Mechanistic study of electrochemical oxidation of 2,5-dihydroxybenzoic acid and 3,4-dihydroxybenzaldehyde in the presence of 3-hydroxy-1H-phenalene-1-one

The mechanism of the electrochemical oxidation of 2,5-dihydroxybenzoic acid and 3,4-dihydroxybenzaldehyde in the presence of 3-hydroxy-1H-phenalene-1-one as a nucleophile has been studied in water/acetonitrile (80/20 v/v) solution using cyclic voltammetry and controlled-potential coulometry methods. The results indicate that the quinones derived from oxidation of 2,5-dihydroxybenzoic acid and 3,4-dihydroxybenzaldehyde participate in Michael addition reactions with 3-hydroxy-1H-phenalene-1-one and via ECE and ECEC mechanisms convert to the different products, with good yield under controlled potential conditions, at carbon electrode.     

Computational study of mixing behaviour of a turbulent jet issuing in a uniform counterflow at low velocity ratios

This paper proposes a computational study for the analysis of the velocity and the scalar concentration field of a round turbulent jet flowing into a uniform stream in opposite direction. The investigation is carried out for a range of low jet-to-counterflow velocity ratios; R = 1.3, 1.6, 2.2, 3.1 and 3.4. The Reynolds stress model is applied in numerical simulation to compare obtained results with experimental data from the literature. It is found that predicted results are in good agreement with the experimental data and that the jet fluid decays faster in the presence of a counterflow. The linearity between the penetration distance and the velocity ratio is verified and the axial fluctuating velocities along jet centreline appear to have two distinct peaks, except for the stronger counterflow. The enhanced mixing efficiency of the counterflowing jet is verified through the radial distribution of velocity and scalar concentration at different streamwise stations.     

Influence of Metal Oxides on Platinum Activity towards Methanol Oxidation in H2SO4 solution

Pt–CeO₂/C, Pt–TiO₂/C, and Pt–ZrO₂/C electrocatalysts were prepared by using a modified microwave‐assisted polyol process. Physical characterization was performed by using XRD, TEM, and EDX analyses. The incorporation of different metal oxides increased the dispersion degree of Pt nanoparticles and reduced their diameter to 2.50 and 2.33 nm when TiO₂ and ZrO₂ were introduced to Pt/C, respectively. The electrocatalytic activity of various electrocatalysts was examined towards methanol oxidation in H₂SO₄ solution by using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. Among the studied composites, Pt–ZrO₂/C was selected to be a candidate electrocatalyst for better electrochemical performance in direct methanol fuel cells.     

Fibril formation of lysozyme upon interaction with sodium dodecyl sulfate at pH 9.2

Fibril formation seems to be a general property of all proteins. Its occurrence in hen or human lysozyme depends on certain conditions, namely acidic pHs or the presence of some additives. This paper studies the interaction of lysozyme with sodium dodecyl sulfate (SDS) at pH 9.2, using UV-visible spectrophotometry, circular dichroism (CD) spectropolarimetry, electron microscopy (EM) and chemometry. Based on observations such as the strange increase in absorbance at 650nm (pH 9.2) and the presence of intermediates, it is assumed that lysozyme fibrils have been formed at pH 9.2 in the presence of SDS as an anionic surfactant. Thioflavin T emission fluorescence and an EM image confirmed this assumption. beta-cyclodextrin was then used as a turbidity inhibitor to establish its effect on the distribution of intermediates that participate in fibril formation.     

Electrosynthesis of symmetric and highly conjugated benzofuran via a unique ECECCC electrochemical mechanism: evidence for predominance of electrochemical oxidation versus intramolecular cyclization

Electrochemical oxidation of hydroquinone, catechol, and some of their monosubstituted derivatives has been studied in the presence of 3-hydroxy-1H-phenalen-1-one (2) as a nucleophile in water/acetonitrile (80/20) solutions using cyclic voltammetry and controlled-potential coulometry methods. The results revealed that quinones derived from oxidation of hydroquinones and catechols participate in Michael addition reactions with 2. The formed adducts convert to the corresponding benzofuran derivatives via different mechanisms. In this work, we derived a variety of products with good yields using controlled potential electrochemical oxidation at a graphite electrode in an undivided cell.     

