Ni(II) selective sensors based on Schiff bases membranes in poly(vinyl chloride)

The two nickel chelates of Schiff bases, 3-hydroxy-N-{2-[(3-hydroxy-N-phenylbutyrimidoyl)-amino]-phenyl}-N′-phenylbutyramidine (M₁) and bis-4-(ethyliminomethyl)naphthalene-1-ol (M₂), have been synthesized and explored as ionophores for preparing PVC-based membrane sensors selective to nickel ion. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w; mg) of (M₁): PVC:NaTPB:CN in the ratio 5:150:5:150. The sensor shows a linear potential response for Ni²⁺ over a wide concentration range 1.6 × 10⁻⁷ to 1.0 × 10⁻² M with Nernstian compliance (30.0 ± 0.2 mV/decade of activity) within pH range 2.5-9.5 and a fast response time of 10 s. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol, and acetonitrile and could be used for a period of 4 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of nickel in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.     

Ultrafast bimolecular electron transfer dynamics in micellar media

Ultrafast photoinduced bimolecular electron transfer (ET) dynamics between 7-aminocoumarin derivatives and N,N-dimethylaniline (DMAN) has been studied in neutral (TX100), cationic (DTAB) and anionic (SDS) micellar media. A very fast decay time constant (tau(fast)) shorter than approximately 10 ps has been observed for the coumarins in the presence of DMAN in all of the three micellar media. In this time scale, reactants in the micellar phase undergo ET interactions without involving diffusion or reorientation of the reactants and thus can be envisaged as equivalent to nondiffusive bimolecular ET reaction. The fastest ET rates estimated as the inverse of the shortest lifetime components of the fluorescence decay (k(et) congruent with tau(fast)(-1)) nicely follow the predicted Marcus inversion behavior with reaction exergonicity (-DeltaG degrees), irrespective of the nature of micelles considered. Onset of inversion in ET rates occur at approximately 0.61 eV lower exergonicity in SDS and TX100 micelles compared with that in DTAB micelle and are rationalized following two-dimensional ET (2DET) theory. These differences suggest the possibility of tuning Marcus inversion by proper selection of micelles. Interestingly, ET rates (k'(et)) obtained from the conventional Stern-Volmer analysis of the relatively longer time constants of the fluorescence decays also exhibit similar Marcus correlation with DeltaG degrees, showing clear inversion behavior. Fitting of Marcus correlation curves for k(et) and k'(et) indicate two largely different values for the electronic coupling parameters. In micellar media, as the interacting donor-acceptor molecules are on an average expected to be separated by an intervening surfactant chain and the reorientation rate of the reactants is quite slow, it is predicted that the ultrafast ET (k(et)) component arises because of the surfactant separated donor-acceptor pairs that are orientated perfectly to give the maximum electronic coupling. The slower ET (k'(et)) is predicted to arise because of those pairs where the donor-acceptor orientations are not very suitable but good enough to give a sizable electronic coupling.     

Quantification of clopidogrel in human plasma by sensitive liquid chromatography/tandem mass spectrometry

A simple, sensitive and rapid high-performance liquid chromatography/positive electrospray ionization tandem mass spectrometry method was developed and validated for the assay of clopidogrel in human plasma. Following liquid-liquid extraction, the analytes were separated using an isocratic mobile phase on a reversed-phase column and analyzed by mass spectrometry in the multiple reaction monitoring mode using the respective [M+H](+) ions, m/z 322/212 for clopidogrel and m/z 264/154 for the internal standard. The assay exhibited a linear dynamic range of 5-6000 pg/mL for clopidogrel in human plasma. The lower limit of quantification was 5 pg/mL with a relative standard deviation of less than 8%. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. A run time of 2.5 min for each sample made it possible to analyze more than 400 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies.     

Efficient Synthetic Route to Access Linear and Angular Dibenzonaphthyridines

Russian Journal of Organic Chemistry - An efficient procedure has been proposed for the synthesis of linear and angular phenyl-substituted dibenzonaphthyridines from anilinoquinolines and benzoic...     

Role of Vitamins B-3 and C in the Fashioning of Granules in UASB Reactor Sludge

Whereas a myriad of possible factors have been reported which effect the formation of granules in a upflow anaerobic sludge blanket (UASB) reactor and influence their properties, there is no study on the effect of vitamins on the granulation of UASB reactor sludge. The present study was undertaken to bridge this gap. It was seen that vitamins helped in better granule formation??as reflected by favorable size distribution, sludge volume index, and settling velocity??compared to controls. The vitamin-spiked reactors also achieved >85?% COD removal efficiency in half the number of days the unspiked reactors took. The vitamin supplements were effective at concentrations????1?mg/l. Hence, their use in expediting granule formation as also in developing better-quality granules appears economically viable.     

