Preliminary Studies on the Stereochemistry and Applications of Ruthenabenzene Complexes

“金属苯”被理论推测和成功合成迄今已20多年，厦门大学夏海平教授及其课题组成功地合成了稳定的钌苯，该络合物为准八面体构型且含有两个单膦配体，有丰富的立体化学信息，并与已发现的通式为[RuCl2(PPh3)2(NN)](NN=双齿氮配体)的Ru(II)催化剂在结构上具有相似性，因此推测钌苯及其衍生物可能具有潜在应用前景。本论文主要考察了钌苯衍生物的配位立体化学，并初步探索其作为手性分子开关以及在催化芳香酮氢转移氢化中的应用。论文主要内容如下： 第一章为绪论，介绍了本文研究背景，选题依据和研究目标。简要介绍了金属苯、八面体配合物的立体化学和手性、手性配合物的制备和...Metallabenzenes were theoretically predicted and successfully synthesized over 20 years. In recent years, Professor Haiping Xia’s group at Xiamen University has made big contributions to the synthesis of stable ruthenabenzenes Ru(C5H3)(PPh3)4Cl3, which are octahedral complexes with abundant stereochemistry information to be explored. Since the ruthenabenzenes contains two single phosphorus ligands...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：2052006115188

Synthesis,Characterization and Solid-State CD Spectra of the Chiral Bisferrocenyl Ligands

以甲酰基二茂铁(1)和手性1,2-二苯基乙二胺[(1R,2R)-1,2-二苯基乙二胺(2R),(1S,2S)-1,2-二苯基乙二胺(2S)]为原料,经缩合、还原和N-烷基化反应,制备了一对新型手性四齿双二茂铁基配体[N,N′-二(二茂铁基甲基)-N,N′-二(2-羟基丙基)-(1R,2R)-1,2-二苯基乙二胺(5R)和N,N′-二(二茂铁基甲基)-N,N′-二(2-羟基丙基)-(1S,2S)-1,2-二苯基乙二胺(5S)].用元素分析、红外(IR)、质子核磁共振(1HNMR)、紫外-可见(UV-Vis)、固体圆二色(CD)光谱等对手性产物(3R-5S)进行了表征.固体CD光谱研究表明,配体5R(或5S)的手性特征和4R(或4S)相似而与3R(或3S)却有一定差别.A pair of novel chiral tetradentate bisferrocenyl ligands [N,N'-bisferrocenylmethyl-N,N'-bis(2-hydroproxypyl)-(1R,2R)-1,2-diphenylethane-diamine(5R),N,N'-bisferrocenylmethyl-N,N'-bis(2-hydroxypropyl)-(1S,2S)-1,2-diphenylethane diamine(5S)] were synthesized from ferrocenylcarboxaldehyde(1)and chiral 1,2-diphenylethane-diamine(2R or 2S)followed by the reduction of the Schiff bases with NaBH4 and subsequent N-alkylation with 1,2-propyleneoxide.All the chiral products(3R-5S)were charactered by elemental analysis,infrared(IR),1H nuclear magnetic resonance(1H NMR),ultraviolet-visible(UV-Vis)and solid-state circular dichroism(CD)spectra.The solid-state CD spectra reveal that the chiral characteristics of 5R(or 5S)are quite similar with 4R(or 4S)and it is also notable that there are some differences between 5R(or 5S)and 3R(or 3S).国家自然科学基金(20373056);; 福建省自然科学基金(2005YZ1020);; 厦门大学科技创新项目(B类,XDKJCX20061027)资

Mechanism of Absolute Asymmetric Synthesis and Solid-State CD Spectroscopy of BPOB

以苯乙酮与间苯二甲酸甲酯为原料经由Claisen缩合制备了1,3-二(3-苯基-3-氧代丙烯醇)苯(BPOB).用元素分析、MS、1H NMR、UV吸收光谱、X射线单晶衍射和固体CD光谱等对其进行了表征.晶体结构数据显示,BPOB属于Sohncke空间群P212121,UV和1H NMR谱表明,BPOB在溶液中主要以烯醇式存在,固体CD光谱和重结晶实验证明,BPOB手性晶体的形成是结晶诱导的绝对不对称合成.1,3-bis(3-phenyl-3-oxopropanoyl)benzene (BPOB) was prepared by Claisen condensation of aceto-phenone and dimethyl isophthalate and characterized by elemental analysis, MS, 1H NMR, UV absorption spectrum, solid-state circular dichroism (CD) spectra, and X-ray single-crystal diffraction. The X-ray crystallographic data indicated that BPOB crystallized in a Sohncke group P212121, UV and 1H NMR showed that the enol tautomer was the most dominant form in solution, and the solid-state CD spectra and repeated recrytallization revealed that the formation of chiral BPOB crystals could be regarded as crystallization-induced asymmetric synthesis.国家自然科学基金(20773098);; 福建省自然科学基金(2005YZ1020);; 厦门大学科技创新工程基金(系列2,XDKJCX20061027)资

