Electrochemiluminescence of tris(2,2 '-bipyridine)ruthenium(II) immobilized in poly(p-styrenesulfonate)-silica-Triton X-100 composite thin-films

The electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) [Ru(bpy)(3)(2+)] immobilized in poly(p-styrenesulfonate) (PSS)-silica-Triton X-100 composite films was investigated. The cooperative action of PSS, sol-gel and Triton X-100 attached Ru(bpy)(3)(2+) to the electrode strongly, and the presence of Triton X-100 prevented drying fractures of the sol-gel films during gelation and even on repeated wet-dry cycles. The modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and NADH in a flow injection analysis (FIA) system with a newly designed flow cell. The detection scheme exhibited good stability, short response time and high sensitivity. Detection limits were 0.1, 0.1 and 0.5 mu mol L-1 for oxalate, TPA and NADH, respectively, and the linear concentration range extended from 0.001 to 1 mmol L-1 for the three analytes. Applications of the flow cell in ECL and electrochemical detection, as well as the immobilization of reagents based on the cooperative action, are suggested.

Synthesis and properties of three tris(1,10-phenanthroline) ruthenium (II) derivatives

Three new asymmetrical ruthenium (II) complexes: [Ru(phen)(2){phen-NHCO(CH2)(4)Br}](PF6)(2), [Ru(phen)(2){phen-NHCO(CH2)(5)Br}](PF6)(2) and [Ru(phen)(2){phen-NHCO(CH2)(10)Br}](PF6)(2) were synthesized, which were confirmed by the technique of FT-IR, H-1 NMR and ESI-MS. The electrochemical and fluorescent properties of three Ru (II) complexes were investigated with cyclic voltammetry and fluorometry.

Two dimensional nuclear magnetic resonance analysis of bis(2,2 '-bipyridine)(2,2 '-bipyridine-4,4 '-dicarboxylic acid)ruthenium(II) hexafluorophosphate

The H-1 and C-13 nuclear magnetic resonance(NMR) spectra are reported for bis(2, 2'-bipyridine)(2, 2'-bipyridine-,4,4'-dicarboxylic acid) ruthenium(II) hexafluoruphosphate that has been used as a tagged molecule of electrochemiluminescent immunoassay. Because of the effect of Ru atom on ligands, it is difficult to assign its NMR spectra. BS' means of two dimensional H-1-H-1 COSY and H-1-C-13 COSY techniques, the H-1 and C-13 NMR spectra of bis (2, 2'-bipylidine) (2, 2'-bipyridine-4, 4-dicarboxylic acid) ruthenium(II) hexafluorophosphate are assigned completely. This provides a basis for NMR characterization of the nerv similar tagged molecules.

Four novel screw-like tris(1,10-phenanthroline) ruthenium(II) bishexafluorophosphate derivatives

Four novel screw-like Ru(II) complexes, tris(5-lauramide-1,10-phenanthroline)Ru(II) bishexafluorophosphate, tris(5-myristamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate, tris(5-palmitamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate and tris (5-stearamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate have been efficiently synthesized. They are confirmed by the techniques of IR, H-1 NMR, H-1-H-1 COSY and ES-MS. Also, their electrochemistry, fluorescence and electrochemiluminescence are reported.

Effects of heteropoly acids and surfactant on electrochemiluminescence of tris(2,2 '-bipyridine) ruthenium(II)

The effects of heteropoly acids and Triton X-100 on electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) are investigated. Triton X-100 prevents the oxidation of oxalate and results in an increase of the ECL signal. H5SiW11VO40 prevents the direct oxidation of oxalate and makes the electrochemical behavior of Ru(bpy)(3)(2+) less reversible, which leads to a decrease of the ECL signal. In contrast, H3PMo12O40 has negligible effect on ECL intensity. Some possible reasons for the effects on the ECL of Ru(bpy)(3)(2+) are discussed based on the adsorption of SiW11VO405- on electrode surface and the ion association between SiW11VO405- and Ru(bpy)(3)(2+). The signal of ECL decreases linearly with the concentration of heteropoly acid in the range from 2x10-6 to 1x10(-4) mol l(-1). The results indicate that ECL of RU(bpy)(3)(2+) is a potential sensitive and selective detection method for heteropoly acids and hence for the elements comprised in them.

A BINUCLEAR NICKEL(II) COMPLEX CONTAINING AN OXAMIDO-BRIDGE - SYNTHESIS, PROPERTIES AND X-RAY CRYSTAL-STRUCTURE OF [NI(OXAE)NI(PHEN)(2)](CLO4)(2)CENTER-DOT-3H2O

The binuclear complex [Ni(oxae)Ni(phen)2](ClO4)(2) . H2O (oxae=N,N'bis(2-aminoethyl) oxamido dianion, phen = 1, 10-phenanthroline) was prepared from the planar monomeric complex Ni(oxae) and characterized through analytical and spectroscopic measurements. The structure of [Ni(oxae)Ni(phen)(2)] (ClO4)2 . 3H(2)O was investigated by single-crystal X-ray analysis. The complex has an extended oxamido-bridged structure and consists of two nickel(II) ions, one of them in a square planar environment and another in a distorted octahedral environment. The Ni-Ni distance is 5.267 Angstrom.