Biological aspects of Schiff base–metal complexes derived from benzaldehydes: an overview

Schiff bases are stable imines containing C=N, where N is bonded to an alkyl or aryl group, but not with hydrogen and are prepared by condensation of aliphatic or aromatic primary amine with carbonyl compounds. They have the general formula R₁R₂C?=?NR₃, where R₃?≠?H. The presence of the basic donor N atom and the stability of the imine function render Schiff bases as the most favored ligands that have the ability to stabilize metal ions in different oxidation states. The chelating environment in a Schiff base profoundly influences the electron distribution in the coordination sphere of metal in a complex and thereby regulates the property of the compounds in a big way. The structural diversity in some of the metal complexes with multidentate Schiff base ligands has triggered a wide range of applications of this class of compounds in sensors, catalysis, biology, medicines, and photonics. This review compiles the synthesis and biological activities (antimicrobial, antioxidant, anticancer, antitubercular, DNA interaction studies) of benzaldehyde-based Schiff bases and their metal complexes.     

Elastomeric polypeptide-based biomaterials

Elastomeric proteins are characterized by their large extensibility before rupture, reversible deformation without loss of energy, and high resilience upon stretching. Motivated by their unique mechanical properties, there has been tremendous research in understanding and manipulating elastomeric polypeptides, with most work conducted on the elastins but more recent work on an expanded set of polypeptide elastomers. Facilitated by biosynthetic strategies, it has been possible to manipulate the physical properties, conformation, and mechanical properties of these materials. Detailed understanding of the roles and organization of the natural structural proteins has permitted the design of elastomeric materials with engineered properties, and has thus expanded the scope of applications from elucidation of the mechanisms of elasticity to the development of advanced drug delivery systems and tissue engineering substrates.     

Purification and Characterization of Enterocin LR/6, a Bacteriocin from <Emphasis Type=Italic>Enterococcus faecium</Emphasis> LR/6

Enterocin LR/6, a bacteriocin obtained from the culture filtrate of Enterococcus faecium strain LR/6, has been purified to homogeneity using ammonium sulfate precipitation, cation-exchange chromatography, gel-filtration, and checked on reverse-phase high-performance liquid chromatography. It is active at high temperatures (boiling as well as autoclaving) and over a wide range of pH (2.0–8.0). Also, it is sensitive to a number of proteolytic enzymes but is stable in the presence of surfactants and organic solvents. The protein could be stored at least up to 1 year at low temperatures (4 °C and −20 °C) without any loss of activity. The N-terminal sequence of enterocin LR/6 showed no homology with known enterocins or other bacteriocins present in the database, suggesting it to be a novel enterocin. Matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry and tricine sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis revealed its mass to be ∼6.1 kDa. It showed a bactericidal mode of action against indicator strain, Micrococcus luteus.     

Optimized Aluminum Reflector for Enhancement of UVC Cathodoluminescence Based-AlGaN Materials with Carbon Nanotube Field Emitters

The far ultraviolet C (UVC) light sources based on carbon nanotube (CNT) field emitters as excitation sources have become promising light sources for sterilization, disinfection, and water purification. However, the low light extraction efficiency of UVC–CNT light sources still hinders the practical application of these structures. Herein, we report an optimized aluminum (Al) reflector to enhance the light extraction efficiency of UVC–CNT light sources. Optical analysis of UVC-CNT light sources covered by the Al reflectors with various thicknesses ranging from 30 to 150 nm was performed to realize the optimized reflector. The UVC-CNT light sources exhibit the highest light extraction efficiency when the Al reflector layer has an optimized thickness of 100 nm. For comparison, the cathodoluminescence (CL) spectra were recorded for UVC–CNT light sources with and without the optimized Al reflector. The measured light output power and the estimated power efficiency of the UVC–CNT light-source-tube with Al reflector were enhanced by about 27 times over the reference. This enhancement is mainly attributed to the outstanding reflection effect of the Al reflector.     

Volumetric Properties of Aqueous 2-Chloroethanol Solutions and Volumes of Transfer of Some Amino Acids and Peptides from Water to Aqueous 2-Chloroethanol Solutions

Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V ₂ ^o = 55.05 ± 0.02 cm³-mol^–1, (V ₂ ^o/T)_p = 0.01486 ± 0.00318 cm³-K^–1-mol^–1, and (² V ₂ ^o/T ²)_p = 0.02972 ± 0.00318 cm³-K^–2-mol^–1. Partial molar volumes of transfer from water to 1 mol-dm^–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol.