA](ClO~4)~2配合物:[Ca(phen)CA].H~2O(1),[Cu~2(phen)~2CA](ClO~4)~2(2),[Cu(NO~2-phen)CA].H~2O(3),[Cu~2(NO~2-phen)~2CA](ClO~4)~2(4)和[Cu~2(bpy)~2CA](ClO~4)~2(5)。经元素分析、红外、固体紫外、顺磁共振、磁化率及变温磁化率的测定对上述各配合物进行了表征。配合物1,3可能是通过水分子中的氢键将两个[CuLCA]单元联接而缔合的假双聚体。配合物2,4,5则由阳[Cu~2L~2CA]^2^+阳离子和弱配位的ClO~4^-阴离子所组成。双核配合物中Cu(II)离子的几何构型可能为畸变的四方锥。所有五种配合物均难溶于水及常见有机溶剂。上述配合物的室温ESR谱呈现ΔM~s=2的从单重态到三重态的半场跃迁。配合物2,5的变温磁化率(4-300K)已测得,利用Heisenberg模型确定交换参数J值为-29.2和-25.7cm^-^1。表明在此类桥联配合物中,两核间存在着反铁磁性交换耦合作用。     

非手性芳香冠醚同β-环糊精配位时所诱导出的圆二色性(ICD)研究

本文报道六种非手性芳香冠醚,即苯并-15-c-5,苯并-18-c-6,4-叔丁基苯并-15-c-5,二苯并-18-c-6,二苯并-24-c-8,4,4’二叔丁基二苯并-30-c-10,在3:2水-甲醇体系中同β-环糊精配位时的紫外光谱及诱导出的圆二色性谱。有趣的是,这些冠醚的邻苯二酚基生色团的~1A_1←~1A_1及~1B_2←~1A_1跃迁区的每一个谱带区均诱导出负正交替的圆二色性,经用Job连续变量法及摩尔比法确定系有两种配合物生成,一种是2:1 β-环糊精-冠醚配合物,另一种是1:2 β-环糊精-冠醚配合物。应用Shimizu等的理论结果,确定了含邻苯二酚基生色团的冠醚在β-环糊精空腔中的取向及其包结形态。就2:1配合物而言,本质上是一种亲脂相互作用,它遵循环糊精包结物的一般规律。对于1:2的β-环糊精-冠醚配合物,不存在β-环糊精空腔对冠醚的邻苯二酚基生色团的包结作用,所以推断其结构可能是,二个冠醚分子分别从β-环糊精圆筒的两端将环糊精分子包结起来,彼此间的作用是一种亲水相互作用。     

卡铂水溶液的光化学研究

本文研究了卡铂水溶液在313nm和254nm的紫外光作用下的反应产物、量子产率和反应机理。光激发配位场~1A_1→~1A_2和~1A_1→~1E d-d跃迁,引起配位取代反应,生成二水二氨合铂(Ⅱ)和四水合铂(Ⅱ),然后进行热水解和聚合,形成多核羟基桥铂配合物,氧气不参与反应;光激发~1A_1→~1A_(2u) Pt←O电荷转移跃迁,引起氧化还原反应,氧气参与反应,在氮气气氛下产生金属铂而在氧气气氛下产生二水二氨合铂(Ⅱ)。     

[(NH_3)_5CoImCu(dien)ImCo(NH_3)_5](ClO_4)_6·4H_2O配合物单晶的ESR研究

研究了咪唑桥联异三核配合物[(NH_3)_5CoImCu(dien)ImCo(NH_3)_5](ClO_4)_6·4H_2O与同构配合物[(NH_3)_5CoImZn(dien)ImCo(NH_3)_5]·4H_2O混合单晶在低温(100 K)下的ESR。应用适于求非同轴g张量和A张量的最小二乘法拟合技术,解出标题配合物的g张量和A张量主值分别为:g_1=2.246,g_2=2.093,g_3=2.048,A_1=1.63×10~(-2)cm~(-1),A_2=0.38×10~(-2)cm~(-1),A_3=0.17×10~(-2)cm~(-1)及g_1=2.245,g_2=2.090,g_3=2.051,A_1=1.64×10~(-2)cm~(-1),A_2=0.37×10~(-2)cm~(-1),A_3=0.17×10~(-2)cm~(-1)。配合物Cu~(2+)的4s、3d轨道上的电子自旋密度分别为0.018和0.557。Cu~(2+)与配体间的键有较强的共价性。     

系列Cu(Ⅱ/Ⅰ)配合物的制备及其表面光电压

采用水热法合成了{[Cu(phen)(H2O)(o-tpha)]·H2O}n(1), [Cu2Cl4(phen)2](2), [Cu4Cl4·(bipy)2](3)和[Cu2Cl2(phen)]n(4)(bipy=2,2'-bipyridyl, phen=1,10-phenanthroline, o-H2tpha=o-phthalic acid)4个铜配合物. X射线单晶衍射结果表明, 配合物1和4是具有一维无限结构的聚合物, 配合物2是双核Cu(Ⅱ) 配合物并由氢键连成超分子, 配合物3是四核Cu(Ⅰ) 簇合物. 常温下测定了4个配合物的表面光电压光谱(SPS)、场诱导表面光电压光谱(FISPS)、IR和UV-Vis-NIR光谱. SPS的测试结果显示, 4个化合物均在300~800 nm范围内存在光伏响应带, 但是它们呈现了不同的特性. 配合物1~3的表面光电压光谱呈现出正的表面光伏响应(SPV), 配合物4的SPS呈现出负的表面光伏响应. 4个配合物的表面光伏响应带的位置、数量以及强度均有明显不同.     

