镧与去甲基斑蝥酸根配合物的合成、结构表征及抗癌活性

合成了具有抗抗癌活性的镧（Ⅲ）与去甲基斑蝥酸根的配合物，Na[La（DCA）2（H2O）]，并借助元素分析、摩尔电导、IR、UV-Vis、1H-NMR及TG-DTA谱等方法对配合物组成和结构进行了表征。结果表明，配合物中去甲基斑蝥根根以两个羧基氧原子和环醚氧原子同时与La（Ⅲ）配位，两个DCA共提供6个氧配位原子，第七个配位原子为H2O的氧原子。此外，用MTT或SRB法测定了配合物对4种具有代表性的癌细胞株的体外抗肿瘤活性。筛选结果证明，Na[La（DCA）2（H2O）]对某些癌细胞显示了比去甲基斑酸钠（Na2DCA）更强的抑制作用。     

新型铂配合物的合成及其抗肿瘤活性

以顺-二碘-二环戊胺合铂(Ⅱ)为起始原料,经聚合反应和胺化反应制得顺式-二碘-异丙胺-环戊胺合铂(Ⅱ)(2);2分别与氯化钾,1,1-环丁基二羧酸钾和一水合草酸钾反应,合成了3个新型的铂配合物:顺式-二氯-异丙胺-环戊胺合铂(Ⅱ)(1a,收率36.6%),顺式-1,1-环丁基二羧酸-异丙胺-环戊胺合铂(Ⅱ)(1b,收率43.6%)和顺式-草酸-异丙胺-环戊胺合铂(Ⅱ)(1c,收率28.1%),其结构经1H NMR,IR,ESI-MS和元素分析表征。采用MTT法测定了1a~1c对肝癌(SMMC-7721),肺癌(A-549),乳腺癌(MCF-7)和结肠癌(SW480)的体外抑制活性。结果表明,1a~1c对部分癌细胞的IC50值小于40μm,具有一定的体外肿瘤生长抑制活性。     

新型铂(Ⅱ)类配合物的合成、表征和抗肿瘤活性

Seven novel platinum(Ⅱ) complexes[Pt(Ⅱ)(NH₃)(H₂O)X](Ⅰ～Ⅶ) {X=(COO^-)₂(oxalato), 2p-CH₃O-C₆H₄-COO^-(p-methyoxbenzolato), 2C₆H₅-COO^-(benzolato), 2CH₃COO^-(acetato), (CH₂)(COO^-)₂(malonato), (CH₂)₂(COO^-)₂(succinato), (CH=CH)(COO^-)₂(maleato)} have been prepared and characterized by elemental analysis, thermal analysis，IR, UV, and ¹H NMR spectroscopy. The antitumor activities of these complexes in vitro against EJ、HCT-8, KB, BGC-823, Bel-7402, HL-60, MCF-7 and Hela cell lines have been studied. Complex Ⅰ and Ⅴ show remarkable antitumor activities against EJ cell line, and the inhibitory rate is 45.96% and 54.32% at concentration of 10 μmol·L^-1, respectively. The inhibitory rate of the complexes Ⅱ and Ⅲ is greater than 50% against HL-60, BGC-823, KB and EJ cell lines. The inhibitory rate of the complex Ⅵ is 51.89% and 57.96% against BGC-823 and EJ cell lines. The complexes Ⅳ and Ⅶ have no antitumor activities against tested tumor cell lines. The complexes Ⅱ, Ⅲ and Ⅵ can stem the cell cycle of HL-60 on the G₂+M.     

