Naphthoxazole‐Based Singlet Oxygen Fluorescent Probes

In this study, we report the synthesis and photochemical behavior of a new family of photoactive compounds to assess its potential as singlet oxygen (¹O₂) probes. The candidate dyads are composed by a ¹O₂ trap plus a naphthoxazole moiety linked directly or through an unsaturated bond to the oxazole ring. In the native state, the inherent great fluorescence of the naphthoxazole moiety is quenched; but in the presence of ¹O₂, generated by the addition and appropriate irradiation of an external photosensitizer, a photooxidation reaction occurs leading to the formation of a new chemical entity whose fluorescence is two orders of magnitude higher than that of the initial compound, at the optimal selected wavelength. The presented dyads outperform the commonly used indirect fluorescent ¹O₂ probes in terms of fluorescence enhancement maintaining the required specificity for ¹O₂ detection in solution.     

Microbial Degradation,Spectral analysis and Toxicological Assessment of Malachite Green Dye by Streptomyces exfoliatus

Malachite green (MG) dye is a common environmental pollutant that threatens human health and the integrity of the Earth’s ecosystem. The aim of this study was to investigate the potential biodegradation of MG dye by actinomycetes species isolated from planted soil near an industrial water effluent in Cairo, Egypt. The Streptomyces isolate St 45 was selected according to its high efficiency for laccase production. It was identified as S. exfoliatus based on phenotype and 16S rRNA molecular analysis and was deposited in the NCBI GenBank with the gene accession number {"type":"entrez-nucleotide","attrs":{"text":"OL720220","term_id":"2159919206","term_text":"OL720220"}}OL720220. Its growth kinetics were studied during an incubation time of 144 h, during which the growth rate was 0.4232 (µ/h), the duplication time (td) was 1.64 d, and multiplication rate (MR) was 0.61 h, with an MG decolorization value of 96% after 120 h of incubation at 25 °C. Eleven physical and nutritional factors (mannitol, frying oil waste, MgSO₄, NH₄NO₃, NH₄Cl, dye concentration, pH, agitation, temperature, inoculum size, and incubation time) were screened for significance in the biodegradation of MG by S. exfoliatus using PBD. Out of the eleven factors screened in PBD, five (dye concentration, frying oil waste, MgSO₄, inoculum size, and pH) were shown to be significant in the decolorization process. Central composite design (CCD) was applied to optimize the biodegradation of MG. Maximum decolorization was attained using the following optimal conditions: food oil waste, 7.5 mL/L; MgSO₄, 0.35 g/L; dye concentration, 0.04 g/L; pH, 4.0; and inoculum size, 12.5%. The products from the degradation of MG by S. exfoliatus were characterized using high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). The results revealed the presence of several compounds, including leuco-malachite green, di(tert-butyl)(2-phenylethoxy) silane, 1,3-benzenedicarboxylic acid, bis(2-ethylhexyl) ester, 1,4-benzenedicarboxylic acid, bis(2-ethylhexyl) ester, 1,2-benzenedicarboxylic acid, di-n-octyl phthalate, and 1,2-benzenedicarboxylic acid, dioctyl ester. Moreover, the phytotoxicity, microbial toxicity, and cytotoxicity tests confirmed that the byproducts of MG degradation were not toxic to plants, microbes, or human cells. The results of this work implicate S. exfoliatus as a novel strain for MG biodegradation in different environments.     

