含有机配体的活性双过氧钒配合物与组氨酸的相互作用研究

在合成和表征了4种具有较强生物活性双过氧钒配合物K_3[VO(O_2)_2(ox)]· 2H_2O,Na[VO(O_2)_2(bipy)]·5H_2O,K[VO(O_2)_2(phen)]·3H_2O和K_2[VO (O_2)_2(pic)]·2H_2O[分别缩写为pV(ox),pV(bipy),pV(phen)和pV(pic),其中 ox为草酸根,bipy为2,2'-联吡啶,phen为邻菲咯啉,pic为2-羧酸吡啶负离子]的 基础上,利用多种NMR技术和电喷雾质谱（ESI-MS）研究了这4种含有机配体双过氧 钒酸合物与组氨酸（His）在溶液中的相互作用以及反应物浓度、时间、pH等对相 互作用体系的影响。~(51)V NMR跟踪监测的结果表明：双过氧钒配合物pV(ox)和 pV(pic)与His在中性水溶液中存在强配位相互作用,而pV(bipy)和pV(phen)与His 在中性水溶液中无明显作用。我们还利用谱学方法确定了pV(ox)和His相互作用后 所生成产物是pV(ox)分别与His在中性水溶液中无明显作用。我们还利用谱学方法 确定了pV(ox)和His相互作用后所生成产物是pV(ox)分别与His咪唑基上的3-N和1- N配位的一对异构体。     

八核钼过氧化合物的合成、表征和转化

以乳酸为模板剂,在强酸性钼过氧水溶液中分离到新的八核钼过氧化合物K_4[Mo_8O_(24)(O_2)2(H_2O)_2]·4H_2O(1)。1在弱酸性条件下转化为七核钼过氧化合物K_6[Mo_7O_(22)(O_2)_2]·9H_2O(2),转化后钼过氧合物的核数发生变化,但过氧基团的数目不变。1的阴离子为γ-Mo_8O_(26)构型,与强酸性钼酸盐溶液中的[Mo_8O_(26)]~(4-)离子结构相似。1的结构中具有罕见的超短过氧基团[1.308(6)],其对应的红外振动吸收峰为953 cm~(-1)。1的紫外可见光谱最大吸收波长为302 cm~(-1),可能是由过氧基团到钼原子的荷移跃迁引起的。     

NMR研究N-甲基咪唑与双过氧钒配合物的相互作用

为探讨过氧钒配合物上有机配体对反应平衡的影响, 在模拟生理条件下(0.15 mol/L NaCl溶液), 应用多核(¹H, ¹³C和⁵¹V)多维(COSY) NMR以及变温技术等谱学方法研究双过氧钒配合物[OV(O₂)₂LL']ⁿ− [n＝1～3, LL'＝oxalate (缩写为oxa)、picolinate(缩写为pic)、bipyridine(缩写为bipy)和1,10-phenanthroline(缩写为phen), 与它们配位的含钒物种分别缩写为bpV(oxa), bpV(pic), bpV(bipy)和bpV(phen)]与N-甲基咪唑(缩写为N-Me-Im)的相互作用, 实验结果表明N-Me-Im与4种双过氧钒配合物的反应活性从强到弱的顺序为: bpV(oxa)＞bpV(pic)＞bpV(bipy)＞bpV(phen). 研究表明金属中心上配体的配位能力和空间位阻都对反应平衡产生较大的影响, 同时竞争配位的结果导致新的过氧物种[OV(O₂)₂(N-Me-Im)]⁻的生成, 而利用上述谱学方法则有助于揭示此类相互作用体系的反应过程和配位方式.     

