The sensitization of the ligand-field state of the hexaammineruthenium(II) complex ion by organic compounds

The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

Twentyfold blue upconversion emission enhancement through thermal effects in Pr3+/Yb3+-codoped fluoroindate glasses excited at 1.064 mu m

Infrared-to-visible upconversion emission enhancement through thermal effects in Yb3+-sensitized Pr3+-doped fluoroindate glasses excited at 1.064 mu m is investigated. A twentyfold increase in the 485 nm blue emission intensity as the sample temperature was varied from 20 to 260 degrees C was observed. The visible upconversion fluorescence enhancement is ascribed to the temperature dependent multiphonon-assisted anti-Stokes excitation of the ytterbium sensitizer and excited-state absorption of the praseodymium acceptor. A model based upon conventional rate equations considering a temperature dependent effective absorption cross section for the F-2(7/2)-->F-2(5/2) transition of the Yb3+ and (1)G(4)-->P-3(0) excited-state absorption of the Pr3+, agrees very well with the experimental results. (C) 2000 American Institute of Physics. [S0021-8979(00)08209-8].

Thermally enhanced cooperative energy-transfer frequency upconversion in terbium and ytterbium doped tellurite glass

Infrared-to-visible frequency upconversion through cooperative energy-transfer and thermal effects in Tb3+/Yb3+-codoped tellurite glasses excited at 1.064 mum is investigated. Bright luminescence emission around 485, 550, 590, 625 and 65 nm, identified as due to the D-5(4) --> F-7(J) (J= 6, 5, 4, 3, and 2) transitions of the terbium ions, respectively, was recorded. The excitation of the D-5(4) emitting level of the Tb3+ ions is assigned to cooperative energy-transfer from pairs of ytterbium ions.. The effect of temperature on the upconversion process was examined and the results revealed a fourfold upconversion enhancement in the 300-500 K interval. The enhancement of the upconversion process is due to the temperature dependence of the Yb3+-sensitizer absorption cross-section under anti-Stokes excitation. A rate-equation. model using multiphonon-assisted absorption for the ytterbium excitation combined with the energy migration effect between Yb-Yb pair, and Tb3+ ground-state depopulation via multiphonon excitation of the F-7(J) excited states describes quite well the experimental results. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Efficient energy upconversion emission in Tm3+/Yb3+-codoped TeO2-based optical glasses excited at 1.064 mu m

Efficient energy upconversion of cw radiation at 1.064 mum into blue, red, and near infrared emission in Tm3+-doped Yb3+-sensitized 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) glasses is reported. Intense blue upconversion luminescence at 485 nm corresponding to the Tm3+ (1)G(4)--> H-3(6) transition with a measured absolute power of 0.1 muW for 800 mW excitation power at room temperature is observed. The experimental results also revealed a sevenfold enhancement in the upconversion efficiency when the sample was heated from room temperature to 235 degreesC yielding 0.7 muW of blue absolute fluorescence power for 800 mW pump power. High brightness emission around 800 nm (F-3(4)--> H-3(6)) in addition to a less intense 655 nm ((1)G(4)--> H-3(4) and F-3(2,3)--> H-3(6)) fluorescence is also recorded. The energy upconversion excitation mechanism for thulium emitting levels is assigned to multiphonon-assisted anti-Stokes excitation of the ytterbium-sensitizer followed by multiphonon-assisted sequential energy-transfer processes. (C) 2001 American Institute of Physics.

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Energy of the Photosubstitutionally Reactive Excited State of Pentaammine(pyridine)ruthenium(II)

The photosensitized aquation of pentaammine(pyridine)ruthenium(II) by several dyes has been studied under conditions where only the sensitizers absorb light. The ratio of the quantum yields for ammine and pyridine substitution was the same as that for direct photoaquation. Sensitization was effective with singlet sensitizers Rhodamine-B (17 452 cm -1) and Safranine-T (17 690 cm -1), as well as the triplet sensitizer biacetyl (19 000 cm -1), but no reaction was observed with Neutral-Red (16 900 cm -1). The results indicate that the excited state precursor of the observed photosubstitution in the complex lies in the energy range between 17 000 and 17 700 cm -1.

