Influence of entropy-fluctuation on the Rayleigh spectrum

We discuss the light scattering cross section due to entropy-fluctuation on the region of the central peak of the spectrum. A back-scattering oblique incidence geometry is used in our theoretical calculations which are based on the linear response function approach. Our results show that the power spectrum varies significantly with the incident angle and frequency and so does the light scattering cross section. The results are illustrated with numerical calculations for silicon.Work partially supported by the Brazilian Research Agencies CNPq and FINEP     

Unimolecular reactions on formaldehyde S0 PES

The competitive unimolecular reactions of formaldehyde, H₂CO→H₂+CO; H₂CO→trans-HCOH and H₂CO→H+HCO, were comparatively studied under the direct dynamics formalism, using Density functional and ab initio levels of theory. In addition, the geometric isomerization trans-HCOH→cis-HCOH was evaluated. Calculated reaction path properties were used in the determination of Rice–Ramsperger–Kassel–Marcus microcanonical rate coefficients. The reaction dynamics was evaluated for each individual process based on the nuclear displacements in the reaction path and normal coordinate analysis. Our results found are in very good agreement with experimental barrier heights and quantum yields trends.     

Preparation,Characterization, Biological Activity and 3D Molecular Modeling of Mn(II), Co(II), Ni(II), Cu(II), Pd(II) and Ru(III) Complexes of Some Sulfadrug Schiff Bases

Mn(II), Co(II), Ni(II), Cu(II), Pd(II) and Ru(III) complexes of Schiff bases derived from the condensation of sulfaguanidine with 2,4‐dihydroxy benzaldehyde ( HL1 ), 2‐hydroxy‐1‐naphthaldehyde ( HL2 ) and salicylaldehyde ( HL3 ) have been synthesized. The structures of the prepared metal complexes were proposed based on elemental analysis, molar conductance, thermal analysis (TGA, DSC and DTG), magnetic susceptibility measurements and spectroscopic techniques (IR, UV‐Vis, and ESR). In all complexes, the ligand bonds to the metal ion through the azomethine nitrogen and α‐hydroxy oxygen atoms. The structures of Pd(II) complex 8 and Ru(III) complex 9 were found to be polynuclear. Two kinds of stereochemical geometries; distorted tetrahedral and distorted square pyramidal, have been realized for the Cu(II) complexes based on the results of UV‐Vis, magnetic susceptibility and ESR spectra whereas octahedral geometry was predicted for Co(II), Mn(II) and Ru(III) complexes. Ni(II) complexes were predicted to be square planar and tetrahedral and Pd(II) complexes were found to be square planar. The antimicrobial activity of the ligands and their metal complexes was also investigated against the gram‐positive bacteria Staphylococcus aures and Bacillus subtilis and gram‐negative bacteria, Escherichia coli and Pesudomonas aeruginosa, by using the agar dilution method. Chloramphenicol was used as standard compound. The obtained data revealed that the metal complexes are more or less, active than the parent ligand and standard. The X‐ray crystal structure of HL3 has been also reported.     

Development and validation of a sensitive UHPLC‐MS/MS method for the simultaneous analysis of tramadol,dextromethorphan chlorpheniramine and their major metabolites in human plasma in forensic context: application to pharmacokinetics

The prerequisites for forensic confirmatory analysis by LC/MS/MS with respect to European Union guidelines are chromatographic separation, a minimum number of two MS/MS transitions to obtain the required identification points and predefined thresholds for the variability of the relative intensities of the MS/MS transitions (MRM transitions) in samples and reference standards. In the present study, a fast, sensitive and robust method to quantify tramadol, chlorpheniramine, dextromethorphan and their major metabolites, O‐desmethyltramadol, dsmethyl‐chlorpheniramine and dextrophan, respectively, in human plasma using ibuprofen as internal standard (IS) is described. The analytes and the IS were extracted from plasma by a liquid–liquid extraction method using ethyl acetate–diethyl‐ether (1:1). Extracted samples were analyzed by ultra‐high‐performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (UHPLC‐ESI‐MS/MS). Chromatographic separation was performed by pumping the mobile phase containing acetonitrile, water and formic acid (89.2:11.7:0.1) for 2.0 min at a flow rate of 0.25 μL/min into a Hypersil‐Gold C₁₈ column, 20 × 2.0 mm (1.9 µm) from Thermoscientific, New York, USA. The calibration curve was linear for the six analytes. The intraday precision (RSD) and accuracy (RE) of the method were 3–9.8 and ?1.7–4.5%, respectively. The analytical procedure herein described was used to assess the pharmacokinetics of the analytes in 24 healthy volunteers after a single oral dose containing 50 mg of tramadol hydrochloride, 3 mg chlorpheniramine maleate and 15 mg of dextromethorphan hydrobromide. Copyright © 2014 John Wiley & Sons, Ltd.     

