C_1化学简介

一、前言未来的化学和化学工业应具有原料来源广泛,节省能源,综合利用,无公害等特点。C_1化学就是顺应这一需要而迅速获得发展的一个新的化学领域。七十年代以来,由于资本主义国     

自掺杂La1—δMn1—5O3化合物的晶体结构和巨磁电阻效应

采用溶胶－凝胶工艺制备了Ｌａ１－δＭｎ１－δＯ３化合物，研究了烧结条件的改变对材料的结构、磁性、导电性、磁电阻效应的影响，首次２发现Ｌａ１－δＭｎ１－δＯ３化合物的电阻－温度曲线的双峰现象。     

红细胞膜上各种磷脂中脂肪酸的测定

应用自制硅胶板的薄层色谱法分离了红细胞膜上四种主要磷脂。将分离后的每种磷脂斑点硅胶涂层刮下，不经萃取，直接在无水甲醇－苯－乙酰氯溶液中进行转移甲基化，然后用毛细管相色谱分离测定其脂肪酸组成和含量。上述方法已成功地用于先天愚型病人和正常人红细胞膜上各种磷脂中脂肪酸轮廓分析，获得有意义的结果。     

优化几何构型对高级别从头算能量的影响

对《ＣＲＣ物理与化学手册》（第７７版）中第三周期以前的无机双原子分子,当其理论优化构型的相对误差大于２％时,分别在实验构型和最大偏差的理论构型下,计算了ＱＣＩＳＤ（Ｔ）／６－３１１＋Ｇ（３ｄｆ,２ｐ）能量并作了比较。结果表明,大多数能量的差别在４．２ｋＪ．ｍｏｌ＾－１以内。由此说明,目前一般采用的构型优化理论方法,多数情况下不至于明显影响单点高级别从头算的计算精度。同时还发现,Ｇ２（ＱＣＩ）的高级     

水溶性金属卟啉肿瘤靶向磁共振成像造影剂的研究

利用显微荧光－阿达玛变换三维图像分析研究了Ｃｕ－ＴＳＰＰ，Ｍｎ－ＴＳＰＰ，Ｃｕ－ＴＭＡＰ，Ｍｎ－ＴＭＡＰ４种水溶性金属卟啉人细胞间质进入肿瘤细胞内的富集过程，对金属卟啉的自旋－晶格驰豫性能（Ｒ１）的天空结果表明，Ｍｎ（Ⅱ）卟啉配合物的Ｒ１、值结Ｇｄ－ＤＴＰＡ提高１．５－２倍。     

高灵敏度无机分光光度法

前言对于分析方法,特别是工业分析方法,一般都希望不使用价格昂贵的特殊装置;操作简便;不论何人、何时、何地使用均能得到可靠的数据。而分光光度法在相当程度上能满足这样的要求。虽然现在各种仪器分析方法得到了迅速的发展,但分光光度法仍然广泛应用于各个领域,日本工业标准等法定的分析方法亦采用分光光度法,其原因恐怕就在于此。如果能将分光光度法韵应用范围从以往的痕量成分分析扩大到超痕量成分分析,那将是非常理想的。从这个观点出发,     

Pt碘乙二胺配合物的DFT和DV-Xα研究

利用密度泛函DFT/LANL2DZ和DV-Xα，对两种Pt(IV)碘配合物trans，cis-[Pt (OAc)_2I_2(en)] (A)，trans，cis-[Pt(OH)_2I_2(en)] (B)及它们的光照产物 [Pt(OAc)_2(OH)I(en)] (C)，[Pt(OH)_3I(en)] (D)完成了几何优化；计算了配合 物能级、光谱、前线轨道组成、电荷布居等性质。计算结果能解释有关的实验现象 。     

聚合物{[CuII(Hpb) (mal)]H2O}n :单体的量子化学计算和磁性研究

{[Cu^Ⅱ（Hpb）（mal）]H=O}n （Hpb=2-2＇-pyridylbenzimidazole, mal=maleic acid） is a helical chain-like polymer complex. In order to investigate the electronic structure of the complex, the monomer Cu^Ⅱ（Hpb）（mal） was obturated with different functional groups respectively. For these selective segments, the geometry optimizations were conducted by using hybrid DFT （B3LYP）methods to find that the structure obturated with H2O was better consistent with the experiment, and then this model would be used to latter calculations, such as the frontier molecular orbital and the NBO charge population analysis. In addition the magnetic behaviors of this complex were analyzed by experiments and the weak antiferromagnetic couple between copper（Ⅱ） ions was observed. The exchange coupling constant was calculated by DFT based on the spin broken symmetry formalism. The calculated coupling constants were in good agreement with the experimental data.     

含芯电子相关能修正的G2理论——G2(ful)

A general method in considering the core electronic correlation energies has been proposed and introduced into the standard Gaussian-2 (G2)[7] theory by small post-Hartree-Fock calculations. In this paper an additional MP2(FC)/6-31G(d) calculation over the G2 procedures is employed and examined in modification in modification to the flaw of Frozen-Core (FC) approximation of G2 vai eq.:
ΔE(full)= E[MP2(full)/6-31G(d)]-E[MP2(FC)/6-31G(d)]
where the MP2(full)/6-31G(d) energy has been obtained in the molecular geometry optimizations. This energy, ΔE(full), is directly added into the total G2 energy of a molecule in facilitating the effect of core electronic correlations for each molecule in chemical reactions. It has been shown that the over-all average absolute deviation for the 125 reaction energies of the G2 test set (test set 1) is slightly reduced from 5.09 to 5.01 kJ, mol(-1) while for the 55 D0 values, which have been used for the derivation of the A coefficient of the empirical High-Level...更多-Correction (HLC), it is also reduced from 4.99 [for both G2 and G2(COMPLETE)[8]]to 4.77 kJ• mol(-1). In addition, larger errors (greater than ±8.4 kJ•mol(-1) for the D0 energies are improved, especially for the largest error of the D0 of SO2 This error is reduced from 21.3 to 15.4 kJ. mol(-1), in which the experimental geometry would further reduce it by 7.1kJ.mol(-1)[8]. Another improvement is the absolute value of the A coefficient in HLC being reduced from 4.81 for G2 to 4.34 milli-hartrees which is believed to be useful in isolating the relationship between the HLC and the FC approximation. Modifications to the original G2 from this work is denoted as G2(fu 1) and thus the G2 (fu 1) total energy for a molecule is
E[G2(fu 1)]= E[G2]+Δ E(full)h
with a new ΔE[HLC] =-0.19α- 4.34nβ milli-hartree.     

铂硅铝催化剂的铂分散度与催化性能的关系

研究了不同类型铂硅铝催化剂的铂分散度,并考察了它和催化剂的酸性及活性等相互之间的关系。发现当改变酸性或铂分散度时,催化剂的铂总面积和酸性以及活性三者之间都有平行变化的趋势。这些结果都可用表面复合体生成的观点解释,但与分离中心的观点有所矛盾。