Structure, characterization and near-infrared emission of a novel 6-connected uninodal 3D network of Nd(III) containing 2,5-thiophenedicarboxylate anion

The novel coordination polymer with the formula {[Nd2(2,5-tdc)3(dmf)2(H2O)2].dmf.H2O}n (2,5-tdc2-=2,5-thiophedicarboxylate anion and dmf=dimethylformamide) has been synthesized and characterized by thermal analysis (TG/DTA), vibrational spectroscopy (FTIR) and single crystal X-ray diffraction analysis (XRD). Structure analysis reveals that Nd(III) ions show dicapped trigonal prism coordination geometry. The 2,5-tdc2- ligands connect four Nd(III) centers, adopting (κ1 - κ1) - (κ1 - κ1) - μ4 coordination mode, generating an interesting 6-connected uninodal 3D network. Photophysical properties were studied using diffuse reflectance spectroscopy (DR) and excitation/emission spectra. The photoluminescence data show the near infrared emission (NIR) with the characteristic 4F3/2→4IJ (J=9/2, 11/2 and 13/2) transitions of Nd(III) ion, indicating that 2,5-tdc2- is able to act as a sensitizer for emission in NIR region. © 2013 Elsevier B.V.

Vidros a base de óxido de telúrio para dispositivos fotônicos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photodynamic therapy in root canals contaminated with Enterococcus faecalis using curcumin as photosensitizer

The aim of the study was to evaluate the photodynamic therapy (PDT) effect on root canals contaminated with Enterococcus faecalis using a light emitting diode (LED) light and a curcumin solution (CUR) as photosensitizer (PS). Eighty root canals from uniradicular human teeth were prepared with Protaper Universal rotary system and contaminated with E. faecalis for 21 days. They were divided as: GIa-PDT (CUR, pre-irradiation for 5 + 5 min of irradiation); GIb-PDT (CUR, pre-irradiation for 5 + 10 min of irradiation); GIIa-(CUR, pre-irradiation for 5 + 5 min without irradiation); GIIb-(CUR pre-irradiation for 5 + 10 min of irradiation); GIIIa-(physiological solution and irradiation for 5 min); and GIIIb-(physiological solution and irradiation for 10 min); positive and negative control groups. Collections from root canals were made at time intervals of 21 days after contamination, immediately after treatment, and 7 days after treatment, and submitted to colony forming units per milliter (CFU mL-1) counts. The data were submitted to ANOVA and Tukey multiple comparison tests, at a level of significance of 5 %. In the immediate post-treatment collection, group GIa showed greater bacterial reduction in comparison with GIIa, GIIb, GIIIa, GIIIb, and positive control (P < 0.05). At 7 days post-treatment, GIa showed significant bacterial reduction only in comparison with GIIIa (P < 0.05). Curcumin as sensitizer was effective by 5 min LED irradiation but not by 10 min irradiation PDT using LED light, and curcumin as PS was not effective in eliminating E. faecalis. No difference was observed for periods of irradiation.

Estudo do efeito de cério como sensibilizador e ativador, em matrizes de difenilfosfinatos de lantânio, dopadas com európio e/ou térbio

