Spectrophotometric and spectrofluorimetric studies of novel heterocyclic Schiff base dyes

Novel heterocyclic Schiff base dyes were prepared by the reaction of salicylaldehyde/2-Hydroxy-1-naphthaldehyde with different heterocyclic amines. Results of the newly synthesized compounds established by FT-IR, ¹H-NMR, ¹³C-NMR and GC–MS spectroscopic experiments were consistent with their chemical structures. Resulted heterocyclic Schiff base dyes were found to be pure from data obtained by the elemental analysis. In addition, spectrophotometric and spectrofluorimetric studies showed that these dyes were good absorbent and fluorescent. Fluorescence polarity study data revealed that some of these compounds were sensitive to the polarity of the microenvironment provided by different solvents. Time-based fluorescence steady-state measurements also showed that these heterocyclic Schiff base dyes have high photostability against photobleaching.     

Fluorescence energy transfer-sensitized photobleaching of a fluorescent label as a tool to study donor-acceptor distance distributions and dynamics in protein assemblies: studies of a complex of biotinylated IgM with streptavidin and aggregates of concanavalin A

A photokinetic method of detection of fluorescence resonance energy transfer (FRET) between special fluorescent labels is applied to study time-averaged spatial distribution of labeled proteins in protein assemblies. Prolonged irradiation of a sample at the absorption maximum of the energy donor initiates FRET-sensitized fluorescence photobleaching of the energy acceptor label, which was monitored by steady-state fluorimetric measurements. Kinetics of the acceptor photobleaching and kinetics of decreasing the efficiency of FRET from donors to unbleached acceptors were determined. The FRET efficiency was found from measuring sensitization of acceptor fluorescence. Analysis of the photokinetic data permits to estimate the time-averaged distribution of acceptors on donor-acceptor distances in the range of characteristic distances of FRET. Dynamic processes influencing donor-acceptor distances can be also investigated by the method. Application of the method is demonstrated by the studies of a complex of biotinylated IgM with streptavidin and aggregates composed of concanavalin A and sodium dodecyl sulphate. A new thiadicarbocyanine dye was used as the acceptor label. R-phycoerythrin and tetramethylrhodamine isothiocyanate were the donor labels. In the IgM-streptavidin complex, 16% of acceptors most contributed to FRET provided 90% of FRET efficiency, whereas acceptors made about the same time-averaged contribution to FRET in the concanavalin A aggregates.     

Photocatalytic bleaching of p-nitrosodimethylaniline in TiO2 aqueous suspensions: A kinetic treatment involving some primary events photoinduced on the particle surface

The photocatalytic bleaching of p-nitrosodimethylaniline (P) has been investigated in aqueous suspensions of TiO₂. It was found that both charge carriers (hole and electron) were reactive to P to result in a bleaching. The roles of O₂ and several hole scavengers (HCOO⁻, EDTA, I⁻) have also been examined. A reaction mechanism has been proposed with consideration of several primary processes photoinduced on TiO₂ surface. The results of the kinetic analysis fit fairly well to those of the experiments. The rate constant (k^h_p) of the reaction between P and the adsorbed hydroxyl radical was estimated to be in the order 10¹⁰ M⁻¹ s⁻¹, which is in good agreement with that obtained from the homogeneous reaction of P with free OH radicals. Of particular interest is the pH dependence of the photobleaching rate. Around both pK_a of P and pH_ZPC of TiO₂, the photobleaching of P was steeply enhanced. This can be reasonably attributed to the mutual interaction (repulsion versus attraction) between P and TiO₂ particles in different pH ranges.     

Photoinduced absorption edge shift of As20Se60Tl20 films

As₂₀Se₆₀Tl₂₀ bulk material was prepared firstly then thermal evaporation method was used to prepare As₂₀Se₆₀Tl₂₀ films. Illumination effect at room temperature for the mentioned films has been studied within the homogeneous glass-forming region. The prepared film samples were amorphous, this is depicted by X-ray chart. Optical properties have been studied using spectrophotometric measurements. The absorption edge was shifted to shorter wavelengths due to light exposure or photobleaching effect. It was found that the extinction coefficient and the optical band gap have opposite character after illumination.     

