Reduction of Lung Metastases by Na[trans-RuCl(4)(DMSO)Im] is not Coupled With the Induction of Chemical Xenogenization

The effects of the treatment of tumor cells of MCa mammary carcinoma and TLX5 lymphoma with the ruthenium complex Na[trans-RuCl(4) (DMSO)lm] for several transplant generations were studied on tumor growth and metastases formation. On TLX5 lymphoma cells, treatment was performed in vitro prior to in vivo inoculation of tumor cells in intact or immunesuppressed mice. Either considering tumor take and growth or its capacity to invade the brain of the inoculated hosts, Na[trans-RuCl(4)(DMSO)lm] did not induce any significant modification. Conversely, in mice with MCa mammary carcinoma, the in vivo treatment of tumor cells in immunesuppressed hosts caused a progressive increase of DNA activity and, starting from the 4th transplant generation, a significantly increased susceptibility of lung metastasis formation to a further treatment in intact mice. These data seem to suggest that Na[trans-RuCl(4)(DMSO)Im] does not induce chemical xenogenization of tumor cells nor its repeated treatment induces resistance in tumor cells. Conversely, it appears that Na[trans-RuCl(4)(DMSO)lm] may select a tumor cell population which maintains its capacity to metastasise to the lung but with enhanced sensitivity to the antimetastatic properties of this compound.     

Interaction of Cis- and Trans-RuCl (2)(DMSO)(4) With Human Serum Albumin

The interaction between cis- and trans- RuCl(2)(DMSO)(4) and human serum albumin have been investigated through UV-Vis, circular dichroism, fluorescence spectroscopy and inductively couplet plasma atomic emission spectroscopy (ICP(AES)) method Albumin can specifically bind 1 mole of cis-isomer and 2 moles of the trans-isomer RuCl(2)(DMSO)(4) complex. The interaction of RuCl(2)(DMSO)(4) with HSA causes: a conformational change with the loss of helical stability of protein; the strong quenching of the Trp 214 fluorescence indicating that the conformational change of the hydrophobic binding pocked in subdomain IIA takes place; a local perturbation of the warfarin binding site and induce some conformational changes at neighbour domains, a changing of the binding abilities towards heme.     

Efficacy of 5-FU Combined to Na[trans-RuCl(4)(DMSO)Im], A Novel Selective Antimetastatic Agent, on the Survival Time of Mice With P388 Leukemia, P388/DDP subline and MCa Mammary Carcinoma

The combinational treatment between the selective antimetastatic agent, sodium-trans-rutheniumtetrachloridedimethylsulfoxideimidazole, Na[trans-RuCl(4)(DMSO)Im], and the cytotoxic drug 5-fluorouracil (5-FU) on primary tumor growth and on the survival time of experimental tumors results in an effect significantly greater than that of each single agent used alone either with the solid metastasizing MCa mammary carcinoma of the CBA mouse or with the lymphocytic leukemia P388 and its platinum resistant P388/DDP subline. Thus the inorganic compound Na[trans-RuCl(4)(DMSO)Im], known for its potent and selective antimetastatic effects, positively interacts with the antitumor action of an organic anticancer agent such as 5-FU on both a solid metastasizing tumor and a tumor of lymphoproliferative type. In particular, the effects of the combinational treatment on the survival time of tumor bearing mice seem to be related to the selective antimetastatic activity of the ruthenium complex that joins the potent cytotoxicity of 5-FU for the tumor. Moreover, these data show that Na[trans-RuCl(4)(DMSO)Im] is almost as effective on the subline of P388 made resistant to cisplatin as it was on the parental line.     

Interaction of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] and [Rh(2)(O(2)CCH(OH)Ph)(2)(phen)(2)(H(2)O)(2)](O(2)C-CH(OH)Ph)(2) With Sulfhydryl Compounds and Ceruloplasmin

The interaction of binuclear rhodium(II) complexes [Rh(2)(OOCCH(3))(4)(H(2)O)(2)], [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] {OOCCH(OH)Ph}(2), [Rh(2)(OOCCH(3))(2)(bpy)(2)(H(2)O)(2)](OOCCH(3))(2) and [Rh(2)Cl(2)(OOCMe)(2)(bpy)(2)](3H(2)O) with ceruloplasmin, cysteine, glutathione and coenzyme A have been investigated using. UV-Vis and CD spectroscopies. The complexes containing phen or bpy at pH = 7.4 and 4.0 are readily reduced with sulfhydryl compounds, while rhodium(II) acetate is relatively stable in these conditions. Complex [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] strongly changes structure of ceruloplasmin leading to the decrease of of alpha-helix content and loss of oxidase activity.     