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

Synthesis, characterization and solid-state CD spectra of the chiral bisferrocenyl ligands

A pair of novel chiral tetradentate bisferrocenyl ligands [N,N '-bisferrocenyimethyl-N,N '-bis(2hydroproxypyl)- (1R, 2R)-1,2-diphenylethane-diamine(5R), N,N '-bisferrocenylmethyl-N,N '-bis(2-hydroxypropyl)-(1S, 2S)-1,2-diphenylethane diamine (5S)] were synthesized from ferrocenylcarboxaldehyde (1) and chiral 1,2-diphenylethanediamine (2R or 2S) followed by the reduction of the Schiff bases with NaBH4 and subsequent N-alkylation with 1,2-propyleneoxide. All the chiral products (3R-5S) were charactered by elemental analysis, infrared (IR), H-1 nuclear magnetic resonance (H-1 NMR), ultraviolet-visible (UV-Vis) and solid-state circular dichroism (CD) spectra. The solidstate CD spectra reveal that the chiral characteristics of 5R (or 5S) are quite similar with 4R (or 4S) and it is also notable that there are some differences between 5R (or 5S) and 3R (or 3S)

Mechanism of absolute asymmetric synthesis and solid-state CD spectroscopy of BPOB

1,3-bis(3-phenyl-3-oxopropanoyl)benzene (BPOB) was prepared by Claisen condensation of acetophenone and dimethyl isophthalate and characterized by elemental analysis, MS, H-1 NMR, UV absorption spectrum, solid-state circular dichroism (CD) spectra, and X-ray single-crystal diffraction. The X-ray crystallographic data indicated that BPOB crystallized in a Sohncke group P2(1)2(1)2(1), UV and H-1 NMR showed that the enol tautomer was the most dominant form in solution, and the solid-state CID spectra and repeated recrytallization revealed that the formation of chiral BPOB crystals could be regarded as cry stallization-induced asymmetric synthesis

三种水生动物细胞系对两株蛙病毒敏感性的比较

利用3个不同物种的水生动物细胞系,包括爪蟾肾细胞系(A6)、大鲵胸腺细胞系(GSTC)和鲤上皮瘤细胞系(EPC),分别用沼泽绿牛蛙蛙病毒(RGV)和大鲵蛙病毒(ADRV)感染,进一步研究细胞病变显微形态、病毒滴度、细胞病变与不同感染时间的相关性等。结果显示,在光镜下可见感染病毒的细胞发生病变,A6和EPC细胞肿胀或破裂;GSTC细胞收缩或聚在一起形成多层。同种水产动物细胞系对不同蛙病毒的敏感性不同,在A6、EPC和GSTC细胞中,RGV的滴度分别为10~(3.6)、10~(5.9)和10~(6.6) TCID_(50)/m L;ADRV的滴度分别为10~(4.3)、10~(5.4)和10~(6.1) TCID_(50)/m L,表明GSTC细胞系对两种蛙病毒都更敏感。研究为后续蛙病毒致病机理提供了有用的信息和重要实验材料

鳜鱼弹状病毒糖蛋白(G)基因的克隆与表达

<正>本实验室于1999年从患病的鳜鱼组织中观察到了一种弹状病毒粒子;随后通过挑斑纯化;分离得到了鳜鱼弹状病毒(Siniperca chustse rhabdovirus;SCRV); 并对其进行理化性质分析、鉴定以及序列的测定。鉴于 SCRV 的糖蛋白(G)在膜融合、决定病毒毒力以及能够诱导机体产生中和抗体等方面起着重要的作

Vehicle Detection under Night Illumination

论文提出了夜间运动车辆检测的一种有效的算法。首先对原始图像做“浮雕”处理,消除车灯对检测结果的影响,再通过两帧差分检测出运动区域,最后利用形态学腐蚀消除孤立噪声点,计算连通域面积去除大的噪声区域,从而提取出准确的运动目标。An effective approach of vehicle detection at night is proposed in this paper.In order to eliminate the influence of headlights and their beams,the original video sequences have been embossed firstly.Then motion area has been detected by two-frame difference.Finally,the isolated noises have been eliminated by morphological erosion and the scattering noise blobs have been removed according to their areas.The moving objects have been properly extracted at last