Pharmacological Evaluation of Novel Organoiron Dendrimers as Antimicrobial and Anti‐Inflammatory Agents

The synthesis of a novel and attractive class of nonsteroidal anti‐inflammatory and antimicrobial organoiron dendrimers attached to the well‐known drug ibuprofen is achieved. The structures of these dendrimers are established by spectroscopic and analytical techniques. The antimicrobial activity of these dendrimers is investigated and tested against five human pathogenic Gram‐positive and Gram‐negative bacteria, and minimum inhibitory concentrations are reported. Some of these synthesized dendrimers exhibit higher inhibitory activity against methicillin‐resistant Staphylococcus aureus, vancomycin‐resistant Enterococcus faecium, and Staphylococcus warneri compare to the reference drugs. As well, the in vitro and in vivo anti‐inflammatory activities of these dendrimers are evaluated. The results of in vivo anti‐inflammatory activity and histopathology of inflamed paws show that all dendrimers display considerable anti‐inflammatory activity; however, second‐generation dendrimer ( G2‐D6 ) shows the best anti‐inflammatory activity, which is more potent than the commercial drug ibuprofen at the same tested dose. Results of the toxicity study reveal that G2‐D6  is the safest drug on biological tissues.     

Global optimization of non-convex piecewise linear regression splines

Multivariate adaptive regression spline (MARS) is a statistical modeling method used to represent a complex system. More recently, a version of MARS was modified to be piecewise linear. This paper presents a mixed integer linear program, called MARSOPT, that optimizes a non-convex piecewise linear MARS model subject to constraints that include both linear regression models and piecewise linear MARS models. MARSOPT is customized for an automotive crash safety system design problem for a major US automaker and solved using branch and bound. The solutions from MARSOPT are compared with those from customized genetic algorithms.     

Separation and sensitive determination of quercetin in <Emphasis Type="Italic">Rosa canina</Emphasis> L. using solidified floating organic drop microextraction followed by high-performance liquid chromatography determination

Quercetin is a polyphenolic flavonoid found in many plants and is used as a nutritional supplement. It has been reported to have biological properties that may play an important role in the prevention of human diseases, such as cancer, cardiovascular diseases, diabetes, ulcer, cataract and allergies. In this research, solidified floating organic drop microextraction coupled to high-performance liquid chromatography was used to extract and determine quercetin in Rosa canina L., growing in different areas of Lorestan Province in Iran. The effect of important experimental variables such as type and volume of extracting organic solvent, extraction temperature and time, pH and effect of ionic strength on the extraction recovery was investigated and optimized. Under the optimum extraction conditions, a linear response was obtained over the range of 0.5–40 µg mL^?1. Relative standard deviation (RSD%) and enrichment factor were found to be 3.4% and 230, respectively. The proposed method was applied successfully for the determination of quercetin in calycles and fruit of R. canina L. samples. The results showed good agreement compared with those obtained by a validated standard method.     

Reaching for two new stable ambiphilic quinoline‐derived N‐heterocyclic carbenes at DFT level

A detailed investigation on the thermodynamic and kinetic stability of four carbenic tautomers of quinoline 1 , including quinoline‐2‐ylidene 2 , quinoline‐3‐ylidene 3 , quinoline‐4‐ylidene 4 , and 3,4‐dihydroquinoline‐4‐ylidene 5 , reveals that singlet planar six‐membered ring N‐heterocyclic carbenes (NHCs) 2 and 4 have less stability than Arduengo type NHC but seems to have enough conceivably for reaching at B3LYP/aug‐cc‐pVTZ//B3LYP/6–31+G* and B3LYP/6–311++G**//B3LYP/6–31+G* levels. All these six‐membered NHCs are extremely ambiphilic with the more nucleophilic and electrophilic characters compared to the Arduengo type one. The aromaticity of singlet 2 and 4 is a significant contributor to their stability which is confirmed through their Nucleus‐independent chemical shift(1)_zz values. Finally, among 2–5 , the normal NHC 2 is thermodynamically preferred but the remote NHC 4 is kinetically proffered over the other isomeric carbenes. The effects of different N‐ or C‐substituted NHCs of 2 are studied using appropriate isodesmic reactions. The trimethylsilyl substituent exhibits slightly larger carbene stabilization in quinoline‐derived NHCs than the pyridine analogue. © 2014 Wiley Periodicals, Inc.