A comparative study of electronic structure and bonding in transition metal monocarbides

The structural, electronic, elastic and bonding properties of four transition metal carbides, ScC, YC (group III), VC and NbC (group V), have been investigated systematically using the first principles density functional theory (DFT). The full potential linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA) for the exchange correlation has been used for the calculation of the total energy. The ground state properties, such as equilibrium lattice constant, bulk modulus, are computed and compared with theoretical and experimental data. The electronic and bonding patterns of the two groups of compounds have been analyzed quantitatively and compared with the available data. It is clear from band structures that all the four transition metal monocarbides are metallic in nature. Analysis of elastic constants reveals that the carbides of group III are ductile in nature while those of group V are brittle.     

Electrical conduction mechanism of polyvinylidenefluoride (PVDF) – polysulfone (PSF) blend film

The electrical conductivity of polyvinylidenefluoride (PVDF) – polysulfone (PSF) blend films have been measured by studying the I–V characteristics in the temperature range of 298–398 K. The results are shown by measuring the dependence of current on field, temperature, and blending compositions in the form of I–V characteristics and analysis has been made by interpretation of Poole–Frenkel, Schottky ln (J) vs. T plots, Richardson and Arrhenius plots. For individual polymers, the conduction mechanism observed to be a Poole–Frenkel type. On blending, the charge conduction appears to be the Schottky emission at lower temperature while Poole–Frenkel mechanism at higher temperature. The analysis of these results suggests that Pool–Frenkel mechanism is mainly responsible for the observed conduction. The conductivity was found to increase with an increase in the polysulfone concentration in the blend; it could be justified in terms of mobility of charge carriers. It is found that mobility of charge carriers increases with the increase in polysulfone concentration in the blend.     

Modification of Dietary Fiber Psyllium with Poly(vinyl pyrrolidone) through Network Formation for Use in Slow Drug Delivery Application

In view of the pharmacological importance of dietary fibre, psyllium, to cure the constipation and diverticulitis, in the present study, an attempt has been made to modify psyllium polysaccharide with PVP to develop the hydrogel meant for slow and controlled drug delivery systems. The polymer was characterized by SEMs, FTIR, XRD, TGA and swelling studies. Swelling of hydrogels and drug (ciprofloxacin) release profile from the drug loaded hydrogels were determined for the evaluation of the swelling/release mechanism. Biomedical properties; biocompatibility and mucoadhesion of the hydrogels, were also studied. Swelling of the hydrogels and release of drugs from drug loaded hydrogels occurred through non-Fickian diffusion mechanism. Here it is pertinent to mention that both psyllium husk polysaccharide and antibiotic drug ciprofloxacin are used for gastrointestinal tract (GIT) problem, especially in case of diverticulitis. Hence, degradation of the polymer matrix and release of drug may exert the synergic effect and the present drug delivery system may act with enhanced potential.     

Ni selective sensors based on meso-tetrakis-{4-[tris-(4-allyl dimethylsilyl-phenyl)-silyl]-phenyl}porphyrin and (sal)2trien in poly(vinyl chloride) matrix

PVC-based membranes of meso-tetrakis-{4-[tris-(4-allyl dimethylsilyl-phenyl)-silyl]-phenyl}porphyrin (I) and (sal)₂trien (II) as electroactive material with dioctylphthalate (DOP), tri-n-butylphosphate (TBP), chloronapthalene (CN), dibutylphthalate (DBP) and dibutyl(butyl) phosphonate (DBBP) as plasticising solvent mediators have been found to act as Ni²⁺ selective sensor. The best performance was obtained with the sensor having a membrane of composition of I: sodium tetraphenyl borate: PVC in the ratio 5:5:150. The sensor exhibits Nernstian response in the activity range 2.5 × 10⁻⁶ to 1.0 × 10⁻¹ M, performs satisfactorily over wide pH range (2–5.5) with a fast response time (8 s). The sensor was found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol or ethanol and acetone and could be used over a period of 4 months. Potentiometric selectivity coefficients determined by matched potential method (MPM) indicate excellent selectivity for Ni²⁺ ions. The sensors could be used successfully in the estimation of nickel in different brand of chocolates and also as an indicator electrode in potentiometric titration.     

