A ruthenium(II) complex-based carbonic anhydrase (CA) inhibitor, [Ru(bpy)2(bpybs)](2+) {bpy = 2,2'-bipyridine and bpybs = 4'-methyl-2,2'-bipyridinyl-4-carboxylic acid (2-{2-[(4-sulphamoylbenzoylamino)ethoxy]ethoxy}ethyl)amide}, tethering a benzenesulfonamide group and a [Ru(bpy)3](2+) moiety has been prepared. The CA activity was effectively suppressed by a synthetic [Ru(bpy)2(bpybs)](2+) inhibitor, and the dissociation constant at pH 7.2 and at 25 °C was determined to be KI = 1.
View Article and Find Full Text PDFCytochrome c (cyt c) derivatives modified with a platinum(II) complex at the lysine residue, cyt c(III)-[Pt(bpy)(dapap)](1) {bpy = 2,2'-bipyridine, and dapap = 3-(2,3-diaminopropionylamino)propionic acid}, have been prepared. The modified residues are Lys8, Lys13, Lys55, Lys60, Lys73, and Lys88. In the case of the cyt c(III)-[Pt(bpy)(dapap)](1) dyad, the photoexcited singlet state of (1)([Pt(bpy)(dapap)](1))* was quenched by the heme Fe(III) moiety through the intramolecular photoinduced energy-transfer reaction via a through-space mechanism.
View Article and Find Full Text PDFThe reconstituted zinc-myoglobin (ZnMb) dyads, ZnMb-[M(II)(edta)], have been prepared by incorporating a zinc-porphyrin (ZnP) cofactor modified with ethylenediaminetetraacetic acid (H(4)edta) into apo-Mb. In case of the monomeric ZnP(edta) cofactor coordinated by one pyridine molecule, ZnP(py)(edta), a spontaneous 1:1 complex with a transient metal ion was formed in an aqueous solvent, and the photoexcited singlet state of ZnP, (1)(ZnP)*, was quenched by the [Cu(II)(edta)] moiety through intramolecular photoinduced electron-transfer (ET) reaction. The rate constant for the intramolecular quenching ET (k(q)) at 25 degrees C was successfully obtained as k(q) = 5.
View Article and Find Full Text PDFA reconstituted zinc-myoglobin (ZnMb) dyad, ZnMb-[Pt(bpy)(en)]2+, has been prepared by incorporating chemically-modified zinc-porphyrin, being capable of DNA-binding of the Pt complex, [Pt(bpy)(en)]2+, where bpy and en are 2,2'-bipyridine and ethylenediamine, respectively. The steady-state fluorescence of the cofactor, [Pt(bpy)(mu-enPP)Zn]Cl2, in MeOH indicates that the excited singlet state of zinc--porphyrin was almost quenched, probably because of the strong hydrophobic and pi-pi stacking interactions between the [Pt(bpy)(mu-enPP)Zn]2+ ions. In the reconstituted ZnMb-[Pt(bpy)(en)]2+, the quenching reaction of 1(ZnMb)* with the [Pt(bpy)(en)]2+ moiety does not occur, indicating apo-Mb matrix is essential.
View Article and Find Full Text PDFIn order to elucidate the intramolecular photoinduced electron-transfer or energy-transfer mechanisms of the zinc myoglobin (ZnMb) dyad and to construct a photoreaction system within a Mb-DNA complex, we newly prepared ZnMb appending an ethidium ion (Et(+)). The steady-state fluorescence of ZnMb-Et(+) at 600 nm and its lifetime (2.2 ns) indicate that the excited singlet state of (1)(ZnMb)* is not quenched by the Et(+) moiety, whereas the lifetime of the excited triplet state of (3)(ZnMb)*-Et(+) was shorter (tau = 4.