由双帽Keggin型簇和钴配合物构筑而成的结构新颖的聚合物（英文）

利用水热合成法得到了有机-无机杂化的钴钼钒簇[Co(en)_2]_4H_4{Co(phen)_2(H_2O)]_2[Mo_9~(VI)V_6~(IV)O_(42)]}[Mo_9~(VI)V_6~(IV)O_(44)]·12H_2O(phen=1,10-邻菲罗啉,en=乙二胺),用元素分析、红外光谱、热分析、磁分析和单晶衍射对该化合物做了表征.该化合物的分子结构单元是由双帽Keggin型多阴离子[Mo_9~(VI)V_6~(IV)O_(42)]~(6-)(简称1)、类似结构的多阴离子[Mo_9~(VI)V_6~(IV)O_(44)]~(10-)(简称2)、过渡金属配合物(两个[Co(phen)_2(H_2O)]~(2+)阳离子和四个[Co(en)_2]~(2+)阳离子)、四个质子和十二个结晶水分子组成.     

镧系硅钨杂多酸胍盐的合成及物性研究

合成了LnL(L代表配体)型镧系硅钨杂多配合物K_5[LnSiW_(11)O_(39)],再分别与盐酸胍盐反应,得(CN_3H_5)_5[LnSiW_(11)O_(39)]·nH_2O。阳离子交换试验证明Ln~(3+)居于配合物内界。用IR、UV、DSC-TGA和XRD分析,对杂多配合物进行了表征。     

三重桥氧三核铁脂肪酸配合物FAB和EI质谱研究

本文报道三重桥氧三核铁脂肪酸配合物[Fe_3(μ_3～O)(μ-O_2CR)_6(H_2O)]_3~+(R=CH_3,C_2H_5,C_3H_7,C_4H_9,C_(15)H_(31)和C_(17)H_(35))的快原子轰击(FAB)和电子轰击(EI)质谱。在FAB—MS谱中观察到四种系列离子:Ⅰ.[Fe_3O(O_2CR)_n]~+n=2-6;Ⅱ.[Fe_3O(O_2CR)_nO]~+n=1-4;Ⅲ.[Fe_2O(O_2CR)_n]~+n=1-3;Ⅳ.[Fe_2(O_2CR)_n]~+n=2-4;以及与底物所形成的加合离子[Fe_3O(O_2CR)_n·NBA-1]~+n=3-5(NBA是间-硝基苄醇)。在EI—MS谱中,除上述Ⅰ—Ⅳ离子(其中n的数目略有差异)外,还观察到含三个配位水的完整阳离子[Fe_3(O_2CR)_6(H_2O)_3]~+及其与配体羧酸的加合离子[Fe_3O(0_2CR)_n(H_20)_3·RCOOH+H]~+n=4-6,(Fe_3O(O_2CR)_nO(H_2O)3·RCOOH+H]~+n=2—4和Fe(O_2CR)_n]~+n=1—3。分析了它们的断裂规律,探讨了从中所获得的有益启示。     

Construction of Two Inorganic-organic Hybrid Vanadogermanates Based on Di-Cd-Substituted Ge-V-O Cluster and Transition-metal Complex Bridges

Two new inorganic-organic hybrid vanadogermanates H[Cd(en)(phen)(H_2O)]-[Cd(en)(phen)]{[Cd(phen)]_2[Ge_8V_(12)O_(41)(OH)_7]}·5H_2O(1)and[Cd(dien)_2][Cd(dien)]_2{[Cd(phen)]_2-Ge_8V_(12)O_(42)(H_2O)(OH)_6}·6.5H_2O(2)(en=ethylenediamine,dien=diethylenetriamine,phen=1,10-phenanthroline)have been synthesized by hydrothermal method.Their structures were measured by single-crystal X-ray diffractions,thermogravimetric analysis,powder X-ray diffractions and infrared spectra.Structural analysis reveals that compound 1 is an infrequent dimeric structure based on di-Cd-substituted Ge-V-O cluster and transition-metal complex bridges,while compound 2 is an infinite 1-D chain constructed from di-Cd-substituted Ge-V-O clusters and dinuclear bridging complexes.Magnetic measurement indicated that both 1 and 2 exhibit antiferromagnetic behaviors.     