大环配合物[Ni (14)4,11-二烯-N4)]Ⅰ2和Co((14)4,11-二烯-N4)]Ⅰ2的合成

在酸性条件下,丙酮缩合成异丙基丙酮,再与乙二胺反应生成β-氨基酮,再与另一酮基缩合得到[(14)4,11-二烯-N4]2HI,最后分别与Ni(OAc)2·4H2O和Co(OAc)2·4H2O进行反应,得到大环配合物[Ni (14)4,11-二烯-N4)]Ⅰ2和[Co (14)4,11-二烯-N4)]Ⅰ2,其结构经IR、...     

配合物[Ni(C_8H_4O_4)(C_(12)H_(30)N_6)]的合成与晶体结构

合成了一个新的镍配合物.通过X射线单晶衍射对其结构进行了表征.结果表明:该配合物属三斜晶系,P1空间群,a=7.581 8(5)A,b=8.397 6(5)A,c=9.759 6(6)A,a=105.506(1)°,β=97.283(1)°,γ=105.853(1)°,V=562.45(6)A3,Z=1,F(000)=256,Dc=1.421 g/cm3,R1=0.030,wR2=0.081.配合物呈链状结构,且这些链是互相平行的.     

Comparison of the Antiproliferative Activity of Two Antitumour Ruthenium(III) Complexes With Their Apotransferrin and Transferrin-Bound Forms in a Human Colon Cancer Cell Line

Two ruthenium(III) complexes, namely trans-indazolium[tetrachlorobis(indazole)- ruthenate(III)], HInd[RuInd(2)Cl(4)] and trans-imidazolium[tetrachlorobis(imidazole)- ruthenate(III)], HIm[RuIm(2)Cl(4)] exhibit high anticancer activity in an autochthonous colorectal carcinoma model in rats. Recently, it has been shown that both complexes bind specifically to human serum apotransferrin and the resulting adducts have been studied through spectroscopic and chromatographic techniques with the ultimate goal of preparing adducts with good selectivity for cancer cells due to the fact that tumour cells express high amounts of transferrin receptors on their cell surface.In order to investigate whether the cellular uptake of the complexes was mediated by apotransferrin or transferrin, we compared the antiproliferative efficacy of HInd[RuInd(2)Cl(4)] and HIm[RuIm(2)Cl(4)] with its apotransferrin- and transferrin-bound form in the human colon cancer cell line SW707 using the microculture tetrazolium test (MTT).Our results show that especially the transferrin-bound forms exhibit high antiproliferative activity, which exceeds that of the free complex, indicating that this protein can act as a carrier of the ruthenium complexes into the tumor cell.     

Interaction of Pd(II) and Pt(II) Amino Acid Complexes With Dinucleotides

The interaction of the dinucleotides d(ApG) and d(ApA) with [Pd(aa)Cl(2)], where aa = L- or D-histidine or the methyl ester of L-histidine, and with [Pt(Met)Cl(2)], where Met = L-methionine was studied by (1)H and (13)C NMR and CD measurements. In the case of the L-histidine and L-histidineOMe, the reaction with d(ApG) appeared to give the bifunctional adducts Pd(L-Histidine)N1(1)N7(2) and Pd(L-HisOMe)N1(1)N7(2), but the behavior with D-histidine suggested the formation of the monofunctional adduct Pd(D-His)N7(2). The reaction of L-histidine with d(ApA) seemed to form the bimetallic adduct (L-His)PdN7(1)N7(2)Pd(L-His). The Pt(II)-L-methionine complex in both reactions with d(ApG) and d(ApA) seemed to yield mainly adducts Pt(L-Met)N7(1)N7(2) but the existence of adducts Pt(L-Met)N1(1)N7(2) cannot be ruled out.     

