Ultrafast proton transfer of three novel quinone cyanine photoacids

Steady-state and time-resolved emission techniques were used to study the photoprotolytic properties of three recently synthesized strong quinone cyanine photoacids (QCy7 and its sulfonated derivatives). The rate coefficient of the excited-state proton transfer (ESPT), k(PT), of the three dyes is roughly 1.5 × 10(12) s(-1), a high value that is comparable to the solvation dynamics rate of large polar organic molecules in H(2)O and D(2)O. It is twice as fast as the proton transfer rate between two adjacent water molecules in liquid water. We found that, as expected, two of the sulfonated photoacids geminately recombines with the proton at an elevated rate. The accelerated geminate recombination process of the sulfonated derivatives is different from a simple diffusion process of protons. The ESPT rate coefficient of these molecules is the highest recorded thus far.     

Ultrafast excited-state intermolecular proton transfer of cyanine fluorochrome dyes

Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D(2)O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, k(PT), of QCy7 excited from its protonated form, ROH, is ~1.5 × 10(12) s(-1). This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τ(S) = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ~1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ~3, but comparable to the KIE on proton diffusion in water of ~1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.     

Injection level dependence of the gain, refractive index variation, and alpha (α) parameter in broad-area InGaAs deep quantum-well lasers

In this study, a single, simple and an accurate computer-aided design model is developed in order to obtain the injection level dependence of the critical quantities of broad-area (with a width of 50 μm or more) InGaAs deep quantum-well (QW) lasers. Each of these quantities (gain, refractive index variation, and alpha (α) parameter) requires lengthy mathematical calculations with the use of different theories, assumptions, approximations, and estimations of some parameter values. The model is based on artificial neural network (ANN) approach that the total computational time is in the order of microseconds for the whole quantities in order to get their accurate values. The results are in very good agreement with the previously obtained results from an InGaAs deep QW laser sample.     

Efficacy of Low‐Dose Ultraviolet A‐1 Phototherapy for Parapsoriasis/Early‐Stage Mycosis Fungoides

Mycosis fungoides (MF) and parapsoriasis (PP) are major dermatologic conditions for which phototherapy continues to be a successful and valuable treatment option. UVA‐1 phototherapy is effective in the management of cutaneous T‐cell mediated diseases. The aim of the study was to evaluate the efficacy and safety of low‐dose UVA‐1 phototherapy for the management of PP/early‐stage MF. A total of 30 patients, diagnosed with MF (n:19) or PP (n:11) were enrolled to the study. All patients were managed with low‐dose UVA‐1 (20 or 30 J cm^?2). Response was assessed clinically and immunohistochemically. UVA‐1 treatment led to clinical and histological complete remission (CR) in 11 of 19 MF patients (57.9%), partial remission (PR) in three of 19 (15.8%), after a mean cumulative dose of 1665 (range, 860–3120) J cm^?2 and mean number of 73 exposure (range, 43–107) sessions. Five patients with PP (45.5%) showed CR, and PR was observed in six patients with PP (54.5%) after a mean cumulative dose of 1723 (range, 1060–3030) J cm^?2 and mean number of 74 exposure (range, 53–101) sessions. We conclude that low‐dose UVA‐1 therapy seems to be an effective, safe, and well‐tolerated treatment option for patients with PP/early‐stage MF.     

Structural alterations and thermal behaviour of mechanically activated alunite ore

Alunite, a potassium alum, was activated mechanically in a planetary ball mill, and the effects of mechanical activation on the structure of alunite have been studied by particle size analysis, scanning electron microscopy, X-ray diffraction and the Fourier transform infrared spectroscopy. The results show that the activation procedure led to amorphisation and structural disordering in the alunite structure. Thermal decompositions of both non-activated and activated alunite samples have been studied by thermogravimetry (TG) and differential thermal analysis (DTA). In non-activated alunite, the dehydration reaction starts after 500 °C. On the contrary, the dehydration of mechanically activated alunite was started after 100 °C. It is observed by X-ray diffraction analysis and thermal analysis that dehydration and desulphation temperatures of alunite decreased with mechanical activation, owing to amorphisation and structural disordering in alunite.     

Numerical study of Sivashinsky equation using a splitting scheme based on Crank‐Nicolson method

The mathematical modeling of a planar solid‐liquid interface in the solidification of a dilute binary alloy is formulating by one of nonintegrable, nonlinear evolution equation known as Sivashinsky equation. In the first part of this paper, the mathematical modeling of Sivashinsky equation is briefly discussed. Since, the exact solutions of this equation is yet unknown, obtaining its numerical solution plays an important role to simulate its behavior. Therefore, in the second part, a second‐order splitting finite difference scheme, based on Crank‐Nicolson method, is investigated to approximate the solution of the Sivashinsky equation with homogeneous boundary conditions. We prove the solvability of the present scheme and establish the error estimate of the numerical scheme.     

A unique paradigm for a Turn-ON near-infrared cyanine-based probe: noninvasive intravital optical imaging of hydrogen peroxide

The development of highly sensitive fluorescent probes in combination with innovative optical techniques is a promising strategy for intravital noninvasive quantitative imaging. Cyanine fluorochromes belong to a superfamily of dyes that have attracted substantial attention in probe design for molecular imaging. We have developed a novel paradigm to introduce a Turn-ON mechanism in cyanine molecules, based on a distinctive change in their π-electrons system. Our new cyanine fluorochrome is synthesized through a simple two-step procedure and has an unprecedented high fluorescence quantum yield of 16% and large extinction coefficient of 52,000 M(-1)cm(-1). The synthetic strategy allows one to prepare probes for various analytes by introducing a specific triggering group on the probe molecule. The probe was equipped with a corresponding trigger and demonstrated efficient imaging of endogenous hydrogen peroxide, produced in an acute lipopolysaccharide-induced inflammation model in mice. This approach provides, for the first time, an available methodology to prepare modular molecular Turn-ON probes that can release an active cyanine fluorophore upon reaction with specific analyte.     

Determination of pharmaceutically related compounds by suppressed ion chromatography: I. Effects of organic solvent on suppressor performance

This overall study aims to investigate gradient elution ion-exchange chromatography of pharmaceutically relevant compounds using universal nebulisation detectors, such as evaporative light scattering detection (ELSD). Addition of organic solvents to the eluent is necessary to minimise hydrophobic adsorption on the polymeric stationary phase and improve solubility of analytes. It is also necessary to de-salt the eluent prior to detection, and in this work, ion chromatography suppressors were used for this step. Such suppressors have been designed for aqueous eluents, so the purpose of the present study was to investigate the effects of methanol and acetonitrile on suppressor performance. Chemical and electrolytic suppressors were evaluated for baseline drift, noise and efficiency of suppression using aqueous/organic eluents containing up to 40% (v/v) methanol or acetonitrile. Chemical suppression of aqueous/organic eluents showed minimal noise levels, uniform low baseline and low gradient drift. Electrolytic suppression gave good performance, but with higher baseline conductivity levels and baseline drift than chemical suppression. The elevated baseline was found not to be caused by incomplete suppression of the eluent, but was attributed to chemical reactions involving the organic solvents and facilitated by high electric currents and heat generation. It was demonstrated that suppressed ion-exchange separation using a complex KOH elution profile could be coupled with ELSD, with the suppressor effectively de-salting the eluent, producing a stable baseline. Finally, complementary separation selectivity was demonstrated using a set of pharmaceutically related organic acids separated by reversed-phase and ion-exchange methods.