混胺丙二酸合铂(Ⅱ)混配配合物的合成、表征、X射线指标化及抗肿瘤活性的初步研究

在制得三个前体配合物 cis-Pt(CH3NH2 ) 2 I2 、[Pt(CH3NH2 ) I2 ]2 和 cis-Pt(NH3) (CH3NH2 ) I2 的基础上 ,成功地获得一种新的混胺丙二酸合铂 ( )类配合物 (NH3) (CH3NH2 ) Pt[(O2 C) 2 CH2 ]· 0 .5 H2 O。用元素分析、红外光谱、紫外光谱、氢核磁共振谱及摩尔电导等方法对其进行了性质表征 ,通过 Dicvol91指标化程序对配合物的 X射线粉末图进行了指标化 ,确定该晶本属单斜晶系 ,晶胞参数 :a=8.744 0 ,b=1 1 .5 90 2 ,c=4.40 96 ,β=96.2 3 3°,z=2。同时采用 MTT法测定了配合物对人的三种白血病细胞 HL-60、K5 62和 U93 7的抗癌活性。     

混胺二元羧酸根合铂(Ⅱ)混配配合物的合成及其抗肿瘤活性

顺铂和卡铂是目前治疗多种癌症的重要药物,但顺铂的肾毒性和肠胃反应,卡铂的有效剂量大等缺点限制了它们在临床上的广泛应用。混胺铂类配合物是一类甚具发展潜力的抗癌活性化合物 [1～ 5],其中有关离去基团为氯离子的混胺类铂配合物的抗癌活性报道颇多,但离去基团为二元羧酸根的混胺铂类配合物由于合成上的困难,而报道甚少,可是它们在化学结构上却兼顾了顺铂及卡铂的优点,故对此类配合物的研究具有重要的意义。我们在制备中用直接加入二元羧酸和碳酸银的方法,成功地合成了三个新的混胺二元羧酸根合铂 ?配合物,并对其进行某些生物活…     

手性钌配合物的合成、抗肿瘤活性及其与血清蛋白的相互作用

合成了手性钌配合物Δ, Λ-[Ru(bpy)₂(pyip)]²⁺, 通过元素分析、核磁共振、质谱和CD光谱对配合物进行了表征. 采用MTT法评价了3种异构体对多种肿瘤细胞株的体外抗肿瘤活性以及对正常细胞的毒性. 结果表明, Δ-[Ru(bpy)₂(pyip)]²⁺的抗肿瘤活性明显优于其异构体, 对A375, SW480, MCF-7和A549的半数抑制浓度低于顺铂. 通过荧光光谱法研究了在生理pH条件下, 手性钌配合物与牛血清白蛋白(BSA)之间的结合作用以及荧光猝灭机制. 依据Scatchard方程测定了结合常数和结合位点数, 根据热力学方程讨论了两者间的主要作用力类型. 结果表明, 钌配合物对牛血清白蛋白的荧光猝灭机制为静态猝灭. Δ-1, 1和Λ-1与牛血清白蛋白的结合常数分别为1.16×10⁵, 5.12×10⁴和3.64×10⁴, 结合位点数均为1, 主要作用力类型是静电作用. 钌配合物在体内能够被血清蛋白存储转运且结合时对蛋白构象无影响.     

阿司匹林铜(Ⅱ)配合物的合成、晶体结构和抗肿瘤活性

合成了阿司匹林铜(Ⅱ)配合物,通过红外、X射线单晶衍射对其结构进行了表征。配合物属单斜晶系,P21/n空间群,晶胞参数为a=8.211(5)nm,b=10.419(5)nm,c=21.003(5)nm,β=98.021(5)°,V=1779.2(14)nm3,Z=4。采用紫外光谱和荧光光谱法及循环伏安法研究了配合物与小牛胸腺DNA(ct-DNA)的相互作用。采用MTT法测定了配合物对体外培养人乳腺癌MCF-7和胃癌MGC-803细胞的抑制活性。当配合物浓度为120μmol/L时,对2种细胞增殖的抑制率分别为80.01%和70.16%。     