[Mn(S-S)(N-N)]配合物的荧光特性与光敏性研究

通过透射电镜表征了标题配合物[Mn(S-S)(N-N)](S-S=mnt2-,1,2-二氰基乙烯-1,2-二硫醇离子;N-N=5-NO2-phen,5-硝基-1,10-邻菲咯啉)固态形貌,TEM和EDP照片显示标题配合物是一种纳米级(颗粒直径约40nm)的微晶粉体。测量了配合物[Mn(S-S)(N-N)]在二甲基亚砜(DMSO)、二甲基甲酰胺(DMF)、丙酮(CH3COCH3)等溶剂中的电子吸收光谱和电子发射光谱,该配合物在350~632nm间显示较强的荧光发射带。报道了掺杂有标题配合物[Mn(S-S)(N-N)]的CdS-PVA复合膜的暗态导电性和光电导性,研究了[Mn(S-S)(N-N)]对CdS的光敏化作用与其电子光谱间的关系。     

Formation of Ni(CO)4 during the Interaction between CO and Silica-Supported Nickel Catalyst: an FTIR Spectroscopic Study

The formation of Ni(CO)₄ during interaction of CO with silica-supported highly dispersed nickel metal (d _av4 nm) was investigated by FTIR spectroscopy. At temperatures below 145 K, in addition to linear and bridged nickel carbonyls, CO adsorption on Ni⁰/SiO₂ leads to the formation of Ni(CO) _x (x=2, 3) subcarbonyls (band at ca. 2090 cm^–1) and negligible amounts of Ni(CO)₄ adsorbed on SiO₂ (band at 2048 cm^–1). Up to this temperature CO causes no detectable erosion of the metal surface. Above 145 K the rate of interaction between CO and the nickel particles significantly increases. Until 235 K Ni(CO)₄ mainly remains in the adsorbed state, while at still higher temperatures the equilibrium between adsorbed and gaseous Ni(CO)₄ (band at 2058 cm^–1) is shifted towards the latter. It is assumed that subcarbonyls formed on defect sites of the metal surface are precursors of the nickel tetracarbonyl. Successive adsorption–evacuation cycles of CO at room temperature result in a decrease in the amount of the Ni(CO)₄ formed, probably due to a reduction of the number of defect metal sites. On the basis of ¹²CO and ¹³CO coadsorption, an alternative interpretation of the band at 2048 cm^–1 to species containing isolated Ni(CO)₃ groups is proposed.     

（氧二亚甲基）双苯并咪唑及其配合物的合成与荧光性质

合成了2,2’-（氧二亚甲基）双苯并咪唑及其Ni（Ⅱ）和La（Ⅲ）的配合物,采用元素分析、红外光谱、紫外光谱和摩尔电导率等进行表征,研究了它们的固体荧光性质,发现它们都是良好的荧光物质。     

Rh(2)(CF(3)CONH)(4): The First Biological Assays of a Rhodium (II) Amidate

The rhodium (II) complexes Rh(2)(tfa)(4).2(tfac) and Rh(2)(tfacam)(4) (tfacam = CF(3)CONH-,tfa = CF(3)COO-,tfac = CF(3)CONH(2)) were synthesized and characterized by microanalysis and electronic and vibrational spectroscopies. Rh(2)(tfacam)(4) was tested both in vitro (U937 and K562 human leukemia cells and Ehrlich ascitic tumor cells) and in vivo for cytostatic activity and lethal dose determination, respectively. This is the first rhodium tetra-amidate to have its biological activity evaluated. The LD(50) value for Rh(2)(tfacam)(4) is of the same order as that of cisplatin, and it was verified that the rhodium complex usually needs lower doses than cisplatin to promote the same inhibitory effects.     

Copper(II) azide complexes of [Cu(acac)(N3)(dpyam)] and [Cu(μ-N3-κN1)(C2N3-κN1)(dpyam)]2: Synthesis,crystal structure and magnetism

Two new compounds, [Cu(acac)(N₃)(dpyam)] (1), (acac = acetylacetonate; dpyam = di-2-pyridylamine) and [Cu(μ-N₃-κ^N1)(C₂N₃- κ^N1) (dpyam)]₂ (2), have been synthesized and characterized by single-crystal X-ray diffraction and magnetic analyses. Compound 1 is a mononuclear compound in which each of two independent Cu(II) ions is penta-coordinated with a distorted square pyramidal geometry with distortion parameters τ = 0.21 and 0.16. In contrast, compound 2 is an azido-bridged dinuclear compound with monodentate dicyanamide anions and the Cu(II) ions display a distorted trigonal bipyramidal geometry with τ = 0.73 and end-on azido bridges providing an equatorial–axial position between the metal ions. The EPR spectra of powdered samples for 1 and 2 have also been investigated. Magnetic susceptibility measurements of compound 2 reveal a very weak ferromagnetic interaction between the Cu(II) ions with a J value of +5.8 cm⁻¹.     

二维层状磷酸铝化合物[Al(HPO4)(H2PO4)(C10H8N2)]的合成与表征

利用溶剂热法成功地合成出一个二维层状磷酸铝化合物[Al(HPO4)(H2PO4)(C10H8N2)].通过X-ray粉末衍射、单晶X射线、ICP、元素分析及热重分析等对该化合物进行了表征.该化合物属于单斜晶系,空间群P21/c(No.14),晶胞参数a = 10.932(2) ?,b = 15.7183(3) ?, c = 8.4177(17) ?,α = 90o,β = 108. 95(3)o ,γ = 90o, V=1368.0(5)?3,Z=4.其骨架由AlO4N2八面体通过共顶点与H2PO4和HPO4四面体连接而形成(4,12)网络层状结构.该网层结构按AA方式堆积,同时相邻层的2,2'-联吡啶分子之间具有Pi-Pi键相互作用.该工作进一步丰富了磷酸铝化合物的结构化学,并且为实现定向设计和合成提供了实验和理论依据.     

光谱法研究2-对氯苯氨基噻吩并[2,3-d]嘧啶-4(3H)-酮与牛血清白蛋白的相互作用

用荧光光谱及紫外可见光谱法研究了2-对氯苯氨基噻吩并[2,3-d]嘧啶-4(3H)-酮与牛血清白蛋白(BSA)之间在不同温度下的相互作用.实验表明,2-对氯苯氨基噻吩并[2,3-d]嘧啶-4(3H)-酮能强烈猝灭BSA的内源荧光,猝灭机理为动态猝灭.在此基础上计算了二者相互作用的结合常数、结合位点数及热力学参数等,结果表明,2-对氯苯氨基噻吩并[2,3-d]嘧啶-4(3H)-酮分子与BSA分子以摩尔比1∶1结合,其结合反应主要是熵驱动,主要作用力是疏水力.同时,应用同步荧光考察了FDT对BSA构象的影响.     

四元混配配合物[Ln(x-MBA)2(NO3)(Phen)]2的合成及表征

在酸性介质,乙醇／水混合溶剂中合成得到了三个系列的四元混配配合物[Ln(x-MBA)2(NO3)(Phen)]2(Ln=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Er;MBA=CH3C6H4COO^-）。用元素分析、IR、UV、DTA－TG和^1H NMR等方法对配合物进行了表征,测量了三个Eu配合物的荧光光谱和三个Gd配合物的ESR谱。     

Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X-Ray Crystal Structures of [Mn(ph)(Phen)(2)(H(2)O)]. 4H(2)O, [Mn(Phen)(2)(H(2)O)(2)](2)(Isoph)(2)(Phen). 12H(2)O and {[Mn(Isoph)(bipy)](4). 2.75biby}(n)(phH(2) = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10-Phenanthroline; bipy = 2,2-Bipyridine)

Manganese(II) acetate reacts with phthalic acid (phH(2)) to give [Mn(ph)].0.5H(2)O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)].2H(2)O (2) and [Mn(ph)(phen)(2)(H(2)O)].4H(2)O (3). Reaction of isophthalic acid (isophH(2)) with manganese(II) acetate results in the formation of [Mn(isoph)].2H(2)O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn(2) (isoph)(2)(phen)(3))].4H(2)O (5), [(Mn(phen)(2)(H(2)O)(2)](2)(isoph)(2)(phen).12H(2)O (6) and {[Mn(isoph)(bipy)](4).2.75 biby}(n) (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the "metal free" 1,10-phenanthroline and its manganese complexes were found to be active.     

Synthesis and crystal structure of trans-nitrosoaquatetraammineruthenium(II) sulphate hydrosulphate, [Ru(NO)(NH3)4(H2O)](SO4)(HSO4)

The reaction between [RuNO(NH₃)₄OH]Cl₂ and an excess of 2 M H₂SO₄ leads to the protonation of the starting complex and crystallisation of the title complex with sulphate and hydrosulphate anions. The crystal structure of the product has been determined. The linear nitroso group and water molecule are coordinated in trans positions.