Bulky organosilicon compounds based on sulfanyltetrazoles: their synthesis and in vitro antibacterial evaluation

The study introduces different organosilicon derivatives incorporating sulfanyltetrazole ring for biological applications. Initially, the sulfanyltetrazole derivatives and halo-analogues (Br, I) were synthesized. Later, selective reaction of tris(trimethylsilyl)methyllithium (TsiLi) in the presence (?46 and 0 °C) and absence (room temperature) of CS₂ with halo-sulfanyltetrazole derivatives yielded new multifunctional sulfanyltetrazole regioisomers with SH, C = S, ethynylthio and SiMe₃ groups, respectively. All the synthesized compounds were characterized by IR, ¹H-NMR, ¹³C-NMR spectra and elemental analysis data. The compounds were screened for their antibacterial activities against clinically important gram-positive and gram-negative bacteria using the spectrophotometric microdilution method. The preliminary screening indicated that the organosilicon derivatives incorporating SH and C = S (mercapto-silyl-thiones) and silyl-thioalkynes have antibacterial activities, whereas no antibacterial activity was observed on compounds containing (Me₃Si)₃C groups. Of the synthesized compounds, compound 5d showed the best activity against all the tested organisms (3.91–31.25 µg/mL).     

Cycloisomerization of dienes and enynes catalysed by a modified ruthenium carbene species

Cycloisomerization is a totally atom economic procedure which converts dienes and enynes into cyclic molecules. Modification of Grubbs' 2nd generation catalysts by reaction with dimethylformamide provides a new species able to catalyse this transformation. Selection of suitable conditions allowed high yields and selectivity. Studies performed in order to identify the catalytic species point to a non-carbenic ruthenium complex that has lost the phosphine. No hydride signals appeared. In addition, the reaction works with enynes and the new species catalyses efficiently crossed cyclotrimerizations of alkynes with diynes.     

Comparative Study of Chromium Biosorption by Mesorhizobium amorphae Strain CCNWGS0123 in Single and Binary Mixtures

The appearance of chromium in the aqueous effluent is a major concern for the modern industry. In this work, Mesorhizobium amorphae strain CCNWGS0123 was investigated as a biosorbent to remove chromium from aqueous solutions. The optimum pH for Cr(III) and Cr(VI) biosorption were 4 and 2, respectively. This isolate showed an experimental maximum Cr(III) adsorption capacity of 53.52 mg?L^?1, while the result was 47.67 mg?L^?1 for Cr(VI), with an initial 100 mg?L^?1 Cr ions and 1.0 g?L^?1 biomass. In terms of time equilibrium, Cr(III) ion was more readily adsorbed than Cr(VI) by this isolate. The biosorption data of both ions fit the Langmuir isotherm better than that of Freundlich model. Meanwhile, this organism exhibited a good capability to release Cr ions, with desorption efficiency of 70 % for Cr(III) and 76 % for Cr(VI). Fourier transform infrared spectroscopy analysis showed that –OH, –COO, –NH, amide I, and C=O were involved in Cr(III) and Cr(VI) binding. The biosorbent was further characterized by scanning electron microscopy and energy-dispersive X-ray spectrometry, which indicated an accumulation of chromium on the cellular level. In the binary mixtures, the removal ratio of total Cr and Cr(III) increased from pH?2 to 4. The highest removal ratio of the total Cr was observed in the 25/25 mg?L^?1 mixture at pH?4. In addition, the removal efficiency of Cr(VI) was closely influenced by Cr(III) in the mixture, decreasing to 23.57 mg?g^?1 in the 100/100 mg?L^?1 mixture system, due to the competition of Cr(III). The potential usage of the chromium-resistant rhizobium for the remediation of chromium-contaminated effluents has been demonstrated based on the above results.     

Effects of gamma radiation on codling moth, Cydia pomonella (L.), eggs

The radiosensitivity of codling moth, Cydia pomonella (L.), eggs in different stages of development was studied. Eggs ranging in age from 1–24 to 97–120 h were exposed, at 24 h intervals, to gamma radiation doses ranging from 10 to 350 Gy. The effects of gamma radiation on egg hatch, pupation and adult emergence was examined. Results showed that the radiosensitivity of codling moth eggs decreased with increasing age. Egg hatch in 1–24 h old eggs was significantly affected at 20 Gy dose and at 60 Gy dose, egg hatch decreased to about 1%. At the age of 25–48 h, however, egg hatch at 60 Gy dose was about 10%, and egg sensitivity to gamma irradiation decreased significantly in the 49–72 h age group; 60 Gy dose had no significant effect on egg hatch. Eggs irradiated few hours before hatch (at the blackhead stage), were the most resistant ones; 100 Gy had no significant effect on egg hatch and at 350 Gy dose over 56% of the eggs hatched. When adult emergence was used as a criterion for measuring effectiveness, however, the effect of gamma radiation was very sever. A dose of 60 Gy completely prevented adult emergence and at 100 Gy dose all resulted larvae died before pupation.     