Xylanase production by Penicillium canescens 10–10c in solid-state fermentation

Filamentous fungi have been widely used to produce hydrolytic enzymes for industrial applications, including xylanases, whose levels in fungi are generally much higher than those in yeast and bacteria. We evaluated the influence of carbon sources, nitrogen sources, and moisture content on xylanase production by Penicillium canescens 10–10c in solid-state fermentation. Among agricultural wastes tested (wheat bran, untreated wheat straw, treated wheat straw, beet pulp, and soja meal), untreated wheat straw gave the highest production of xylanase. Optimal initial moisture content for xylanase production was 83%. The addition of 0.4 g of xylan or easily metabolizable sugar, such as glucose and xylose, at a concentration of 2% to wheat straw enhanced xylanase production. In solid-state fermentation, even at high concentrations of glucose or xylose (10%), catabolic repression was minimized compared to the effect observed in liquid culture. Yeast extract was the best nitrogen source among the nitrogen sources investigated: peptone, ammonium nitrate, sodium nitrate, ammonium chloride, and ammonium sulfate. A combination of yeast extract and peptone as nitrogen sources led to the best xylanase production.     

First carbonyl metallo immunoassay in the environmental area: application to the herbicide chlortoluron

We report a new, non‐isotopic, immunoassay (CMIA) for chlortoluron, a pesticide of the phenylurea family. The novel feature of this assay is the use of metal carbonyl complexes as tracers and Fourier‐transform infrared (FT‐IR) spectroscopy as the detection method. We describe the synthesis of three tracers, derivatives of chlortoluron with an attached cyclopentadienyl manganese tricarbonyl moiety. Quantitative analysis of these tracers, by FT‐IR spectroscopy was performed by simple measurement of the absorbance peak at 2033 cm^?1, characteristic of the ν_CO of the metal‐carbonyl unit. Immunoassays were carried out using the IgG fraction of rabbit antiserum. Standard curves obtained by CMIA for the three tracers showed the feasibility of this technique for chlortoluron assay. However, the IC₅₀ and IC₉₀ values obtained with the three tracers varied widely, with the long‐chain tracer 12 giving the most sensitive assay for chlortoluron, with an IC₅₀ value of 50 pmol (21 µg l^?1) and an IC₉₀ of 6.5 pmol (2.7 µg l^?1). Copyright © 2002 John Wiley & Sons, Ltd.     

Viscous dissipation of Rankine vortex profile in zero meridional flow

An analytical solution is given for a time-decay Rankine vortex profile due to viscous effects. The vortex filament is assumed to be isolated, strong, concentrated and having zero-meridional flow (i.e. radial and axial velocities are equal to zero). Zero-meridional renders the governing equations for an unsteady, incompressible and axisymmetric vortex in a simple form. Based on the tangential momentum equation, the spatial-temporal distributions of the swirl velocity are given in terms of Fourier-Bessel series by using separation of variables technique. A general formula is derived by total differentiation of the swirl velocity with respect to time, depicting the viscous dissipation for Oseen and Taylor-like vortex profiles. This analysis is validated by comparison with previous experimental data.     

On the Brownian-directed polymer in a Gaussian random environment

In this paper, we introduce a model of Brownian polymer in a continuous random environment. The asymptotic behavior of the partition function associated to this polymer measure is studied, and we are able to separate a weak and strong disorder regime under some reasonable assumptions on the spatial covariance of the environment. Some further developments, concerning some concentration inequalities for the partition function, are given for the weak disorder regime.     

Investigation of the mechanism of the cell wall DD-carboxypeptidase reaction of penicillin-binding protein 5 of Escherichia coli by quantum mechanics/molecular mechanics calculations

