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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 79(5): 1876-80, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21676645

RESUMO

A sensitive fluorescent probe 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenol (HBIZ) for pH and Zn2+ has been developed. Great changes have taken place in the UV-vis absorption and fluorescence spectra for HBIZ upon increasing pH of its aqueous solution, acting as a pH-induced emission "off-on-off" switch with large enhancement factors of ∼290 and ∼75 over the pH range of 1.00-5.40 and 5.20-10.40. A over 100-fold fluorescence enhancement was also observed after complexation of HBIZ to Zn2+ in N,N-dimethylformamide.


Assuntos
Corantes Fluorescentes/química , Imidazóis/química , Fenóis/química , Zinco/análise , Dimetilformamida , Fluorescência , Formamidas/química , Concentração de Íons de Hidrogênio , Estrutura Molecular , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta
2.
J Inorg Biochem ; 105(3): 435-43, 2011 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-21421130

RESUMO

Three binuclear Ru(II) complexes with two [Ru(bpy)(2)(pip)](2+)-based subunits {where bpy=2,2'-bipyridine and pip=2-phenylimidazo[4,5-f][1,10]phenanthroline} being linked by varied lengths of flexible bridges, were synthesized and characterized by (1)H NMR, elemental analysis, UV-visible (UV-vis) and photoluminescence spectroscopy. The structures of the three complexes were optimized by density functional theory calculations. The interaction of the complexes with calf thymus DNA was investigated by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN)(6)](4-), DNA competitive binding with ethidium bromide, DNA melting experiments, and viscosity measurements. The experimental results indicated that the three complexes bound to the DNA most probably in a threading intercalation binding mode with high DNA binding constant values three orders of magnitude greater than the DNA binding constant value reported for proven DNA intercalator, mononuclear counterpart [Ru(bpy)(2)(p-mopip)](2+) {p-mopip=2-(4-methoxylphenyl)imidazo[4,5-f][1,10]phenanthroline}.


Assuntos
2,2'-Dipiridil/química , DNA/metabolismo , Compostos Organometálicos/química , Compostos Organometálicos/metabolismo , Fenantrolinas/química , Rutênio/química , Sítios de Ligação , Cátions Bivalentes , DNA/química , Medições Luminescentes , Compostos Organometálicos/síntese química , Análise Espectral , Viscosidade
3.
J Nanosci Nanotechnol ; 10(3): 2053-9, 2010 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-20355626

RESUMO

New hybrid multilayer films containing Prussian blue (PB) and a binuclear Ru(II) complex were successfully fabricated using the electrostatic layer-by-layer self-assembly technique. The process was carefully monitored by ultraviolet-visible (UV-vis) spectroscopy. A linear increase in the UV-vis absorbance with the number of deposited layers indicated that the film deposition was uniform and reproducible. The electrochemical and photoelectrochemical properties of these hybrid multilayer films were investigated in an aqueous Na2SO4 solution. PB and the binuclear Ru(II) complex assembled in the film were redox active with surface confined characteristics. The surface concentration and molecular area of RuL in the film were calculated according to a UV-vis absorption spectrum and cyclic voltammetry, respectively. The photocurrent generated by switching on the light irradiation of the film increased linearly as the deposited bilayers increased. The photocurrent action spectrum was in agreement with metal-to-ligand charge-transfer (MLCT) band of RuL in the absorption spectrum, which indicated that the photocurrent was generated based on MLCT excitation of the RuL in the (PB/RuL) film.

4.
Inorg Chem ; 49(8): 3752-63, 2010 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-20337492

RESUMO

A new heteroleptic ruthenium(II) complex of [Ru(Hipdpa)(Hdcbpy)(NCS)(2)](-).0.5H(+).0.5[N(C(4)H(9))(4)](+) Ru(Hipdpa) {where Hdcbpy = monodeprotonated 4,4'-dicarboxy-2,2'-bipyridine and Hipdpa = 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-N,N-diphenylaniline} was synthesized and characterized by elementary analysis, standard spectroscopy techniques, and cyclic voltammetry. The ground- and excited-state acid-base properties of Ru(Hipdpa) were studied by means of UV-vis absorption spectrophotometric and spectrofluorimetric titrations in 4:1(v/v) Britton-Robinson/dimethylformamide buffer solution. The four-step separate protonation/deprotonation processes were found in the ground states, and one of which taking place near the physiological pH range. The two observable excited-state protonation/deprotonation processes were found for the Ru(Hipdpa), constituting pH-induced "off-on-off" emission switches. The performance of the complexes as photosensitizers in nanocrystalline TiO(2)-based liquid solar cells containing an electrolyte solution (0.05 M I(2), 0.5 M LiI, and 0.5 M 4-tert-butylpyridine in 50% acetonitrile and 50% propylene carbonate) was investigated and found to achieve a much improved device performance (a short-circuit photocurrent density of 18.7 mA cm(-2), an open-circuit voltage of 630 mV, and an overall conversion efficiency of 6.85%) compared to a triphenylamine-free parent complex [Ru(Hpip)(Hdcbpy)(NCS)(2)](-).[N(C(4)H(9))(4)](+)-based device {Hpip = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} and a comparable performance to that of cis-bis(isothiocyanato)bis(2,2'-bipyridine-4,4'-dicarboxylic acid)ruthenium(II) (N3) under identical experimental conditions. A density functional theory calculation of the molecular structures and electronic properties of the complexes was also carried out in an effort to understand their effectiveness in TiO(2)-based solar cells.

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