Study on Chiral Symmetry Breaking, Synthesis and Resolution Mechanisms of Co(III) Complexes

摘要在化学中分子的手性特征虽常见但却令人迷眩。许多复杂的生命现象可通过分子的手性识别去理解。由于手性在化学、生物化学、医药以及材料科学等领域发挥着越来越重要的作用，研究手性的起源、对称性破缺、传递与放大、手性分子间的相互识别作用以及手性化合物的制备方法等已引起科学家们极大关注。本文主要进行手性金属钴配合物的绝对不对称合成、手性拆分以及立体选择性合成Ni(II)和Co(III)的环己二胺配合物等方面的研究工作，探讨了绝对不对称合成以及相关的拆分和手性识别机理。主要研究结果如下：1.研究了手性cis-[CoBr(NH3)(en)2]Br2的绝对不对称合成及其外消旋体的改进拆分，并对反应产物进行了T...Abstract Chirality or handedness in chemistry is a common but fascinating attribute of a molecule. Many complex phenomena in life are easily understood through the recognition of molecular chirality. Studies on chirality such as chiral origin, chiral symmetry breaking, propagation and amplification of chirality, chiral discrimination among chiral molecules, preparation of chiral compounds, have...学位：理学硕士院系专业：化学化工学院化学系_无机化学学号：20032500

综合化学新实验——手性Co(Ⅲ)络合物的不对称自催化合成和表征

本实验是新开设的化学系硕士生综合化学实验,其构思来自于手性Co(Ⅲ)络合物的不对称自催化合成。研究生可通过本实验从实践和理论上发现和探讨手性Co(Ⅲ)络合物的不对称自催化合成的奇妙现象以及掌握对手性络合物组成、结构和手性性质的各种表征方法

Absolute Asymmetric Synthesis and Resolution Mechanism of Chiralcis-bromoamminebis(ethylenediamine)cobalt(III) Bromide

分别用绝对不对称合成和改进的拆分方法制备标题配合物!-(+)D-cis-[CoBr(NH3)(en)2]Br2(1)和"-(-)D-cis-[CoBr(NH3)(en)2]Br2(2),以及制备了cis-[CoBr(NH3)(en)2]Br·22H2O(3)(en=1,2-乙二胺).用元素分析、差热-热重、旋光度、UV-Vis、CD光谱等对产物进行了表征.通过CD光谱法获得了绝对不对称合成Co(III)配合物的产物ee值分布图.当利用绝对不对称合成得到的手性Co(III)配合物去“逆向拆分”外消旋溴代樟脑磺酸铵[NH4(dl-BCS)]时只获得部分拆分,初步认为这与交互拆分过程中阴阳离子之间的有效手性识别有关,对于手性Co(III)配合物的绝对不对称合成还提出了一个新的反应机理,即“催化-结晶诱导”机理.The absolute asymmetric synthesis of the title complexes ?撰-(+)D-cis-[CoBr(NH3)(en)2]Br2(1) and ?驻-(-)D-cis-[CoBr(NH3)(en)2]Br2(2)(en=1,2-ethylenediamine) as well as the improved optical resolution of cis-[CoBr(NH3)(en)2]Br2·2H2O(3) are described in detail. The products were characterized by means of elemental analysis, TG-DTA, optical rotation, UV-Vis, and CD spectra. The distribution of enantiomeric excess(ee) of cis-[CoBr(NH3)(en)2]Br2 in the absolute asymmetric synthesis was obtained by the measurements of their CD spectra. It was found that the complete resolution of rac-cis-[CoBr(NH3)(en)2]Br2·2H2O was achieved by use of NH4(d-BCS) (ammonium d-α-bromocamphor-π-sulfonate) or NH4(l-BCS) while NH4(dl-BCS) could only be partially resolved by chiral cis-[CoBr(NH3)(en)2]Br2 at the same condition. It is deduced that there are notable differences in the chiral discrimination of the reciprocal resolution between cis-[CoBr(NH3)(en)2]Br2 and NH4BCS. Moreover, a new "catalysis-crystal induction" mechanism in the preparation of the chiral Co(III) complex is put forward.国家自然科学基金(20171037,20373056);; 福建省自然科学基金(C0020001)资助项

p62 antigenic analysis with IgG class of autoantibody from patients with cancers

目的 :研究p6 2不同区域的抗原性。方法 :取p6 2全长重组子及克隆其不同区域的 3个重组子进行表达和纯化。以各重组蛋白为包被抗原 ,建立检测IgG类抗p6 2自身抗体的ELISA技术。结果 :恶性肿瘤患者血清中抗p6 2各片段自身抗体阳性率以抗p6 2 1为最高 ,抗p6 2 3次之 ,抗p6 2 2最低 ,3者均低于抗全长p6 2。抗全长p6 2的阳性率与抗p6 2 1的阳性率无明显差异 ,而与抗p6 2 2和抗p6 2 3均有非常显著差异。除肺癌外 ,肝癌、胃癌、肠癌、食管癌和乳腺癌患者的 3个抗原片段的自身抗体的叠加阳性率均低于全长p6 2。结论 :p6 2的抗原性主要位于p6 2 1,但其结构的完整性对维持其抗原性具有重要意义。Objective:To carry out p62 antigenic analysis with IgG class of autoantibody from patients with cancers.Methods:Three fragments of p62 gene, named as p62 1, p62 2 and p62 3, were cloned using cloned p62 as template Purified recombinant p62, p62 1, p62 2 and p62 3 were used as coating antigen for establishment of ELISA to detect anti p62 of class of IgG Results:The positive rates of autoantibody to p62 fragments were anti p62 1 > anti p62 3 > anti p62 2 in patients with cancers All of them were lower than that of autoantibody against full length p62 The frequency of autoantibody to full length p62 was significantly higher than that of anti p62 2 and anti p62 3, but no difference with anti p62 1 Totally positive rates of autoantibody against the three fragments were lower than those of full length p62 in patients with hepatocellular cancer, gastric cancer, colorectal cancer, esophagus cancer and breast cancer but with lung cancer Conclusion:Antigenic sites in p62 were mainly located in p62 1 and the integrity of p62 structure is important for antigenic expression教育部优秀青年骨干教师资助课题和国家自然科学基金资助课题( 3 0 0 80 0 2 9