Penicillin-binding protein 5 (PBP 5) of Escherichia coli hydrolyzes the terminal D-Ala-D-Ala peptide bond of the stem peptides of the cell wall peptidoglycan. The mechanism of PBP 5 catalysis of amide bond hydrolysis is initial acylation of an active site serine by the peptide substrate, followed by hydrolytic deacylation of this acyl-enzyme intermediate to complete the turnover. The microscopic events of both the acylation and deacylation half-reactions have not been studied. This absence is addressed here by the use of explicit-solvent molecular dynamics simulations and ONIOM quantum mechanics/molecular mechanics (QM/MM) calculations. The potential-energy surface for the acylation reaction, based on MP2/6-31+G(d) calculations, reveals that Lys47 acts as the general base for proton abstraction from Ser44 in the serine acylation step. A discrete potential-energy minimum for the tetrahedral species is not found. The absence of such a minimum implies a conformational change in the transition state, concomitant with serine addition to the amide carbonyl, so as to enable the nitrogen atom of the scissile bond to accept the proton that is necessary for progression to the acyl-enzyme intermediate. Molecular dynamics simulations indicate that transiently protonated Lys47 is the proton donor in tetrahedral intermediate collapse to the acyl-enzyme species. Two pathways for this proton transfer are observed. One is the direct migration of a proton from Lys47. The second pathway is proton transfer via an intermediary water molecule. Although the energy barriers for the two pathways are similar, more conformers sample the latter pathway. The same water molecule that mediates the Lys47 proton transfer to the nitrogen of the departing D-Ala is well positioned, with respect to the Lys47 amine, to act as the hydrolytic water in the deacylation step. Deacylation occurs with the formation of a tetrahedral intermediate over a 24 kcal x mol(-1) barrier. This barrier is approximately 2 kcal x mol(-1) greater than the barrier (22 kcal x mol(-1)) for the formation of the tetrahedral species in acylation. The potential-energy surface for the collapse of the deacylation tetrahedral species gives a 24 kcal x mol(-1) higher energy species for the product, signifying that the complex would readily reorganize and pave the way for the expulsion of the product of the reaction from the active site and the regeneration of the catalyst. These computational data dovetail with the knowledge on the reaction from experimental approaches.     

Simultaneous determination of piracetam and vincamine by spectrophotometric and high-performance liquid chromatographic methods

A mixture of piracetam and vincamine was determined by 3 different methods. The first was the determination of piracetam and vincamine using the ratio-spectra first-derivative (DD1) spectrophotometric technique at 209 and 293 nm in concentration ranges of 10-45 and 2-14 microg/mL with mean recoveries of 99.22 +/- 0.72 and 99.67 +/- 0.79%, respectively. The second method was based on the resolution of the 2 components by bivariate calibration depending on a mathematic algorithm that provides simplicity and rapidity. The method depended on quantitative evaluation of the absorbencies at 210 and 225 nm in concentration ranges of 5-45 and 2-14 microg/mL, with mean recoveries of 100.33 +/- 0.54 and 100.44 +/- 0.98% for piracetam and vincamine, respectively. The third method was reversed-phase liquid chromatography using 0.05 M potassium dihydrogen phosphate-methanol (50 + 50, v/v) as the mobile phase, with the pH adjusted to 3.5 with phosphoric acid. The eluent was monitored at 215 nm in concentration ranges of 5-100 and 2-200 microg/mL, with mean recoveries of 99.62 +/- 0.67 and 99.32 +/- 0.85% for piracetam and vincamine, respectively. The suggested procedures were checked using laboratory-prepared mixtures and were successfully applied for the analysis of their pharmaceutical preparation. The methods retained their accuracy and precision when applying the standard addition technique. The results obtained by applying the proposed methods were statistically analyzed and compared with those obtained by the manufacturer's method.     

LOWER BOUNDS FOR SUP＋INF AND SUP＊INF AND AN EXTENSION OF CHEN-LIN RESULT IN DIMENSION 3

We give two results about Harnack type inequalities. First, on Riemannian surfaces, we have an estimate of type sup ＋ inf. The second result concern the solutions of prescribed scalar curvature equation on the unit ball of Rn with Dirichlet condition. Next, we give an inequality of type （supK ^u）^2s-1 × infπu ≤ c for positive solutions of △u = V u^5 on Ω belong toR^3, where K is a compact set of Ω and V is s-Holderian, s ∈] - 1/2, 1]. For the case s = 1/2 and Ω = S3, we prove that, if minΩ u 〉 m 〉 0 （for some particular constant m 〉 0）, and the H¨olderian constant A of V tends to 0 （in certain meaning）, we have the uniform boundedness of the supremum of the solutions of the previous equation on any compact set of Ω.