三齿配体酰(氧)钒配合物的晶体结构研究——Ⅰ.双聚{1-(2,4-戊二酮-(3-硝基苯甲酰)-单腙-2-乙氧基合氧钒(Ⅳ)}和双聚{1-(2,4-戊二酮-(3-硝基苯甲酰)-单腙-2-甲氧基合氧钒(Ⅳ)的晶体结构

以二乙酰丙酮氧钒VO(Acac)_2与间硝基苯甲酰肼m-NO_2PhCONHNH_2分别在乙醇和甲醇中反应,得[VO(C_(12)H_(12)N_3O_4)(C_2H_5O)]_2(Ⅰ)和[VO(C_(12)H_(12)N_3O_4)(CH_3O)]_2(Ⅱ)两种晶体。晶体(Ⅰ)属空间群P(?),晶胞参数a=8.123(2),b=10.409(5),c=10.822(4),α=65.78(3)°,β=85.50(3)°,r=89.04(3)°。晶体(Ⅱ)属空间群P2_1/a,a=7.745(2),b=19.164(5),c=10.787(4),β=107.87(2)°。两个晶体均具有共同的结构特征:通过缩合形成的三齿配体占据四个赤道配位位置中的三个,男一个赤道配位位置由醇氧基RO~-所补充而RO~-中的氧原子又兼作桥氧向另一个钒原子的第六位配位,从而导致文献中未报道过的新型双核钒配合物的形成。     

对“一维链状冠醚配合物[K(B18-C-6)]2[M(SCN)4](M=Pd,Pt)的合成与结构”一文的更正

我们合成、表征了苯并18-冠-6（B18-C-6）与K_2[Pd-(SCN)_4]，K_2[Pt(SCN) _4]生成的一维链状配合物[K(B18-C-6)]_2[Pd(SCN)_4](1)，[K(B18-C-6)]_2[Pt (SCN)_4](2)和[K(B18-C-6)]_2[Pt(SCN)_4]·C_2H_4Cl_2(3)。其中3为三斜晶系， 空间群P1[化学学报2002，60（8），1465]。厦门大学胡盛志教授认为该化合物的 空间群应为P-1。经将原始数据重新还原、修正，3的空间群的确为P-1，现予以更 正。     

钨硅铁杂多酸盐的Mossbauer谱研究

首次测定了K_5SiFe(H_2O)W_(11)O_(39)·21H_2O和它的二聚体K_(12)O(SiFeW_(11)O_(39))_2·22H_2O的Mossbauer谱,并结合磁化率、XPS和红外光谱,证实了二聚体中Fe—O—Fe桥键含有d-pπ键,推测其阴离子结构为[SiW_(11)O_(39)FeOFeO_(39)W_(11)Si]~(12-).     

Spectroscopic Characterization and Properties of Some Bioactive- Peroxovanadium Complexes in Aqueous Solution

1　ＩＮＴＲＯＤＵＣＴＩＯＮＰｅｒｏｘｏｖａｎａｄｉｕｍ ( ｐＶ )ｃｏｍｐｌｅｘｅｓａｒｅ ｐｏｔｅｎｔｐｒｏｔｅｉｎｔｙｒｏｓｉｎｅｐｈｏｓｐｈａｔａｓｅｉｎ ｈｉｂｉｔｏｒｓｗｉｔｈｉｎｓｕｌｉｎ ｍｉｍｅｓｉｓｐｒｏｐｅｒｔｉｅｓａｎｄｃｏｕｌｄｐｏｓｓｉｂｌｙｂｅｄｅｖｅｌｏｐｅｄｉｎｔｏａｎｅｗｋｉｎｄｏｆｏｒａｌｄｒｕｇｆｏｒｔｈｅｔｒｅａｔｍｅｎｔｏｆｄｉａｂｅｔｅｓ[1～ 3].Ｒｅｃｅｎｔｌｙ ,ｔｈｉｓｋｉｎｄｏｆｃｏｍｐｏｕｎｄｈａｓｒｅｃｅｉｖｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｔｅｎｔ…     

Interactions between Bioactive Diperoxovanadate Complexes and Imidazole： Insights into Their Solution Structures by NMR and ESI-MS

1 INTRODUCTION As a required metal for some enzymes such as haloperidases and nitrogenases, vanadium com- pounds are capable of having many biological acti- vities. Similar to inorganic phosphates, vanadium compounds activate the functions of a numb…     

