Influence of light and oxygen on the color stability of five calcium silicate-based materials.

INTRODUCTION: Difficult handling, long setting time, and potential discoloration are important drawbacks of white mineral trioxide aggregate (WMTA). The development of Biodentine, a recently developed calcium silicate-based material (CSM), has overcome some of these shortcomings; however, there are no available data on its color stability. A previous study showed that WMTA discolors under light irradiation in an oxygen-free environment. The present study evaluated the influence of light irradiation and oxygen on the color stability of 5 CSMs. METHODS: Fifteen samples of 5 CSMs (ProRoot WMTA, Angelus WMTA, White Portland Cement [PC], PC with bismuth oxide, and Biodentine) were divided into 5 groups. Each group was exposed to different oxygen and light conditions. A spectrophotometer was used to determine the color of each specimen at 0, 120 seconds, and 5 days. Data were analyzed by using analysis of variance and Tukey honestly significant difference test. RESULTS: The materials PC with bismuth oxide, Angelus WMTA, and ProRoot WMTA showed dark discoloration after light irradiation in an oxygen-free environment, which was statistically significantly different from Biodentine and PC. In groups that were exposed to no light irradiation or to an oxygen atmosphere, all materials showed color stability over time, and no significant differences were observed among them. PC and Biodentine maintained color stability in all conditions over time and showed no significant differences. CONCLUSIONS: The combination of light and anaerobic conditions (similar to those in clinical situations) results in differences in color of the tested CSMs during a period of 5 days, of which Biodentine and PC demonstrated color stability.

Photosensitized generation of singlet oxygen from rhenium(I) and iridium(III) complexes.

Photophysical properties in dilute acetonitrile solution are reported for a number of iridium(III) and rhenium(I) complexes. The nature of the lowest excited state of the complexes under investigation is either metal-to-ligand charge transfer ((3)MLCT) or a ligand centred ((3)LC) state. Rate constants, k(q), for quenching of the lowest excited states by molecular oxygen are in the range 1.5 x 10(8) to 1.4 x 10(10) M(-1) s(-1). Efficiency of singlet oxygen production, f(Delta)(T), following oxygen quenching of the lowest excited states of these complexes, are in the range of 0.27-1.00. The rate constants and the efficiency of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition between a non-charge transfer (nCT) and a CT deactivation channel. The balance between CT and nCT deactivation channels, which is described by the relative contribution p(CT) of CT induced deactivation, is discussed. The kinetic model is found to be successfully applied in the case of quenching of the excited triplet states of coordination compounds by oxygen in acetonitrile, as was proposed for the quenching of pi-pi* triplet states by oxygen.

Spectroscopy and photophysics of flavin-related compounds: 3-benzyl-lumiflavin.

Molecular structure, spectroscopic and photophysical data for the singlet state of 3-benzyl-lumiflavin in different solvents are presented. Theoretical studies concerning singlet-singlet and triplet-triplet excitation energies were carried out using time-dependent density functional theory (TD-DFT) calculations. These predictions are in good agreement with the experimental results, which reflect the solvent interactions. All the observable singlet-singlet transitions have pi-pi* character. The title compound appears to be an efficient sensitizer of the production of singlet oxygen (phi(Delta)= 0.53). The crystal structure of 3-benzyl-lumiflavin is also presented, along with its solid-state photophysical data.

Photolysis of chiral 1-pyrazolines to cyclopropanes: mechanism and stereospecificity.

The photodenitrogenation of chiral trisubstituted 1-pyrazolines has been studied by laser flash photolysis. These experiments have permitted the detection of two transients that have been assigned, for each pyrazoline, to the trimethylene-type diradical resultant from the extrusion of nitrogen (lifetime tau = 0.1-0.8 micros) and to the pyrazoline triplet (tau < 9 ns), respectively. The efficiency of the photosensitization process has been evaluated by determination of the corresponding quenching rate constant in each instance. Theoretical calculations support a mechanistic pathway involving a trimethylene radical as intermediate that rapidly evolves to the corresponding cyclopropane derivative. The cyclopropane ring-closure is predicted to be faster than rotation around the C-C bond, thus accounting for the observed stereospecificity.

Photophysics of alloxazines on cellulose.

We report the UV-Vis absorption, fluorescence and transient absorption spectra of selected methylalloxazines adsorbed on cellulose from a polar solvent. The ground-state properties of these probe molecules in the cellulose matrix are similar to those in polar protic solvents. Fluorescence decay data allowed identification of three emitting species for every molecule studied, excluding 1-methyllumichrome which lacks the capacity to rearrange into an isoalloxazinic form. The short-lived emission component was attributed to the neutral form of the molecule, and the two longer-lived components were assigned to the two distinct deprotonated monoanionic forms resulting from dissociation at the respective N(3) and N(1) nitrogen atoms. The two monoanions coexist due to their very similar pKa, values. Transient absorption experiments detected two species created by the laser pulse in these systems. The short-lived species was identified as the triplet excited state, and the long-lived species as the semireduced radical, formed by hydrogen atom or proton transfer from the glycosidic unit to the alloxazine carbonyl group.

Photochemistry of single wall carbon nanotubes embedded in a mesoporous silica matrix.

By embedding single wall carbon nanotubes in a mesoporous silica matrix (SWNT@SiO2) the photochemical properties have been measured upon laser excitation at 266 nm; the SWNT@SiO2 exhibits long-lived emission (lambda em = 400 nm, tau = 0.95 microsecond), transient absorption (lambda max = 390 nm, tau = 11 microseconds) and is able to generate singlet oxygen in D2O.