吲哚醌类Schiff碱及其配合物的合成与抗肿瘤活性研究

合成了两种吲哚醌类Schiff碱配体及其过渡金属Cu(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)的配合物,并用电子光谱、红外光谱、1H NMR加以表征。采用MTT比色法测定了配合物的体外抗肿瘤活性。经电子光谱、红外光谱、1H NMR所研究的结构与所预测的基本一致,并获得了L1·Zn、L2·Cu、L2·Zn、L2·Mn、L2·Co、L2·Ni等配合物的体外抗肿瘤活性测试结果。L1·Zn配合物对肺癌细胞SPCA-1、舌癌细胞Tb、胃癌细胞MGC以及白血病细胞K562的抑制作用较弱,吲哚醌单Schiff碱配体及金属Zn均可能是导致L1.Zn配合物抗肿瘤活性较弱的因素。L2的配合物对癌细胞都有一定的杀伤作用,尤其是Cu(II)的配合物,其对这几种细胞的抑制作用明显好于其他配合物。     

铑配合物的抗肿瘤活性及其作用机制研究

自从Rosenberg等人发现顺铂具有抗肿瘤活性以来，金属配合物的抗肿瘤活性引起了人们的广泛关注。本文综述了近年来铑配合物抗肿瘤活性的研究进展，并对铑配合物的抗肿瘤机制和构效关系进行了探讨，为进一步寻找高效低毒和抗肿瘤谱广的新药物揭示了可循的途径。     

Synthesis and physicochemical studies on Co(III) complexes

Complexes of Co(III) with 2-hydroxyacetophenone-thiosemicarbazone, 2-hydroxy-3-methylacetophenonethiosemicarbazone and 2-hydroxy-4-methyl-acetophenonethiosemicarbazone, and the addition complexes of 2-hydroxy-acetophenone thiosemicarbazone with ammonia, pyridine, aniline,o-toluidine,m-toluidine andp-toluidine have been synthesized and characterized on the basis of their conductivities, electronic and infrared spectral data. All complexes are low-spin octahedral in nature. Various parameters have been obtained using ligand field theory.     

Studies on Co(II) and Co(III) complexes of di-2-pyridyl ketone N(4)-cyclohexyl and N(4)-phenyl thiosemicarbazones

Six new Co(II) and Co(III) complexes (1–6) of di-2-pyridyl ketone N(4)-cyclohexyl thiosemicarbazone (HL¹) and di-2-pyridyl ketoneN(4)-phenyl thiosemicarbazone (HL²) have been synthesized and spectrochemically characterized. HL¹ is newly synthesized and has been structurally characterized by single crystal X-ray diffraction studies, while HL² has been previously reported. HL¹ crystallizes into a monoclinic lattice with the space group P2₁. The complexes are characterized by magnetic, EPR, NMR and other spectroscopic studies. The EPR spectra of the paramagnetic complexes reveal axial features with eight hyperfine lines clearly resolved in the perpendicular region.     

Synthesis,characterization and cytotoxicity evaluation of new cerium(III), lanthanum(III) and neodymium(III) complexes

Complexes of cerium(III), lanthanum(III) and neodymium(III) with coumarin‐3‐carboxylic acid (HCCA) were synthesized by mixing of equimolar amounts of the respective metal nitrates and coumarin‐3‐carboxylic acid in ethanol. The complexes were characterized and identified by elemental analysis, IR and Raman spectroscopy. DTA and TGA were applied to study the compositions of the compounds. The vibrational study showed bidentate coordination of CCA^? to Ln(III) ions through the carbonyl oxygen and the carboxylic oxygen atoms. The newly synthesized compounds were assayed for cytotoxicity against SKW‐3, HL‐60 and Reh cells. The complexes of cerium(III) and lanthanum(III) showed marginal cytotoxic activity against SKW‐3 and Reh cells as compared with the inorganic salts at concentration 200 µM . The complex of neodymium(III) induced approximately 50% reduction of the survival HL‐60 and SKW‐3 cells at concentration 200 µM . Copyright © 2007 John Wiley & Sons, Ltd.     