This paper aims the preparation, characterization and study of luminescence, particularly as for the cerium ion action as activator or sensitizer, in diphenylphosphinate of lanthanum compounds trivalent ions cerium-, europium-, and/or terbium-doped. The following compounds were prepared and studied: i) La1-(x+y)CexEuy(DFF)3; ii) La1-(x+y)CexTby(DFF)3; iii) La1-(x+y+z)CexEuyTbz(DFF)3, with x = 10%, y = 5% e z = 5%. The diphenylphosphinate of lanthanum, Ln[(Ph2)PO2]3, are complexes obtained by the mixture of lanthanides chlorides with diphenylphosphinic acid, ethanol medium. These compounds make white powders, crystalline, insoluble in normal temperature and pressure, and are chemically and thermally stable. When doping with Ce3+, Eu3+ and/or Tb3+, the compounds present characteristic luminescence. Luminescent materials are made of a host matrix incorporated with few amounts of ions called activators, which are able to present luminescence after being excited by UV light or high energy radiation, and sensitizer ions, which have the role of absorbing excitation energy and transfer it to the activator, for it to emit luminescence radiation. The infrared vibrational spectroscopy indicates that the coordination occurs by the oxygens of phosphorile group with ΔνPO of about 40 cm-1 compared to the free ligand. The X Ray difractograms of compounds Eu- and/or Tb-doped are similar, but they present profile of diffraction different observed by Stucchi and col. In previous papers, indicated an influence of Ce in the crystalline phase formation of these matrices. In luminescence spectrums, the excitation that can be made by the levels of ligand in 273 nm, or cerium ion in area between 300 and 400 nm were observed. In the emission spectrum, with excitation in 273 nm, is possible to observe the emission of Ce3+ below 400 nm and the Eu3+ in 592, 611 and 617 nm, and the...as a sensitizer to.

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Two novel coordination polymers with the formula {[Ln(2)(2,5-tdc)(3)(dmso)(2)].H2O}(n) (Ln = Tb(III) for (1) and Dy(III) for (2)), (2,5-tdc(2-) = 2,5-thiophenedicarboxylate and dmso = dimethylsulfoxide) have been synthesized by the diffusion method and characterized by thermal analysis, vibrational spectroscopy and single crystal X-ray diffraction analysis. Structure analysis reveals that 2,5-tdc(2-) play a versatile role toward different lanthanide ions to form three-dimensional metal-organic frameworks (MOFs) in which the lanthanides ions are heptacoordinated. Photophysical properties were studied using excitation and emission spectra, where the photoluminescence data show the high emission intensity of the characteristic transitions D-5(4 ->) F-7(J) (J= 6, 5, 4 and 3) for (1) and (F9/2 -> HJ)-F-4-H-6 (J = 15/2, 13/2 and 11/2) for (2), indicating that 2,5-tdc(2-) is a good sensitizer. (C) 2012 Elsevier Ltd. All rights reserved.

Effect of photodynamic therapy with different formulations of methylene blue in teeth contaminated by Enterococcus faecalis

The aim of this study was to compare the disinfection of dentine using photodynamic therapy with methylene blue in different formulations. Thirty bovine teeth roots were autoclaved and incubated with a suspension of Enterococcus faecalis. The specimen were randomly divided into three groups: G1, the roots were filled with 10 mM methylene blue dissolved in water; G2, the roots were filled with 10 mM methylene blue dissolved in a mixture of glycerol: ethanol: water; G3, roots filled with 100 mM methylene blue dissolved in water. The groups were irradiated with a 660 nm diode laser with an output power of 100 mW for 4 min, energy density of 850 J/cm2 and after this procedure, the sensitizer was removed and microbial samples were collected from within the root canals. The samples were plated on mEnterococcus to count the colony-forming units (CFU/mL). The means were: Group 1=513×103, Group 2=1431×103 and Group 3=2.96×103. The statistical analysis detected higher disinfection achieved by G3 when compared with groups G1 and G2, and no significant difference between the groups G1 and G2 (P>0.05). The increase of the concentration of methylene blue dye achieved higher disinfection in photodynamic therapy.

Necrosis response to photodynamic therapy using light pulses in the femtosecond regime