View Article and Find Full Text PDFThree types of reconstituted met- and zinc-myoglobin (metMb and ZnMb) dyads, ZnMbAc(4)Me+, ZnMbAc(6)Me+, and metMbAc(6) have been prepared by incorporating chemically modified metalloporphyrin cofactor appending an acridine (Ac) or a methylacridinium ion ([AcMe]+) into apo-Mb. In the bimolecular system between ZnMb and [AcMe]+, the photoexcited triplet state of ZnMb, 3(ZnMb)*, was successfully quenched by [AcMe]+ to form the radical pair of ZnMb cation (ZnMb*+) and reduced methylacridine ([AcMe]*), followed by a thermal back ET reaction. The rate constants for the intermolecular quenching ET (kq) and the back ET reaction (kb) at 25 degrees C were successfully obtained as kq = (8.
View Article and Find Full Text PDFIn order to understand the detailed mechanism of the stereoselective photoinduced electron-transfer (ET) reactions of zinc-substituted myoglobin (ZnMb) with optically active molecules by flash photolysis, we designed and prepared new optically active agents, such as N,N'-dimethylcinchoninium diiodide ([MCN]I2) and N,N'-dimethylcinchonidinium diiodide ([MCD]I2). The photoexcited triplet state of ZnMb, 3(ZnMb)*, was successfully quenched by [MCN]2+ and [MCD]2+ ions to form the radical pair of ZnMb cation (ZnMb.+) and reduced [MCN].
View Article and Find Full Text PDFHexafluorophosphate salts of mononuclear complexes [Ru(II)Cl(L)(terpy)]+ (L = dmbpy (1); dpbpy (2), sambpy (3), and dpp (7), and binuclear complexes [Ru(II)2Cl2(dpp)(terpy)2]2+ (8) and [Ir(III)Ru(II)Cl2(dpp)(terpy)2]3+ (9) were prepared and characterized. Abbreviations of the ligands are bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine, dpbpy = 4,4'-diphenyl-2,2'-bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine, sambpy = 4,4'-bis((S)-(+)-alpha-1-phenylethylamido)-2,2'-bipyridine, and terpy = 2,2':6',2''-terpyridine. The absorption spectra of 8 and 9 are dominated by ligand-centered bands in the UV region and by metal-to-ligand charge-transfer bands in the visible region.
View Article and Find Full Text PDFFour useful polypyridine iridium(III) complexes in the form of [IrCl2L2]+ were prepared and their spectroscopic and electrochemical properties as well as X-ray crystallography were investigated. The ligands used were L = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, and 2,2'-biquinoline. Synthetic methods were developed by a sequential ligand-replacement, which occurred in the reaction vessel using a microwave oven.
View Article and Find Full Text PDFWe have designed and synthesized new optically active bisviologens ([BNMV](4+)) containing a binaphthyl moiety to examine the stereoselective photoinduced electron-transfer (ET) reactions with zinc-substituted myoglobin (ZnMb) by flash photolysis. The photoexcited triplet state of ZnMb, (3)(ZnMb)*, was successfully quenched by [BNMV](4+) ions to form the radical pair of a ZnMb cation (ZnMb(.+)) and a reduced viologen ([BNMV](.
View Article and Find Full Text PDFPhotoinduced electron-transfer reactions between zinc-substituted myoglobin and optically active viologens and bisviologens, containing ((naphthyl-, ((phenyl-, and ((cyclohexyl)ethyl)carbamoyl)methyl groups, have been studied at 25 degrees C, pH 7.0 (a 0.01 M phosphate buffer), and various ionic strengths.
View Article and Find Full Text PDFA new series of oxo-centered acetate-bridged triruthenium comlexes having two redox-active N-methyl-4,4'-bipyridinium ions (mbpy(+)) have been prepared, and their reversible multistep and multielectron electrochemical properties are reported: [Ru(III)(2)Ru(II)(&mgr;(3)-O)(&mgr;-CH(3)CO(2))(6)(mbpy(+))(2)(CO)](2+) and [Ru(III)(3)(&mgr;(3)-O)(&mgr;-CH(3)CO(2))(6)(mbpy(+))(2)(L)](3+) (L = H(2)O, pyrazine (pz), pyridine (py), imidazole (Him), and 4-(dimethylamino)pyridine (dmap)). Among these series, the CO complex, [Ru(III)(2)Ru(II)(&mgr;(3)-O)(&mgr;-CH(3)CO(2))(6)(mbpy(+))(2)(CO)](ClO(4))(2).2DMF (1b.
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