Mononuclear gallium(III) complexes based on salicylaldoximes: Synthesis,structure and spectroscopic characterization

The reactions of Ga(acac)₃ with salicylaldoxime (saoH₂) and methyl-salicylaldoxime (Me-saoH₂) in dichloromethane/hexane afforded the complexes [Ga(acac)(saoH)₂] (1) and [Ga(acac)₃][Ga(acac)(MesaoH)₂] (2), respectively, in high yields. The crystal structures of 1 and 2 have been determined by single-crystal X-ray crystallography. Both complexes are mononuclear with the Ga(III) atoms being in octahedral environments surrounded by two bidentate chelate R-saoH⁻ and one bidentate chelate acac⁻ ligands. A [Ga(acac)₃] moiety has co-crystallized along with the methylsalicylaldoximato complex. Characteristic IR as well as NMR data are discussed in terms of the nature of bonding in the structures of the two complexes. ¹H and ¹³C NMR data in CDCl₃ indicate that the salicylaldoximato complexes isomerize in solution.     

DNA binding and cleavage properties of certain ethylenediamine cobalt(III) complexes of modified 1,10-phenanthrolines

Two complexes of the type [Co(en)₂IP]³⁺ (IP = imidazo[4,5-f][1,10]-phenanthroline) and [Co(en)₂PIP]³⁺ (PIP = 2-phenylimidazo[4,5-f][1,10]-phenanthroline) have been synthesized and characterized by UV–VIS, IR and¹H NMR spectral methods. Absorption spectroscopy, emission spectroscopy, viscosity measurements and DNA melting techniques have been used to investigate the binding of these two complexes with calf thymus DNA and photocleavage studies have been used to investigate the binding of these complexes with plasmid DNA. The spectroscopic studies together with viscosity measurements and DNA melting studies support that complexes 1 and 2 bind to CT DNA(=calf thymus DNA) by an intercalation mode via IP or PIP into the base pairs of DNA. Complex 2 binds more avidly to CT DNA than 1, which is consistent with the extended planar ring π system of PIP. Noticeably, the two complexes have been found to be efficient photosensitisers for strand scissions in plasmid DNA.     

Synthesis, spectral and structural studies of 1-ethoxycarbonyl-piperazine-4-carbodithioate and its Co(III), Zn(II) and Cd(II) complexes

The new complexes [Co(ecpzdtc)₃] (2) [Zn(ecpzdtc)₂(py)] (3) and [Cd(ecpzdtc)₂(py)]·H₂O (4) have been synthesized from sodium 1-ethoxycarbonyl-piperazine-4-carbodithioate [(Na⁺(ecpzdtc)⁻]. The ligand and the complexes have been characterized by elemental analyses, IR, magnetic susceptibility and single crystal X-ray data. The [Zn(ecpzdtc)₂(py)] and [Cd(ecpzdtc)₂(py)]·H₂O complexes contain pyridine as the co-ligand. [Co(ecpzdtc)₃] (2) crystallizes in the monoclinic system, whereas [Zn(ecpzdtc)₂(py)] (3) and [Cd(ecpzdtc)₂(py)]·H₂O (4) crystallize in the triclinic system. The sulfur donor sites of the bidentate ligand chelate the metal center, forming a four-membered CS₂M ring. The cobalt complex has a distorted octahedral geometry, the zinc complex is almost between trigonal bipyramidal and square pyramidal, whereas the cadmium complex is square pyramidal. The crystal structures of all the complexes are stabilized by various types of inter and intramolecular hydrogen bonding.     

Thermogravimetric and spectroscopic studies on La(III) and Ce(III) complexes with some thio-schiff bases

Solid complexes of five derivatives of thio-Schiff bases with La(III) and Ce(III) ions were prepared and characterized by elemental and thermogravimetric analyses. The suggested general formula of the solid complexes is [ML₂(H₂O)X]·2H₂O, whereM=trivalent lanthanide ion,L=Schiff base andX=Cl^? or ClO ₄ ^? . Information about the water of hydration, the coordinated water molecules, the coordination chemistry and the thermal stability of these complexes was obtained and is discussed. Additionally, a general scheme of thermal decomposition of the lanthanide-Schiff base complexes is proposed.     

