[Ru(bpy)2L]2+、[Ru(phen)2L]2+(L=pytp,pztp)电子结构与抗癌活性研究

Theoretical studies on the complexes Ru(bpy)2L2+, Ru(phen)2L2+ (L=pytp,pztp) were carried out by using the density functional theory (DFT) method at B3LYP/LanL2DZ level. The relation between electronic structures and anti-cancer activities of complexes was investigated. The increasing of N in the main ligand can strengthen the interaction of complexes with DNA and anti cancer activities of complexes. The calculation results show that for complexes I-IV, their energies of LUMO orbital are in the order of εI>εII, εIII>εIV, the electron cloud components of LUMO come mainly from main ligands and the content distributing is in the order of I相似文献   

Synthese und Kristallstruktur von Te3O3(PO4)2, einer Verbindung mit fünffach koordiniertem Tellur(IV)

Synthesis and Crystal Structure of Te₃O₃(PO₄)₂, a Compound with 5‐fold Coordinate Tellurium(IV) Polycrystalline Te₃O₃(PO₄)₂ is formed during controlled dehydration of (Te₂O₃)(HPO₄) with (Te₈O₁₀)(PO₄)₄ as an intermediate product. Colourless single crystals were prepared by heating stoichiometric amounts of the binary oxides P₂O₅ und TeO₂ in closed silica glass ampoules at 590 °C for 8 hours. The crystal structure (P2₁/c, Z = 4, α = 12.375(2), b = 7.317(1), c = 9.834(1)Å, β = 98.04(1)°, 1939 structure factors, 146 parameters, R[F² > 2σ(F²)] = 0.0187, wR2(F² all) = 0.0367) was determined from four‐circle diffractometer data and consists of [TeO₅] polyhedra und PO₄ tetrahedra as the main building units. The framework structure is made up of cationic zigzag‐chains of composition [Te₂O₃]²⁺ which extend parallel to [001] and anionic [Te(PO₄)₂]^2— units linked laterally to these chains. This leads to the formation of [Te₂O₃][Te(PO₄)₂] layers parallel to the bc plane which are interconnected via weak Te‐O bonds.     

Photoinitiated DNA Binding by cis-[Ru(bpy)2(NH3)2]2+

The ligand-loss photochemistry of cis-[Ru(bpy)(2)(NH(3))(2)](2+) (bpy = 2,2'-bipyridine) was investigated in water and in the presence of added ligands such as bipyridine and chloride. Irradiation of the complex results in the covalent binding to 9-methyl- and 9-ethylguanine, as well as to single-stranded and double-stranded DNA. This photoinduced DNA binding is not observed for the control complex [Ru(bpy)(2)(en)](2+) (en = ethylenediamine) under similar irradiation conditions. The results presented here show that octahedral Ru(II) complexes with photolabile ligands may prove useful as photoactivated cisplatin analogs.     

Base-Modified DNA Labeled by [Ru(bpy)3]2+ and [Os(bpy)3]2+ Complexes: Construction by Polymerase Incorporation of Modified Nucleoside Triphosphates,Electrochemical and Luminescent Properties,and Applications

Modified 2′-deoxynucleoside triphosphates (dNTPs) bearing [Ru(bpy)₃]²⁺ and [Os(bpy)₃]²⁺ complexes attached via an acetylene linker to the 5-position of pyrimidines (C and U) or to the 7-position of 7-deazapurines (7-deaza-A and 7-deaza-G) have been prepared in one step by aqueous cross-couplings of halogenated dNTPs with the corresponding terminal acetylenes. Polymerase incorporation by primer extension using Vent (exo-) or Pwo polymerases gave DNA labeled in specific positions with Ru²⁺ or Os²⁺ complexes. Square-wave voltammetry could be efficiently used to detect these labeled nucleic acids by reversible oxidations of Ru^2+/3+ or Os^2+/3+. The redox potentials of the Ru²⁺ complexes (1.1–1.25 V) are very close to that of G oxidation (1.1 V), while the potentials of Os²⁺ complexes (0.75 V) are sufficiently different to enable their independent detection. On the other hand, Ru²⁺-labeled DNA can be independently analyzed by luminescence. In combination with previously reported dNTPs bearing ferrocene, aminophenyl, and nitrophenyl tags, the Os-labeled dATP has been successfully used for “multicolor” redox labeling of DNA and for DNA minisequencing.     

Synthesis,characterization and DNA binding and photocleavage studies of [Ru(bpy)2BDPPZ]2+, [Ru(dmb)2BDPPZ]2+ and [Ru(phen)2BDPPZ]2+ complexes and their antimicrobial activity

Polypyridyl ligand 9a,13a‐dihydro‐4,5,9,14‐tetraaza‐benzo[b]triphenylene‐11‐yl)‐phenyl‐methanone (BDPPZ) and its complexes [Ru(bpy)₂BDPPZ]²⁺, [Ru(dmb)₂BDPPZ]²⁺ and [Ru(phen)₂BDPPZ]²⁺ (where bpy = 2,2′‐bipyridine, dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized and characterized by elemental analysis, IR, UV–vis, ¹H‐NMR, ¹³C‐NMR and mass spectra. The DNA‐binding properties of the complexes were investigated by absorption, emission, melting temperature and viscosity measurements. Experimental results indicate that the three complexes can intercalate into DNA base pairs. Photo activated cleavage of pBR‐322 DNA by the three complexes was also studied. Further, all three Ru(II) complexes synthesized were screened for their antimicrobial activity. Copyright © 2009 John Wiley & Sons, Ltd.