A BIS(2,6-DI-TERT-BUTYL-4-METHYLPHENOLATO)-SAMARIUM(II) COMPLEX, [SM(OAR)2(THF)3]-THF

The title complex, bis(2,6-di-tert-butyl-4-methyl-phenolato-O)tris(tetrahydrofuran-O)samarium tetrahydrofuran solvate, [Sm(C15H23O)2(C4H8O)3].C4H8O, has distorted trigonal bipyramidal geometry around the Sm(II) atom. The 0(2), 0(3) and 0(4) atoms of the

SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF [EU(ETA-6-C6ME6)(ALCL4)2]4 - THE 1ST CYCLOTETRAMERIC LANTHANIDE(II) COMPLEX WITH A NEUTRAL PI-LIGAND

The reaction of EuCl3, AlCl3 and C6Me6 in toluene gives the Eu(II) complex [Eu(eta-6-C6Me6)(AlCl4)2]4; X-ray crystal determination shows the molecule to be a cyclotetramer, in which the four Eu(C6Me6)AlCl4 units are connected via four groups of eta-2-AlCl4.

Isolation and characterization of the oxygen-evolving photosystem II complex from the economical red alga Bangia fusco-purpurea

The highly pure and active photosystem II (PSII) complex was isolated from Bangia fusco-purpurea (Dillw) Lyngb., an important economic red alga in China, through two steps of sucrose density gradient ultracentrifugation and characterized by the room absorption and fluorescence emission spectra, DCIP (2,6-dichloroindophenol) reduction, and oxygen evolution rates. The PSII complex from B. fusco-purpurea had the characteristic absorption peaks of chlorophyll (Chl) a (436 and 676 nm) and typical fluorescence emission peak at 685 nm (Ex = 436 nm). Moreover, the acquired PSII complex displayed high oxygen evolution (139 mu mol O-2/(mg Chl h) in the presence of 2.5 mM 2,6-dimethybenzoqinone as an artificial acceptor and was active in photoreduction of DCIP (2,6-dichloroindophenol) by DPC (1,5-diphenylcarbazide) at 163 U/(mg Chl a h). SDS-PAGE also suggested that the purified PSII complex contained four intrinsic proteins (D1, D2, CP43, and CP47) and four extrinsic proteins (33-kD protein, 20-kD protein, cyt c-550, and 14-kD protein).

Characterisation of bifunctional ruthenium(ii) complexes, potential DNA photo-probes. Presence of folded and unfolded conformers

Novel bifunctional ruthenium(n) complexes, [Ru(TAP)2(POQ-Nmet)]2+ and [Ru(BPY)2(POQ-Nmet)]2+(la, 2a), containing a metallic and an organic moiety, have been prepared as photoprobes and photoreagents of DNA(TAP = 1,4,5,8-tetraazaphenanthrene, POQ-Nmet = 5-[6-(7-chloroquinolin-4-yl)-3-thia-6-azaheptanamido]-l,10phenanthroline). The ES mass spectrometry and 'H NMR data in organic solvents indicate that the quinoline moiety exists in both the protonated and non-protonated form. Moreover, the comparison of the NMR data with those of the corresponding monofunctional complexes(without quinoline) evidences that [Ru(TAP).2(POQ-Nmet)]2+ and [Ru(BPY)J(POQ-Nmet)]2+ are unfolded when the quinoline unit is protonated whereas deprotonation permits folding of the molecule. In the folded state the spatial proximity of the electron donor(the organic moiety) and electron acceptor(the metallic moiety) in [Ru(TAP)2(POQ-Nmet)]2+ favours intramolecular photo-induced electron transfer, which has been shown in a previous study to be responsible for the very low luminescence of la in non-protonating solutions. The restoration of the luminescence by protonation of the quinoline moiety as observed previously is in agreement with the unfolding of the molecule demonstrated in this work. The existence of such folding-unfolding processes related to protonation is crucial for studies of la with DNA. © The Royal Society of Chemistry 2000.

The isolation and secondary functionalisation of fac-tris2,2'-bipyridine complexes of ruthenium(II)

Fac-ruthenium(II) tris-(5-carboxy-2,2'-bipyridine) has been synthesised as a single geometric isomer for the first time, and proves to be a good "building-block" to introduce new functionality with retention of the isomeric integrity.