Synthesis, characterisation and catalytic potential of hydrazonato-vanadium(V) model complexes with [VO]3+ and [VO2]+ cores

Reaction between [VO(acac)2] and H2L (H2L are the hydrazones H2sal-nah I or H2sal-fah II; sal = salicylaldehyde, nah = nicotinic acid hydrazide and fah = 2-furoic acid hydrazide) in methanol leads to the formation of oxovanadium(IV) complexes [VOL.H2O](H2L = I: 1, H2L = II: 4). Aerial oxidation of the methanolic solutions of 1 and 4 yields the dinuclear oxo-bridged monooxovanadium(V) complexes [{VOL}2mu-O](H2L = I: 2, H2L = II: 5). These dinuclear complexes slowly convert, in excess methanol, to [VO(OMe)(MeOH)L](H(2)L = I: 9, H(2)L = II: 10), the crystal and molecular structures of which have been determined, confirming the ONO binding mode of the dianionic ligands in their enolate form. Reaction of aqueous K[VO3] with the ligands at pH ca. 7.5 results in the formation of [K(H2O)][VO2L](H2L = I: 3, H2L = II: 6). Treatment of 3 and 6 with H2O2 yields (unstable) oxoperoxovanadium(v) complexes K[VO(O2)L], the formation of which has been monitored spectrophotometrically. Acidification of methanolic solutions of 3 and 6 with HCl affords oxohydroxo complexes, while the neutral complexes [VO2(Hsal-nah)] 7 and [VO2(Hsal-fah)] 8 were isolated on treatment of aqueous solutions of 3 and 6 with HClO4. These complexes slowly transform into 9 and 10 in methanol, as confirmed by 1H, 13C and 51V NMR. The anionic complexes 3 and 6 catalyse the oxidative bromination of salicylaldehyde in water in the presence of H2O2/KBr to 5-bromosalicylaldehyde and 3,5-dibromosalicylaldehyde, a reaction similar to that exhibited by vanadate-dependent haloperoxidases. They are also catalytically active for the oxidation of benzene to phenol and phenol to catechol and p-hydroquinone.     

Static fluid spheres admitting Karmarkar condition

We explore a new relativistic anisotropic solution of the Einstein field equations for compact stars based on embedding class one condition.For this purpose,we use the embedding class one methodology by employing the Karmarkar condition.Employing this methodology,we obtain a particular differential equation that connects both the gravitational potentials e^λ and e^ν.We solve this particular differential equation choosing a simple form of generalized gravitational potential grr to describe a complete structure of the space-time within the stellar configuration.After determining this space-time geometry for the stellar models,we discuss thermodynamical observables including radial and tangential pressures,matter density,red-shift,velocity of sound,etc.,in the stellar models.We also perform a complete graphical analysis,which shows that our models satisfy all the physical and mathematical requirements of ultra-high dense collapsed structures.Further,we discuss the moment of inertia and M-R curve for rotating and non-rotating stars.     

Engineered Nanomaterial Assisted Signal‐amplification Strategies for Enhancing Analytical Performance of Electrochemical Biosensors

The design and development of modern biosensors for sensitive and selective detection of various biomarkers is important in diversified arenas including healthcare, environment, and food industries etc. The requirement of more robust and reliant biosensors lead to the development of various sensing modules. The nanomaterials having specific optical, electrical, and mechanical strength can pave the way towards development of ultrafast, robust, and miniaturized modules for biosensors. It can provide not only the point‐of‐care applicability but also has tremendous commercial as well as industrial justification. In order to improve the performance of the sensor systems, various nanostructure materials have been readily studied and applied for development of novel biosensors. In the last few years, researchers are engaged on harnessing the unique atomic and molecular properties of advance‐engineered materials including carbon nanotubes, graphene nanosheets, metal nanoparticles, metal oxide nanoparticles, and their nano‐conjugates. In view of such recent developments in nanomaterial engineering, the current review has been formulated emphasizing the role of these materials in surface engineering, biomolecule conjugation, and signal amplification for development of various ultrasensitive and robust biosensors having commercial as well as industrial viability. Attention is given on the electrochemical biosensors incorporating various nanomaterials and their conjugates. Importance of nanomaterials in the analytical performance of the various biosensor has also been discussed. To put a perceptive insights on the importance of various nanomaterials, an extended table is incorporated, which includes probe design, analyte, LOD, and dynamic range of various electrochemical biosensors.     

Chemical constituents of Bacopa procumbens

Phytochemical investigation of Bacopa procumbens afforded two new phenolic glycosides 1 and 2, for the first time, along with 12 known compounds 3-14. Structures of these compounds were established based on spectral and chemical evidences.     

