溴代作用对竹红菌乙素分子性质影响的量子化学研究

用半经验量子化学方法ＡＭ１和ＰＭ３对竹红菌乙素及其溴代物进行了对比计算,考究了溴代作用对竹红菌乙素分子性质的影响,两种方法所得结果的均表明,溴代作用使分子的生成热、前线轨道能级及偶极矩等参数都有所降低,溴代作用也影响了竹红菌乙素分子内氢健的性质,并能使其对光的吸收产生红移。『     

L—赖氨酸锌配合物结构的理论研究

采用量子化学半经验PM3方法,优化了L-赖氨酸锌配合物的几何结构,对L-赖氨酸锌配合物的结构、电子性质进行了分析,结果表明：计算结果与实验得到的晶体结构基本吻合,证实了L-赖氨酸锌配合物中Zn具有五配位结构,同时对体系的净电荷分布及前线轨道成分进行了分析。     

Mechanisms of the reactions of propane with CBr3+ cation and superelectrophilic complex CBr4+·AlBr3- containing a bromine-centered cationic center: a theoretical study

Fragments of the potential energy surfaces (PES) of the systems [C₃H₈ + CBr₃ ⁺] and [C₃H₈ + Br₂CBr⁺·Br₂AlBr₂ ^–] were simulated by the MNDO/PM3 method. Energy minima corresponding to weakly bound adducts of propane molecule with the CBr₃ ⁺ cation or neutral complex CBr₃ ⁺·AlBr₄ ^– were found on the PES's of both systems. These are adducts with the coordination of a H atom of the methylene group of the propane molecule to the electrophile at the Br atom carrying the largest positive charge. As the fragments of the adducts are brought close together, the coordinated H atom migrates to the C atom of the CBr₃ ⁺ fragment. The potential barriers of these migrations were found to be low for both systems. The reactions proceed without formation of cyclic intermediates or transition states typical of the Olah mechanism.     

Excimer fluorescence and structures of the inclusion complexes of β-cyclodextrin with naphthalene and its derivatives

Fluorescence of the inclusion complexes with different compositions formed by naphthalene-h₈, naphthalene-d₈, 2,7-dimethylnaphthalene (DMN), and 2-benzylnaphthalene (BN) with β-cyclodextrin (β-CD) in water was studied. Two types of fluorescence are observed, monomer (MF) and excimer (EF_ fluorescence. The excimer fluorescence of the 2∶2 complex emitted by aggregated light-dispersing crystals forming a precipitate, whereas is the MF is concentrations, EF predominates for the resulting complexes. A proposed structure of the inclusion complexes was derived from MNDO/PM3 semiempirical quantum-chemical calculations. The EF is caused by the structure of the complex, in which both naphthalene molecules are separated by a distance of 4.7 Å: they lie in parallel orientation to each other, whereby one ring is displaced from the other by one-fourth of the length of the naphthalene ring. The complexes of 2,7-DMN and 2-benzylnaphthalene with β-CD do not exhibit EF. For the 2∶2 complex of 2,7-DMN with β-CD, this is due to the fact that the aromatic fragments are removed too far from one another 2-Benzylnaphthalene is unable to form an inclusion complex with β-CD, in whose structure the aromatic fragments inside the cavity could be arranged in parallel planes; instead, it forms a 1∶2 complex with β-CD.     

Simulation of molecular and electronic structure of polyhydrogenated (n,0)-tubulenes and their analogs intercalated with lithium

