Visual detection of cysteine and homocysteine

The determination of cysteine and homocysteine levels is of great current interest for the monitoring of desease states. A new colorimetric method for the simultaneous detection of l-cysteine and l-homocysteine has been developed. A fluorescein derivative reacts with the above amino acids, producing their respective thiazolidines resulting in color changes. Interference from other amino acids and proteins is minimal.     

Design and characterization of libraries of molecular fragments for use in NMR screening against protein targets

We have designed four generations of a low molecular weight fragment library for use in NMR-based screening against protein targets. The library initially contained 723 fragments which were selected manually from the Available Chemicals Directory. A series of in silico filters and property calculations were developed to automate the selection process, allowing a larger database of 1.79 M available compounds to be searched for a further 357 compounds that were added to the library. A kinase binding pharmacophore was then derived to select 174 kinase-focused fragments. Finally, an additional 61 fragments were selected to increase the number of different pharmacophores represented within the library. All of the fragments added to the library passed quality checks to ensure they were suitable for the screening protocol, with appropriate solubility, purity, chemical stability, and unambiguous NMR spectrum. The successive generations of libraries have been characterized through analysis of structural properties (molecular weight, lipophilicity, polar surface area, number of rotatable bonds, and hydrogen-bonding potential) and by analyzing their pharmacophoric complexity. These calculations have been used to compare the fragment libraries with a drug-like reference set of compounds and a set of molecules that bind to protein active sites. In addition, an analysis of the overall results of screening the library against the ATP binding site of two protein targets (HSP90 and CDK2) reveals different patterns of fragment binding, demonstrating that the approach can find selective compounds that discriminate between related binding sites.     

Predicted rate enhancements of dephosphorylation in functional oximate comicelles

The rate enhancements of dephosphorylation of p-nitrophenyldiphenyl phosphate by comicelles of cetyltrimethylammonium bromide with a functional cosurfactant are due wholly to increased concentration of the nucleophile in the micelle.     

Time- and frequency-domain measurements of carrier lifetimes in GaN epilayers

Results on time-resolved study of GaN photoluminescence (PL) in a power density range from 0.5 mW/cm² under CW excitation by ultraviolet light emitting diode (UV LED) to 1 GW/cm² under pulsed excitation by YAG:Nd laser in the temperature range from 8 to 300 K are presented. Measurements of PL response in the frequency domain by using amplitude-modulated emission of a UV LED as well as time-resolved PL measurements using a streak camera and light-induced transient grating technique have been used in the study. Yellow luminescence (YL) intensity increases with increasing temperature up to 120 K and faster components in YL decay switch to slower components with increasing temperature under UV LED excitation. At low carrier densities, the trapping decreases the carrier lifetime below 250 ps, while the carrier lifetime in the same GaN sample under excitation ensuring saturation of the traps equals 2 ns.     

Macrocycle-Derived Functional Xanthenes and Progress Towards Concurrent Detection of Glucose and Fructose

The detection of saccharides in biological media is of great current importance for the monitoring of disease states. We have previously reported that solutions of boronic acid-functionalized macrocycles form acyclic oligomeric materials in situ. The oligomers contain fluorescent xanthene moieties. Current efforts are aimed at modulating the spectroscopic responses of these materials for the analysis of specific sugars. We describe conditions whereby the xanthene boronic acids exhibit high colorimetric fructose selectivity. In contrast, at physiological levels selective glucose monitoring can be achieved via fluorescence. Additionally, we describe a method which exhibits promise for detecting both glucose and fructose at dual wavelengths in the UV-Vis region. Mechanistic rationale for each of these findings is presented.     

Skin Microbiome Compositional Changes in Atopic Dermatitis Accompany Dead Sea Climatotherapy

Dead Sea climatotherapy (DSC) is a well‐established therapeutic modality for the treatment of several diseases, including atopic dermatitis. Skin microbiome studies have shown that skin microbiome diversity is anticorrelated with both atopic dermatitis severity and concurrent Staphylococcus aureus overgrowth. This study aimed to determine whether DSC induces skin microbiome changes concurrent with clinical improvements in atopic dermatitis. We sampled 35 atopic dermatitis patients and ten healthy controls on both the antecubital and popliteal fossa. High‐resolution microbial community profiling was attained by sequencing multiple regions of the 16S rRNA gene. Dysbiosis was observed in both lesional and nonlesional sites, which was partially attenuated following treatment. Severe AD skin underwent the most significant community shifts, and Staphylococcus epidermidis, Streptococcus mitis and Micrococcus luteus relative abundance were significantly affected by Dead Sea climatotherapy. Our study highlights the temporal shifts of the AD skin microbiome induced by Dead Sea climatotherapy and offers potential explanations for the success of climatotherapy on a variety of skin diseases, including AD.     

Ultrasound mediated green synthesis of rhodanine derivatives: Synthesis,chemical behavior,and antibacterial activity

A variety of rhodanine derivatives were synthesized via a three-component reaction of carbon disulfide, amines, and dialkyl acetylenedicarboxylate in polyethylene glycol under conventional stirring or ultrasound irradiation. The sonochemical-assisted procedure provides an improved and accelerated conversion when compared to the conventional reaction, with increased rate of reaction and quality of product obtained. The product formed, 2a, could be readily converted to bis-rhodanine under microwave conditions. Moreover, the pyranothiazoles 9a,b were prepared from the corresponding rhodanines 2a,b and malononitrile. Fifteen compounds were screened for their antibacterial activities against nine human, animal and plant pathogenic Gram-positive and Gram-negative bacteria using the agar well diffusion method. Out of these derivatives, compounds 2g and 2h were the most effective against all tested bacteria.     

Appraisal of through-bond and through-space substituent effects via molecular electrostatic potential topography

Through-bond (TB) and through-space (TS) substituent effects in substituted alkyl, alkenyl, and alkynyl arenes are quantified separately using molecular electrostatic potential (MESP) topographical analysis. The deepest MESP point over the aromatic ring (V(min)) is considered as a probe for monitoring these effects for a variety of substituents. In the case of substituted alkyl chains, the TS effect (79.6%) clearly dominates the TB effect, whereas in the unsaturated analogues the TB effect (～55%) overrides the TS effect.     

Surface morphology studies on sublimation grown GaN by atomic force microscopy

Bulk single crystals and selectively grown gallium nitride (GaN) have been obtained using the sublimation technique. Crystals of size about 2–3 mm in length and 0.8–1.0 mm in width have been grown successfully. Atomic force microscopy has been employed to analyze the surface morphology of the as-grown samples to understand the growth mechanism. In free standing bulk GaN single crystals, two-dimensional growth is dominated by step growth mechanism. However, in the selective growth of GaN by sublimation, spiral growth originating from screw dislocation dominates.