Studies on the Interactions between Potassium oxalato-oxodiperoxovanadate and Histidine by NMR and MS

K3[VO(O2)2(C2O4)]2H2O, (abbr. BpV (ox)) pertains to peroxovanadium (abbr. pV) complexes, which have been attracted considerable attention nowadays, since they are inhibitors of tyrosine phosphatase and may be developed into a new kind of drugs for the treatment of diabetes1. According to the evidence on water-biperoxovanadium, the molecular mechanism of insulin-like effects of pV involves in irreversibly oxidizing the catalytic cysteine at the active site of the target enzyme2,3. However…     

Interaction Studies Between Peroxovanadium Complexes and Model Peptide in Active Center of Tyrosine Phosphatase

Peroxovanadium(pV) complexes are potent protein tyrosine phosphatase inhibitors and possibly could be developed into a new kind of oral drugs for treatment of diabetes^[1,2]. They have been paid considerable attention nowadays. Their action mechanism of insulin-mimetic effects involved in irreversibly oxidizing the catalytic cysteine of the enzyme according to the latest evidence^[3]. However, little was studied on the structure-function relationship of pV complexes until our latest paper^[4] in which we suggested that it related to the interaction between pV and functional groups in active center of tyrosine phosphatase except for their oxidizing ability. In order to convince our assumption, histidine and glutathione with model functional groins of imidazole and sulfhydryl residue in the active domain of target enzyme^[5] were selected as study object of interaction with pV complexes.     

Luminescent piano-stool complexes incorporating 1-(4-cyanophenyl)imidazole: synthesis, spectral, and structural studies

Three novel luminescent piano-stool arene ruthenium complexes of general formula [(eta(6)-arene)RuCl(2)(CPI)] (eta(6)-arene = benzene, 1, p-cymene, 2, and hexamethylbenzene, 3; CPI=1-(4-cyanophenyl)imidazole were prepared. The molecular structures of 2 and 3 were determined crystallographically. Reaction of 1-3 with EPh(3) (E = P, As, or Sb) and N-N donor bases such as 2,2'-bipyridine and 1,10-phenanthroline afforded cationic mononuclear complexes of general formula [(eta(6)-arene)RuCl(CPI)(EPh(3))](+) (eta(6)-arene = C(6)H(6), E = P (1a), E = As (1b), E = Sb(1c); eta(6)-arene = C(10)H(14), E = P (2a), E = As (2b), E = Sb (2c); eta(6)-arene = C(6)Me(6), E = P (3a), E = As (3b), E = Sb (3c)) and [(eta(6)-arene)Ru(N-N)(CPI)](2+) (eta(6)-arene = C(6)H(6), N-N = bipy (1d), N-N = phen (1e); eta(6)-arene = C(10)H(14), N-N = bipy (2d), N-N = phen (2e); eta(6)-arene = C(6)Me(6), N-N = bipy (3d), N-N = phen (3e)). Molecular structures of 1a and 2a were also confirmed by X-ray crystallography. Structural studies of the complexes 2, 3, 1a, and 2a supported coordination of CPI through the imidazole nitrogen and the presence of a pendant nitrile group. Structural data also revealed stabilization of crystal packing in the complexes 2, 3, and 2a by C-H...X (X = Cl, F) type inter- and intramolecular interactions and in complex 1a by pi-pi stacking. Moreover, neutral homonuclear bimetallic complexes 2f,g were prepared by using complex 2 as a metallo-ligand, where CPI acts as a bridge between two metal centers. Emission spectra of the mononuclear complexes [(eta(6)-arene)RuCl(2)(CPI)] and its derivatives exhibited intense luminescence when excited in the metal to ligand charge-transfer band.     

系列Co-aip聚物的合成、结构及表面光电性能

采用水热法合成了3种以5-氨基间苯二甲酸根为桥连配体的Co(Ⅱ)配聚物:[Co2(aip)2(bipy)]n·2nH2O(1),[Co(aip)(imH)]n(2)和[Co(aip)(phen)]n(3)(H2aip=5-氨基间苯二甲酸,bipy=2,2′-联吡啶,imH=咪唑,phen=1,10-邻菲啰啉).通过X射...     