Peptide Cysteine Thiols Act as Photostabilizer of Avobenzone through Stabilizing the Transition State of Keto-Enol Tautomerization

Photostabilizers have been used to impart stability to an FDA-approved chemical UV-A filter avobenzone against the UV-A radiations and sunlight. The thiol group of glutathione plays a critical role in imparting the photostabilization activity of glutathione on avobenzone. The current report aims to evaluate the photostabilization activity of multiple thiols containing cysteine peptides on avobenzone. Cysteine-tripeptide and cysteine-pentapeptide were chemically synthesized and characterized using mass spectrometry. Synthetic peptides were assessed for their photostabilization activity on the enolic-form of the avobenzone under natural sunlight using UV spectroscopy in both protic and aprotic solvents. Unlike glutathione, which has pronounced activity in protic solvents, cysteine-pentapeptide exhibits similar photoprotection activity in both protic and aprotic solvents. Computational calculations using DFT suggest that peptide cysteine thiols may assist in the reversal of the photoketonization process of avobenzone thereby exhibiting the photoprotection activity to the enolic-form of avobenzone. Peptide cysteine thiols lower the activation energy barrier of keto-to-enol tautomerization of avobenzone by 30 kcal mol⁻¹ by assisting the proton shuttle through a six-membered transition state. The current report emphasizes the applications of peptide thiols in cosmetics and may help in the development of peptides as aesthetic medicines.     

Microsphere based continuous-flow immunoassay in a microfluidic device for determination of clinically relevant insulin levels

This paper describes a miniaturized microsphere-based immunoassay integrated into a microfluidic device for rapid quantitation of insulin. Analysis of bionic pancreas studies have revealed that the rates of absorption of insulin analogs vary from patient to patient, and even within patients on different occasions. Thus development of an approach to monitor insulin continuously allows the pharmacokinetic characteristics of insulin analogs to be determined in real-time. The authors have developed a microsphere-based continuous flow assay in a microfluidic chip that allows for the detection of insulin within seconds with high sensitivity and specificity. The method was applied to near real-time monitoring of clinical samples. Calibration plot were established for different insulin analogs such as insulin aspart (Novolog), insulin lispro (Humalog), and regular human insulin (RHI) and the insulin detection limit was 0.26 ng.mL^?1 (44 pM). This sensitivity allows to detect the fasting insulin levels of T1D patients, which are reported in the range of 50–180 pM (0.3–1 ng.mL^?1), after treatment with subcutaneous insulin administration. This fast approach was also applied to sera collected in intervals from T1D patients after a bolus of insulin aspart delivery. The insulin profile obtained by this method is similar to the basal and peak insulin levels as determined using the standard non-continuous ELISA reference method. In our perception, this assay will improve healthcare by personalizing diagnostics for better clinical outcome and provide real-time feedback on sensing and actuation.

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Graphical abstract Schematic illustration of the microfluidic microsphere based Microfluidic Lab-On-Chip device for near real-time insulin monitoring.

     

Generation,spectroscopic characterization and antioxidant activity of tetracoordinate and hexacoordinate complexes of diethylgermanium(IV) of relatively sterically undemanding N-protected amino acids and sterically demanding heterocyclic β-diketones containing radical sensitive Ge-O bond

Two new sets of diethylgermanium(IV) complexes of the types Et₂GeA₂ and Et₂GeB₂ have been generated by the reactions of diethylgermanium(IV) dichloride with sodium salts of N-protected amino acids (AH) [where AH = , R = -CH(CH₃)C₂H₅: A₁H, R = -CH₂CH(CH₃)₂: A₂H, R = -CH(CH₃)₂: A₃H] and with sodium salts of sterically demanding heterocyclic β-diketones (BH) [where BH = , R’ = -C₆H₅: B₁H, R’ = -p-(Cl)C₆H₄: B₂H, R’ = -CH₃: B₃H, R = -C₂H₅: B₄H], respectively in 1:2 molar ratios in refluxing dry benzene. Plausible structures of these complexes were suggested on the basis of physico-chemical and spectroscopic studies. It is suggested that the complexes of the types Et₂GeA₂ and Et₂GeB₂ contain four coordinated and six coordinated germanium centers, respectively. The ligands and organogermanium(IV) complexes were evaluated for their free radical scavenging activity by DPPH method. These compounds/complexes demonstrate potential antioxidant activity.     

I/O-efficient algorithms for computing planar geometric spanners

We present I/O-efficient algorithms for computing planar Steiner spanners for point sets and sets of polygonal obstacles in the plane.