Molecular and electronic structure of four polyhydrogenated (n,0)-tubulenes, namely, [−C₂₄H₄−] _m (1), two isomers of composition [−C₂₈H₄−] _m (2 and3), and [−C₃₂H₄−] _m (4) withn benzene rings in the cross section (n=6, 7, 7, and 8, respectively), was simulated atm>1 (m is the number of repeating fragemnts). It was assumed that hydrogen atoms are attached to all carbon atoms lying on the two most distant elements of the cylinders of the corresponding tubulenes. The energy band structures of macromolecules1–4 and their Li-intercalated analogs [−C₂₄H₄Li−] _m (5) [−C₂₈H₄Li−] _m (two isomers,6 and7), and [−C₃₂H₄Li−] _m (8), containing one Li atom per repeating unit at each center, were obtained in the EHT approximation by the crystal orbital method. Geometric parameters of repeating units of structures1–8 were found after MNDO/PM3 optimization of the energies of hydrocarbon molecules C₇₂H₂₄, C₈₄H₂₆ (two geometric isomers), and C₉₆H₂₈, containing three repeating units of corresponding tubulenes1–4 each. The conductivity types of polyhydrogenated tubulenes1–4 are the same as those of their precursors, (6,0)-, (7,0)-, and (8,0)-tubulenes. Dispersion curves of systems5–8 are much the same as those of macromolecules1–4; however, electron energy spectra of5–8 possess metallic conductivity type and the positions of Fermi levels for these systems are higher than for compounds1–4. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2061–2067, November, 1999.     

空气中PM2.5的扩散衰减与预测分析

以西安市2013年1月1日-9月19日的空气污染监测数据为例,采用非稳态的二维多箱模型,综合考虑了风向、季节等因素的影响,对西安市PM2.5的面源污染扩散和衰减规律进行模拟预测,计算模型相对误差;再选用高斯模型对某一天西安市突发情况下PM2.5浓度扩散情况进行点源污染扩散预测,并评价模型的有效性.     

PM2.5成因的逐步回归分析及治理方案研究

应用逐步回归分析方法获得了PM2.5与3个既与综合治理又与专项治理有关的因素SO_2、NO_2、PM10的最优二次回归方程,在将治理基准年与五年后目标的PM2.5浓度折算为对应的AQI指标之后,结合数据分析计算出了基准年的PM2.5、SO_2、NO_2、PM10这4个基准指标值.然后结合PM2.5综合治理与专项治理的费用经验公式,按照五年治理投入总经费最小的原则建立了一个标准的非线性规划模型,并求解出了最少的五年总投入经费及每年经费投入.对于指导PM2.5的治理工作有一定实际意义.     

Evaluation of the electronic density at critical points of hydrogen bonds: PM7 a good alternative to ab-initio methods

Hydrogen bonds are of vital importance in the formation and functioning of organic molecules; their characterization with theoretical tools is a task of interest to the scientific community. Commonly, the electron density at the bond critical point is used to characterize bonds. Generally this task is carried out with ab-initio methods. In this study, the PM7 semi-empirical approach is used to evaluate the quality of the electron density at the hydrogen bond critical points (HBCPs). The research takes into account dimers, nucleobases and alpha-helices bonded by hydrogen bonds: $$, $$, $$, $$, $$, and $$. The results are compared with second-order Møller–Plesset and density functional theory. The findings demonstrate that PM7 is a reliable alternative for explaining the electron density trends at the HBCPs.     

Carbon-13 NMR Study of 2,4,6-Triaryl Pyridinium Salts

The carbon-13 chemical shift of seventeen N-substituted 2,4,6-triphenyl pyridinium salts (TPP) and N-substituted 2,4,6-triaryl pyridinium (TsPP) salts have been determined.     

O_2/CO_2气氛添加高岭石对燃煤PM_(2.5)排放的影响

采用管式炉研究了在O2/CO2气氛下添加高岭石对PM2.5(空气动力学直径小于2.5μm的颗粒物)排放特性的影响。实验采用荷电低压撞击器(ELPI)采集和分析燃烧后的PM2.5。结果表明,添加高岭石是燃烧过程中影响PM2.5生成的重要因素。添加高岭石后,生成PM1的数量和质量浓度均降低,而PM1-2.5的数量和质量浓度均略有增加,PM2.5粒径分布均呈双峰分布,峰值点分别出现在0.2μm和2.0μm左右。随着高岭石添加质量比的增加,PM2.5中的S、Pb、Cu、Na和K五种元素的浓度呈下降趋势。粒径小于0.317μm的亚微米颗粒通过气化-凝结机理形成,而超微米颗粒则是通过亚微米颗粒凝聚、聚结和矿物质熔融、破碎、聚结形成。