One of the clinical limitations of the photodynamic therapy (PDT) is the reduced light penetration into biological tissues. Pulsed lasers may present advantages concerning photodynamic response when compared to continuous wave (CW) lasers operating under the same average power conditions. The aim of this study was to investigate PDT-induced response when using femtosecond laser (FSL) and a first-generation photosensitizer (Photogem) to evaluate the induced depth of necrosis. The in vitro photodegradation of the sensitizer was monitored during illumination either with CWor an FSL as an indirect measurement of the PDT response. Healthy liver of Wistar rats was used to evaluate the tissue response. The photosensitizer was endovenously injected and 30 min after, an energy dose of 150 Jcm-2 was delivered to the liver surface. We observed that the photodegradation rate evaluated via fluorescence spectroscopy was higher for the FSL illumination. The FSL-PDT produced a necrosis nearly twice as deep when compared to the CW-PDT. An increase of the tissue temperature during the application was measured and was not higher than 2.5 °C for the CW laser and not higher than 4.5 °C for the pulsed laser. FSL should be considered as an alternative in PDT applications for improving the results in the treatment of bulky tumors where higher light penetration is required.

Photo- and redox-active supramolecular systems containing metal complexes

The aim of this Ph.D. project has been the photophysical and photochemical characterization of new photo- and redox-active supramolecular systems. In particular we studied two different classes of compounds: metal complexes and dendrimers. Two different families of bis-cyclometalated neutral Ir(III) complexes are presented and their photophysical properties are discussed. The first family of complexes contains two 2-phenylpyridyl (ppy) or 2-(4,6-difluorophenyl)pyridyl (F2ppy) cyclometalated ligands and an ancillary ligand constituted by a phenol-oxazoline (phox), which can be substituted in the third position with a fluorine group (Fphox). In the second part of this study, we present another family of bis-cyclometalated Ir(III) complexes in which the ancillary ligand could be a chiral or an achiral bis-oxazoline (box). We report on their structural, electrochemical, photophysical, and photochemical properties. Complexes containing phox and Fphox ancillary ligands show blue luminescence with very high quantum yield, while complexes with box ligands do not show particularly interesting photophysical properties. Surprisingly these complexes give an unexpected photoreaction when irradiated with UV light in presence of dioxygen. This photoreaction originates a stable, strong blue emitting and particularly interesting photoproduct. Three successive generations of a family of polyethyleneglycol (PEG)-coated Pd(II) tetrabenzoporphyrin (PdTBP)-based dendritic nanoprobes are presented, and their ability to sensitize singlet oxygen and inflict cellular photodamage are discussed. It was found that the size of the dendrimer has practically no effect on the singlet oxygen sensitization efficiency, that approximate the unity, in spite of the strong attenuation of the triplet quenching rate with an increase in the dendrimer generation. Nevertheless, when compared against a commonly used singlet oxygen sensitizer, as Photofrin, the phosphorescent probes were found to be non-phototoxic. The lack of phototoxicity is presumably due to the inability of PEGylated probes to associate with cell surfaces and/or penetrate cellular membranes. The results suggest that protected phosphorescent probes can be safely used for oxygen measurements in biological systems in vivo. A new family of two photoswitchable (G0(Azo) and G1(Azo)) dendrimers with an azobenzene core, two cyclam units as coordination sites for metal ions, and luminescent naphthalene units at the periphery have been characterized and their coordination abilities have been studied. Because of their proximity, the various functional groups of the dendrimer may interact, so that the properties of the dendrimers are different from those exhibited by the separated functional units. Both the naphthalene fluorescence and the azobenzene photoisomerization can be observed in the dendrimer, but it has been shown that (i) the fluorescent excited state of the naphthalene units is substantially quenched by excimer and exciplex formation and by energy transfer to the azobenzene units, and (ii) in the latter case the fluorescence quenching is accompanied by the photosensitized isomerization of the trans → cis, and, with higher efficiency, the cis → trans reaction. Complexation of these dendrimers, both trans and cis isomers, with Zn(II) ions shows that complexes of 1:1 and 2:1 metal per dendrimer stoichiometry are formed showing different photophysical and photochemical properties compared to the corresponding free ligands. Practically unitary efficiency of the sensitized isomerization of trans → cis and cis → trans reaction is observed, as well as a slight increase in the naphthalene monomer emission. These results are consistent with the coordination of the cyclam amine units with Zn(II), which prevents exciplex formation. No indication of a concomitant coordination of both cyclam to a single metal ion has been obtained both for trans and cis isomer.