A_(a_1)B_(b_1)—A_(a_2)B_(b_2)缩聚反应的分布函数和高分子矩

本文用概率统计方法,得到了A_(a1)B_(b1)—A_(a2)B_(b2)缩聚反应的分布函数。应用分布函数定义了高分子各类矩。用直接微商法,得到了计算矩的循环公式。解决了用矩表征这类反应的问题。本文也得到了凝胶化条件。     

Industrial irradiator radiation safety program assessments

Considerable attention is typically given to radiation safety in the design of irradiators and initially establishing the program. However, one component that may not receive enough attention is applying the continuous improvement philosophy to the radiation safety program. Periodic total program assessments of radiation safety can ensure that the design and implementation of the program continues to be applicable to the operations. The first step in the process must be to determine what is to be covered in the program assessment. While regulatory compliance audits are a component, the most useful evaluation will extend beyond looking only at compliance and determine whether the radiation safety program is the most appropriate for the particular operation. Several aspects of the irradiator operation, not all of which may routinely be considered “radiation safety”, per se, should be included: Design aspects of the irradiator and operating system, system controls, and maintenance procedures, as well as the more traditional radiation safety program components such as surveys, measurements and training.     

Calculation of chromatographic dead times and retention indices with the aid of a computer program in BASIC

A computer program is presented for calculating chromatographic dead time from the observed retention times of an homologous series of standards using the iterative approximation procedure of Guardino et al. The program is written in BASIC and is readily adaptable to most microcomputers capable of using BASIC. Corrected retention times and capacity factors of standards and of samples are also calculated by the program. Examples of applications in gas chromatography and reversed-phase high-pressure liquid chromatography are presented. A listing of the BASIC program is given.     

The MMP2 calculational method

The molecular mechanics (MMP2) program and procedures for the treatment of conjugated hydrocarbons, and some of the results which they can achieve are described. The program is an updated version of the similar MMP1 program, but contains some differences. It is based on an SCF π system calculation, rather than on the VESCF method used earlier. All parameters are compatible with those in the MM2 program. Hence it is possible to calculate heats of formation, resonance energies, and structures for conjugated hydrocarbons in a way that is consistent with the calculations on non-conjugated molecules. The overall results as far as structure and energy are somewhat better than they were with the MMP1 program.     

A Computer Program for the Evaluation of Non-isothermal Kinetic Parameters

A program for the evaluation of non-isothermal kinetic parameters is presented. The program allows evaluation of the kinetic parameters under constant heating rate or constant reaction rate conditions. The simulation of temperature vs. conversion curves is also possible. A regression method is included, which allows a discrimination between various conversion functions and also evaluation of the activation parameters. The program was tested with various simulated decomposition curves and the non-isothermal decomposition curves of calcium oxalate. The program is written in Visual BASIC 4.0 and can be run under Windows 95 ©.     

Automated classification of candidate structures for computer-assisted structure elucidation

In computer-assisted structure elucidation, a large number of candidate structures for the unknown compound can be generated. A computer program designed to aid in the recognition of significant differences between these structures is described. The goal of the program is to group the candidates into meaningful classes with a minimum of input from the user; each class is distinguished by a substructure its members have in common. A computational approach is developed based on the combinatorial problem of set covering. The program evaluates its results using an information-theoretical criterion. An application of the program to a real-word structure problem is presented.     

中药注射剂三维荧光等高线图识别程序的设计与检验

用统计模式识别法设计了中药注射剂三维荧光指纹图谱的识别程序,对刺五加、红花、血栓通和香丹4种注射剂进行了识别,识别结果正确。研究表明:该程序分辨率高,便于自动化,可用于中药注射剂的真伪鉴别和质量监控。     

Computer program for neutron activation analysis with the SLOWPOKE reactor

A FORTRAN computer program for automatic neutron activation analysis is presented. The program locates and identifies peaks in a gamma-ray spectrum, calculates peak areas and the concentrations of the elements of interest in the sample. This program was specifically designed for the SLOWPOKE reactor, it uses a semi-absolute method and does not need standards or flux monitors. The program was written so as to minimize the computation time, and a typical 4096-channel spectrum is processed in five seconds by an IBM 360/75 computer.     

Dechaos — A program for automatic or interactive analysis of gamma-ray spectra

DECHAOS is a gamma-ray spectral analysis program for personal computers. The program offers two modes of operation, automatic or interactive. The spectra to be analyzed can be acquired using any pulse height analyzer. The program includes routines for energy calibration, peak shape and efficiency calibration. Complex multiplets can be resolved automatically with the peak areas being determined using least-squares fitting techniques. Output tables include all data used in the calculation and peak information. The program is public domain software.     

角度重叠模型的应用 Ⅰ.计算过渡金属配合物电子光谱的微机程序

按照角度重叠模型,用FORTRAN语言编写了计算过渡金属配合物电子光谱的微机程序。     

MAPOS: a computer program for organic synthesis design based on synthon model of organic chemistry

The program MAPOS is a logically oriented computer program for computer-aided organic synthesis design suitable both for forward and retrosynthetic synthesis planning. It is based on the synthon model of organic chemistry, introduced by the authors. The fundamentals of the model as well as the basic algorithms are described. Examples of the use of the program are given.