Fluorescence Recovery Under Decaying Photobleaching Irradiation: Concept and Experiment

A novel modification of photobleaching method for measurement of lateral diffusion is developed. In this approach fluorescence recovery kinetics is measured under decaying photobleaching irradiation, termed as fluorescence recovery under decaying photobleaching (FRDP). The time evolution of fluorescence intensity normalized to input irradiation starts from the photobleaching kinetics and transforms into the kinetics of fluorescence recovery at a later stage resulting in appearance of minimum. The analytical solution for the kinetics of fluorescence for Gaussian lineshape of laser beam and hyperbolic decay of irradiation in the first order approximation on bleaching rate was obtained. The accuracy of the analytical function was evaluated with exact numerical solution computed with finite differentiates method. The FRDP method was successfully applied to fluorescein solution in the glycerol/water mixture (80%) under various experimental settings using home-made experimental set-up. The FRDP approach demonstrated 25–30 fold enhancement in signal intensity over classical fluorescence recovery after photobleaching (FRAP) method at 3–5 fold increase in total irradiation. Among other advantages of the FRDP is the opportunity to perform measurements on varying time scales under constant size of the bleaching spot, including “safe” long time measurements. The potential extra advantage of FRDP method for analysis of complex diffusion in the biological system is discussed.     

Spectroscopic studies of tin ethyl etiopurpurin in homogeneous and heterogeneous systems

Tin ethyl etiopurpurin is a promising second generation photosensitizer for photodynamic treatment of cancer. This compound is only poorly soluble in aqueous media and, therefore, needs a delivery system for administration to animals. Successful tumor eradication has previously been reported, following light exposure of rats previously administered with the purpurin formulated as a Cremophor El emulsion, in dipalmitoyl—phosphatidyl—choline liposomes or with gamma cyclodextrins. In this paper, we describe some absorbance and fluorescence studies of tin ethyl etiopurpurin in homogeneous and heterogeneous systems. In general, absorption and emission maxima were found to be red shifted as the environment changed from polar to non-polar. The viscosity and dielectric constant of the medium affected the purpurin fluorescence intensity. The liposome preparations were characterized by particle size determination, differential scanning calorimetry and by sensitizer fluorescence quenching studies. Photobleaching studies also showed variation owing to changes in the environment in which the dye was located.     

The efficacy of photostabilizers on the color change of wood filled plastic composites

In this study, we compared the performance of different hindered amine light stabilizers and ultraviolet absorbers as photostabilizers of wood plastic composites (WPC). We showed how their functional groups and molecular weights influence the photostabilization of WPC subjected to natural weathering for 2000 h. The changes were followed using color measurements and FTIR spectroscopy which provided insight into the photodegradation mechanism of weathered WPC.The results indicate that weathering causes color fading and changes in yellowing. We propose that WPC undergo two competing redox reactions upon UV exposure. The first is the oxidation of lignin which leads to the formation of paraquinone chromophoric structures which is dominant in the first 250 h of exposure. The second is the reduction of the paraquinone structures to hydroquinones which leads to photobleaching.High molecular weight diester HALS were found to be the most effective in controlling long term fading and yellowing changes. Furthermore, the addition of a benzotriazole ultraviolet absorber shows great synergism in controlling fading when added to a diester HALS.     

厦门湾有色溶解有机物光漂白的三维荧光光谱研究

利用荧光激发-发射矩阵光谱(excitation-emission matrix spectroscopy,EEMs)研究了厦门湾九龙江河口中、低盐度区表层水样中有色溶解有机物在秋季天然太阳辐照下的光化学漂白。结果表明,光漂白未引起水样中类腐殖质(C, A, M)和类蛋白质(T,B)荧光峰位置的移动。5个峰的荧光强度均随辐照时间的增加而减少,其中低盐度水样的降低幅度更大,并以指示陆源河流输入的特征荧光峰C的光漂白程度最大。根据漂白速率可将各荧光团区分出易漂白和难漂白两类组分。光漂白导致T、C峰及A、C峰之间的荧光强度比值增加,说明光漂白可引起海水中溶解有机物性质的明显改变,并且也是近海类蛋白质荧光相对类腐殖质荧光占优势的一个重要控制因素。研究结果对于探究陆源有机物在近海的转化及去除过程以及海洋光学有一定的参考价值。