From model compounds to protein binding: syntheses, characterizations and fluorescence studies of [RuII(bipy)(terpy)L]2+ complexes (bipy = 2,2'-bipyridine; terpy = 2,2':6',2''-terpyridine; L = imidazole, pyrazole and derivatives, cytochrome c)

Compounds [RuII(bipy)(terpy)L](PF6)2 with bipy = 2,2'-bipyridine, terpy = 2,2':6',2"-terpyridine, L = H2O, imidazole (imi), 4-methylimidazole, 2-methylimidazole, benzimidazole, 4,5-diphenylimidazole, indazole, pyrazole, 3-methylpyrazole have been synthesized and characterized by 1H NMR, ESI-MS and UV/Vis (in CH3CN and H2O). For L = H2O, imidazole, 4,5-diphenylimidazole and indazole the X-ray structures of the complexes have been determined with the crystal packing featuring only few intermolecular C-H...pi or pi-pi interactions due to the separating action of the PF6-anions. Complexes with L = imidazole and 4-methylimidazole exhibit a fluorescence emission with a maximum at 662 and 667 nm, respectively (lambdaexc= 475 nm, solvent CH3CN or H2O). The substitution of the aqua ligand in [Ru(bipy)(terpy)(H2O)]2+ in aqueous solution by imidazole to give [Ru(bipy)(terpy)(imi)]2+ is fastest at a pH of 8.5 (as followed by the increase in emission intensity). Coupling of the [Ru(bipy)(terpy)]2+ fragment to cytochrome c(Yeast iso-1) starting from the Ru-aqua complex was successful at 35 degrees C and pH 7.0 after 5 d under argon in the dark. The [Ru(bipy)(terpy)(cyt c)]-product was characterized by UV/Vis, emission and mass spectrometry. The location where the [Ru(bipy)(terpy)] complex was coupled to the protein was identified as His44 (corresponding to His39 in other numbering schemes) using digestion of the Ru-coupled protein by trypsin and analysis of the tryptic peptides by HPLC-high resolution MS.     

两个由2-(4′-氯-苯甲酰基)苯甲酸构筑的铜、锌配合物的合成及晶体结构

通过水热法合成了2个新的配合物Cu2(cbba)4(phen)2(1)和Zn(cbba)2(bipy)(2)(Hcbba=2-(4′-氯-苯甲酰基)苯甲酸,phen=1,10-邻菲罗啉,bipy=2,2′-联吡啶),并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。这2个配合物通过π-π相互作用形成了三维超分子网状结构。此外,还研究了配合物2的荧光性质。     

NMR and theoretical study on the coordination and solution structures of the interaction between diperoxovanadate complexes and histidine-like ligands

To simulate the types of coordination and solution structures of the active site of haloperoxidases, the interaction systems between diperoxovanadate complexes [OV(O2)2L]n- (n = 1 or 3, L = oxalate or H2O) and a series of histidine-like ligands in solution have been studied by using 1D multinuclear (1H, 13C, and 51V) NMR, 2D diffusion ordered spectroscopy, and variable-temperature NMR in 0.15 mol/L NaCl ionic medium, representing the physiological conditions of human blood. Some direct NMR data are given for the first time. The reactivity among the histidine-like ligands is imidazole > 2-methylimidazole > carnosine approximately 4-methylimidazole > histidine. Competitive coordination interactions result in a series of new peroxovanadate species [OV(O2)2L']- (L' = histidine-like ligands). When the ligands are 4-methylimidazole, histidine, and carnosine, a pair of isomers have been observed, which are attributed to different types of coordination between vanadium atom and ligands. The results of density functional theory calculations provided a reasonable explanation on the relative reactivity of the histidine-like ligands and the molar ratios of isomers. Theoretical results signify the importance of the solvation effect for the reactivity and stability of the interaction systems.