Polysaccharide Chemistry in Drug Delivery,Endocrinology, and Vaccines

Polysaccharides, due to their outstanding properties, have attracted the attention of researchers, working in the biomedical field and especially of those working in drug delivery. Modified/functionalized polysaccharides further increase the importance for various applications. Delivery of therapeutics for diverse ailments in different endocrine glands and hormones safely, is a focal point of researchers working in the field. Among the routes followed, the transdermal route is preferred due to non-exposure of active moieties to the harsh gastric environment and first-pass metabolism. This review starts with the overview of polysaccharides used for the delivery of various therapeutic agents. Advantages of polysaccharides used in the transdermal route are addressed in detail. Types of polysaccharides will be elaborated through examples, and in this context, special emphasis will be on the polysaccharides being used for synthesis of the membranes/films. Techniques employed for their modification to design novel carriers for therapeutics delivery will also be discussed. The review will end with a brief discussion on recent developments and future perspectives for delivery of therapeutic agents, and vaccine development.     

Prospects and Challenges of Microwave-Combined Technology for Biodiesel and Biolubricant Production through a Transesterification: A Review

Biodiesels and biolubricants are synthetic esters produced mainly via a transesterification of other esters from bio-based resources, such as plant-based oils or animal fats. Microwave heating has been used to enhance transesterification reaction by converting an electrical energy into a radiation, becoming part of the internal energy acquired by reactant molecules. This method leads to major energy savings and reduces the reaction time by at least 60% compared to a conventional heating via conduction and convection. However, the application of microwave heating technology alone still suffers from non-homogeneous electromagnetic field distribution, thermally unstable rising temperatures, and insufficient depth of microwave penetration, which reduces the mass transfer efficiency. The strategy of integrating multiple technologies for biodiesel and biolubricant production has gained a great deal of interest in applied chemistry. This review presents an advanced transesterification process that combines microwave heating with other technologies, namely an acoustic cavitation, a vacuum, ionic solvent, and a supercritical/subcritical approach to solve the limitations of the stand-alone microwave-assisted transesterification. The combined technologies allow for the improvement in the overall product yield and energy efficiency. This review provides insights into the broader prospects of microwave heating in the production of bio-based products.     

Coordination of carbonyl oxygen in the complexes of polymeric <Emphasis Type="Italic">N</Emphasis>-crotonyl-2-hydroxyphenylazomethine

The Schiff base N-crotonyl-2-hydroxyphenylazomethine HL, derived from the reaction of acrylamide and salicylaldehyde, was synthesised. Polymeric complexes were obtained from the reaction of polymeric HL with divalent metals. The mode of bonding and overall geometry of the complexes were determined through physico-chemical and spectroscopic methods and compared with that previously reported for the analogous monomeric ligand. These studies revealed tetrahedral geometries around the metal centres for Mn(II), Co(II), Zn(II), Cd(II) and Hg(II) complexes of general formula [M(L)Cl], octahedral for Ni(II) and Cu(II) complexes of general formula [M′(L)Cl(H₂O)₂], and square planar for Pd(II) complex of general formula [Pd(L)Cl].     

Multi-residue analytical method for human pharmaceuticals and synthetic hormones in river water and sewage effluents by solid-phase extraction and liquid chromatography–tandem mass spectrometry

Pollutants such as human pharmaceuticals and synthetic hormones that are not covered by environmental legislation have increasingly become important emerging aquatic contaminants. This paper reports the development of a sensitive and selective multi-residue method for simultaneous determination and quantification of 23 pharmaceuticals and synthetic hormones from different therapeutic classes in water samples. Target pharmaceuticals include anti-diabetic, antihypertensive, hypolipidemic agents, β2-adrenergic receptor agonist, antihistamine, analgesic and sex hormones. The developed method is based on solid phase extraction (SPE) followed by instrumental analysis using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC–ESI-MS/MS) with 30 min total run time. River water samples (150 mL) and (sewage treatment plant) STP effluents (100 mL) adjusted to pH 2, were loaded into MCX (3 cm³, 60 mg) cartridge and eluted with four different reagents for maximum recovery. Quantification was achieved by using eight isotopically labeled internal standards (I.S.) that effectively correct for losses during sample preparation and matrix effects during LC–ESI-MS/MS analysis. Good recoveries higher than 70% were obtained for most of target analytes in all matrices. Method detection limit (MDL) ranged from 0.2 to 281 ng/L. The developed method was applied to determine the levels of target analytes in various samples, including river water and STP effluents. Among the tested emerging pollutants, chlorothiazide was found at the highest level, with concentrations reaching up to 865 ng/L in STP effluent, and 182 ng/L in river water.     

Highly efficient orthopalladated complexes of second and third benzyl amine for catalyzing the Suzuki cross‐coupling reaction

In this work, ortho‐palladated complexes [Pd(µ‐Cl)(C₆H₄CH₂ NRR′‐κ²‐C,N)]₂ and [Pd(C₆H₄CH₂NH₂‐2‐C,N)Cl(Y)] were tested in the Suzuki–Miyaura cross‐coupling reaction. Cyclopalladated Pd(II) complexes as thermally stable catalysts can activate aryl bromides and chlorides. These complexes were active and efficient catalysts for the Suzuki–Miyaura reaction of aryl bromides and even less reactive aryl chlorides. The cross‐coupled products of a variety of aryl bromides and aryl chloride with phenylboronic acid in methanol as solvent at 60 °C were produced in excellent yields. Copyright © 2010 John Wiley & Sons, Ltd.