Microwave Irradiation: Alternative Heating Process for the Synthesis of Biologically Applicable Chromones,Quinolones, and Their Precursors

Microwave irradiation has become a popular heating technique in organic synthesis, mainly due to its short reaction times, solventless reactions, and, sometimes, higher yields. Additionally, microwave irradiation lowers energy consumption and, consequently, is ideal for optimization processes. Moreover, there is evidence that microwave irradiation can improve the regioselectivity and stereoselectivity aspects of vital importance in synthesizing bioactive compounds. These crucial features of microwave irradiation contribute to its inclusion in green chemistry procedures. Since 2003, the use of microwave-assisted organic synthesis has become common in our laboratory, making our group one of the first Portuguese research groups to implement this heating source in organic synthesis. Our achievements in the transformation of heterocyclic compounds, such as (E/Z)-3-styryl-4H-chromen-4-ones, (E)-3-(2-hydroxyphenyl)-4-styryl-1H-pyrazole, (E)-2-(4-arylbut-1-en-3-yn-1-yl)-4H-chromen-4-ones, or (E)-2-[2-(5-aryl-2-methyl-2H-1,2,3-triazol-4-yl)vinyl]-4H-chromen-4-ones, will be discussed in this review, highlighting the benefits of microwave irradiation use in organic synthesis.     

Recombinant Thaumatin-Like Protein (rTLP) and Chitinase (rCHI) from Vitis vinifera as Models for Wine Haze Formation

Cross-linking net aggregates of thermolabile thaumatin-like proteins (TLPs) and chitinases (CHIs) are the primary source of haze in white wines. Although bentonite fining is still routinely used in winemaking, alternative methods to selectively remove haze proteins without affecting wine organoleptic properties are needed. The availability of pure TLPs and CHIs would facilitate the research for the identification of such technological advances. Therefore, we proposed the usage of recombinant TLP (rTLP) and CHI (rCHI), expressed by Komagataella phaffii, as haze-protein models, since they showed similar characteristics (aggregation potential, melting point, functionality, glycosylation levels and bentonite adsorption) to the native-haze proteins from Vitis vinifera. Hence, rTLP and rCHI can be applied to study haze formation mechanisms on a molecular level and to explore alternative fining methods by screening proteolytic enzymes and ideal adsorptive resins.     

Interplay between H‐Bonding and Preorganization in the Evolution of Self‐Assembled Systems

Cooperative π–π interactions and H‐bonding are frequently exploited in supramolecular polymerization; however, close scrutiny of their mutual interplay has been largely unexplored. Herein, we compare the self‐assembly behavior of a series of C₂‐ and C₃‐symmetrical oligophenyleneethynylenes differing in their amide topology (N‐ or C‐centered). This subtle structural modification brings about drastic changes in their photophysical and supramolecular properties, highlighting the reciprocal impact of H‐bonding vs. preorganization on the evolution and final outcome of supramolecular systems.     

Simulation and Experimental Study for Degradation of Organic Dyes Using Dual pin‐to‐plate Corona Discharge Plasma reactors for Industrial Wastewater Treatment

This work researches the possibility of increasing the dye removal efficiency from wastewater using nonthermal plasma. A study for the optimal air gap distance between dual pin and surface of Acid Blue 25 dye solution and thickness of ground plate is carried out using 3D‐EM simulator to find maximum electric field intensity at the tip of both pins. The consequences display that the best gap for corona discharge is approximately 5 mm using 15 kV source. In addition, the optimum plate thickness is 0.1 mm. These distance and thickness were mentioned are constant during the study of other factors. Dual pin‐to‐plate high‐voltage corona discharge plasma system is presented to investigation experimentally the gap distance, thickness of ground plate, initial dye concentration, pH solution and conductivity on the amount of Acid Blue 25 dye color removal efficiency from wastewater. There is a large consensus among the simulation and experimental work in the air gap and thickness of ground plate. Where the decolorization for air gap 5 mm is 95.74 at time 35 min compared with 91% and 17% for 1 mm and 20 mm gap distance respectively. Also, the discharge energy at each air gap are calculated. Measurement results for the impact of thickness of an Aluminum ground plate on color removal competence showed color removal efficiencies of 86.3%, 90.78% and 98.06%, after treatment time 15 min for thicknesses of 2, 0.5 and 0.1 mm respectively. The decolorization behavior utilizing dual pin‐to‐plate corona discharge plasma system display 82% pigment evacuation proficiency inside 11min. The complete decolorization was accomplished within 28min for distinctive examined introductory color focuses 5 ppm up to 100 ppm. Likewise, the impacts of conductivity by utilizing diverse salts as AlCl3, CaCl2, KCl and NaCl and with distinctive focuses have been explored. The rising of the solution conductivity leads to the reduction of decolorization efficiency. The decolorization efficiency and discharge energy are calculated at different concentration molarity for AlCl3, CaCl2, KCl and NaCl. It was observed that the presence of salts at the same concentration level substantially decreased the rate and the extent of decolorization. The results indicate that the optimum pH for the decolorization of Acid Blue 25 dye is in the range between 3 and 6. Furthermore the conductivity and discharge energy were measurement at each value of pH. Energy yield for decolorization and Electrical Energy per Order (EE/O) under different initial pH value were calculated. A kinetic model is used to define the performance of corona discharge system under different value of pH. The model of pseudo ‐zero, pseudo‐first order, and pseudo‐second order reactions kinetic are utilized to investigate the decolorization of Acid Blue 25 dye. The rate of degradation of Acid Blue 25 dye follows the pseudo‐first order kinetics in the dye concentration. Energy consumption requirements for decolorization was considered. The outcomes will be useful for designing the plasma treatment systems suitable for industrial wastewaters. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)