Studies on the structural,thermal and optical behaviour of solution grown organic NLO material: 8‐hydroxyquinoline

Single crystal of 8‐hydroxyquinoline (8HQ) having chemical formula C₉H₇NO, an organic nonlinear optical (NLO) material has been successfully grown by slow evaporation solution growth technique at room temperature. The crystal system has been confirmed from the powder X‐ray diffraction (PXRD) analysis. The crystalline perfection was evaluated by high resolution X‐ray diffractometry (HRXRD). From this analysis we found that the quality of the crystal is quite good. However, a very low angle (tilt angle 14 arc sec) boundary was observed which might be due to entrapping of solvent molecules in the crystal during growth. Its optical behavior has been examined by UV‐Vis. analysis, which shows the absence of absorbance between the wavelengths ranging from 400 to 1200 nm. From the thermal analysis it was observed that the material exhibits single sharp weight loss starting at 113°C without any degradation. The laser damage threshold was measured at single shot mode and the SHG behavior has been tested using Nd:YAG laser as a source. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rapid determination of rifaximin on dried blood spots by LC‐ESI‐MS

The use of blood spot collection cards is a simple way to obtain specimens for therapeutic drug monitoring, assessing adherence to medications and preventing toxicity in a clinical setting. A high‐throughput liquid chromatography–electrospray ionization mass spectrometric (LC‐ESI‐MS) method for determination of rifaximin on dried blood spots (DBS) was developed and validated. It involves solvent extraction of a punch of DBS followed by reversed‐phase LC on a monolithic column consisting of a silica rod with bimodal pore structure and detection by ESI‐MS. Rifampicin was used as an internal standard (IS). The run time was within 5.0 min with a very low back‐pressure at a flow rate of 0.5 mL/min. The assay was linear from 0.1 to 10 ng/mL. The mean recovery was 98.42%. The developed method is very simple, rapid and useful for clinical applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Frequency detuning dependence of oscillation condition for a semilinear photorefractive optical resonator in a photorefractive material with reflection gratings

Frequency detuning dependence of four-beam coupling in a photorefractive crystal pumped with two counter-propagating waves for a semilinear coherent optical resonator on the oscillation conditions has been analyzed in the case of non-degenerate-wave mixing under the slowly varying amplitude approximation method. Self oscillation can be achieved when the gain arising from the four-beam coupling is large enough to overcome the cavity loss. The effects of frequency detuning (i.e., non-degeneracy), dielectric constant and photoconductivity of the photorefractive materials on the performance of the semilinear photorefractive coherent resonator with the reflection grating configuration have also been studied in detail. The phase-conjugate reflectivity of the pumped crystal and oscillation intensity has been calculated for different input pump beam intensity ratio, intensity reflectivity of the conventional mirrors, degenerate energy coupling strength of the interacting beams. It has been found that for the higher value of the photoconductivity σ_p(>2.0 pS/cm) of photorefractive crystal, the semilinear resonator can oscillate at almost any frequency detuning (Ω) of the oscillation beam with respect to the fixed frequency of the pump waves whereas for the lower value of photoconductivity σ_p(<0.1 pS/cm) oscillation occurs only when the frequency detuning is limited to small region around Ω = 0. But reverse of the case is found for dielectric constant (?), pump intensity ratio (p) and conventional mirror reflectivity (R).     

Decreased Activity of Ca++-ATPase and Na+/K+-ATPase during Aging in Humans

Aging is a biological process characterized by a progressive functional impairment which is associated with increased susceptibility to a variety of diseases. The main purpose of this study is to understand the gender-based relationship between human aging and activities of two erythrocyte membranes bound enzymes, Ca⁺⁺-ATPase and Na⁺/K⁺-ATPase. Ca⁺⁺-ATPase and Na⁺/K⁺-ATPase activities were determined as per the previous reports. Statistical differences were analyzed with Student’s t test. Our results show a significant (p?<?0.0001) decrease in the Ca⁺⁺-ATPase and Na⁺/K⁺-ATPase activities in males and females as a function of age. We also correlate the activities of ATPases with total antioxidant capacity of the plasma in term of ferric reducing ability of plasma values. The Ca⁺⁺-ATPase and Na⁺/K⁺-ATPase activities positively correlated with ferric reducing ability of plasma value. No significant differences in the ATPase activity between males and females were observed. Decreased activity of Ca⁺⁺-ATPase and Na⁺/K⁺-ATPase during human aging may be due to increased free radical generation which leads to oxidative stress and alter the erythrocyte membrane transport function and other activities. Our results emphasize the need to establish age-dependent reference values for membrane bound enzymes in studies involving its role in different disease conditions.