Complex formation constants and thermodynamic parameters for La(III) and Y(III)L-serine complexes

Summary The stoichiometric stability constants for La(III) and Y(III)L-serine complexes were determined by potentiometric methods at different ionic strengths adjusted with NaClO₄ and at different temperatures. The overall changes in free energy (G ^o), enthalpy (H ^o), and entropy (S ^o) during the protonation ofL-serine and that accompanying the complex formation with the metal ions have been evaluated.

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Komplexbildungskonstanten und thermodynamische Parameter für La(III)- und Y(III)-L-Serin-Komplexe

Zusammenfassung Die stöchiometrischen Komplexbildungskonstanten für La(III)- und Y(III)-L-Serin-Komplexe wurden mittels potentiometrischer Methoden bei verschiedenen Ionenstärken (mit NaClO₄ adjustiert) und bei verschiedenen Temperaturen bestimmt. Die Änderungen in der freien Energie (G ^o), Enthalpie (H ^o) und Entropie (S ^o) während der Protonierung und der Komplexbildung mit den Metallionen wurden ermittelt.

     

Synthesis and cytotoxicity study of gold(III) porphyrin complexes and their derivative in breast cancer cells

Gold(III) [Au(III)] complexes exhibit potential anticancer activities. A series of Au(III) porphyrin complexes containing different meso-substituent groups (phenyl, methoxyphenyl, butyloxyphenyl, octyloxyphenyl, and decyloxyphenyl) was synthesized. The synthesized compounds were characterized using mass spectrometry, infrared spectroscopy, UV–visible and fluorescence spectroscopy, and electron paramagnetic resonance spectroscopy. Moreover, the in vitro cytotoxicity of these Au(III) porphyrin complexes was investigated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide surrogate viability assay on an MCF7 human breast cancer cell line. The Au(III) complexes with 5,10,15,20-tetraphenylporphyrin (AuTPP) and 5,10,15,20-tetrakis(4-methyloxyphenyl)porphyrin (AuTOMPP) demonstrated high anticancer activity with IC₅₀ values against MCF7 cells at 4.30 and 25.35 µM, respectively. The toxicity of the Au(III) porphyrin complexes against the LLC-MK2 rhesus monkey kidney epithelial cell line, a representative normal cell line, was investigated. All the tested Au(III) porphyrin complexes were non-cytotoxic in LLC-MK2 cells. For AuTPP, more than 80% LLC-MK2 cell viability was observed at concentrations lower than 5 μM.     

Synthesis,characterization, photocleavage,antimicrobial activity and DNA binding of [Co(bpy)2MHPIP]3+, [Co(dmb)2MHPIP]3+, and [Co(phen)2MHPIP]3+ complexes

4-Methyl-2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline) (MHPIP) and its complexes [Co(bpy)₂MHPIP]³⁺ (1) (bpy = 2,2′-bipyridine), [Co(dmb)₂MHPIP]³⁺ (2) (dmb = 4,4′-dimethyl-2,2′-bipyridine), and [Co(phen)₂MHPIP]³⁺ (3) (phen = 1,10-phenanthroline) have been synthesized and characterized by UV/VIS, IR, EA, ¹H, ¹³C-NMR, and mass spectra. The binding of the three complexes with calf-thymus-DNA (CT-DNA) has been investigated by absorption and emission spectroscopy, DNA-melting techniques, viscosity measurements, and DNA cleavage assay. The spectroscopic data and viscosity results indicate that these complexes bind to CT-DNA via an intercalative mode. The complexes also promote photocleavage of plasmid pBR322 DNA and were screened for antimicrobial activity.