Experimental investigations of thermal stability of some morpholinecarbamic acid complexes of copper(II) and zinc(II)

Some new carbamates, viz. M(MorphcbmH)₂X₂ (MorphcbmH = morpholinecarbamic acid, M = Cu, X = Cl, ClO₄,NO₃; M = Zn, X = Cl, ClO₄, NO₃, CH₃COO and X₂ = SO₄), have been synthesized and investigated. Compounds were characterized by elemental analysis, molar conductance, FT infrared, fluorescence, NMR (¹H and ¹³C) and solution electronic absorption spectral studies. Room temperature field-dependent magnetic susceptibility measurements, PXRD spectral and cyclic voltametric studies were also conducted. Chelating bidentate mode of coordination of ligand, MorphcbmH with four coordination around metal ion has been proposed. Ligand and its compounds have also been studied using non-isothermal thermogravimetric analysis and differential scanning calorimetric analytical techniques which inferred formation of metal oxide/MCO₃ as final thermal decomposition products. Compounds were screened against the lipase enzyme for assaying their enzyme activity and were found to retard the lipase activity from 48.16 to 0.044 µmol mL^?1 min^?1.     

Capillary zone electrophoresis for the analysis of glycoforms of cellobiohydrolase

Cellobiohydrolase (CBH) is an important enzyme for the conversion of lignocellulosic biomass to ethanol. This work separated the glycoforms of CBH possessing different numbers of neutral mannoses using capillary zone electrophoresis (CZE) in a 50 mM, pH 7.5 phosphate buffer. The method analysed CBH in an intact form using a polyacrylamide coated fused silica capillary without requiring additives or labelling of the enzyme. The migration time of the major peak was found to be 21.6±0.1 min (n=3) and the approach is suitable for testing of batch-to-batch consistency of CBH. Ease-of-use, automation and speed are the other benefits due to which the use of CZE for analysing glycoforms of CBH was concluded to be ideal.     

Triorganotin(IV) derivatives of umbelliferone (7-hydroxycoumarin) and their adducts with 1,10-phenanthroline: synthesis, structural and biological studies

New triorganotin(IV) derivatives of the general formula R₃Sn(Umb) (where, R = Me, n-Bu and Ph; Umb = umbelliferone anion) have been synthesized using sodium salt method. Further, the adducts of the general formula R₃Sn(Umb) · phen (where R = Me and Ph; phen = 1,10-phenanthroline) have also been synthesized by the interaction of the triorganotin(IV) derivatives of umbelliferone with 1,10-phenanthroline. The bonding and coordination behavior of these derivatives are discussed on the basis of IR, NMR (¹H, ¹³C and ¹¹⁹Sn), and ¹¹⁹Sn Mössbauer spectroscopic studies. These investigations indicate that umbelliferone acts as a monoanionic bidentate ligand in R₃Sn(Umb) coordinating through O(7) and O(1) in the solid-state. These polymeric R₃Sn(Umb) derivatives (where R = Me and n-Bu) have been proposed to have a trans-trigonal bipyramidal geometry with the three R groups in equatorial positions, while the axial positions are occupied by a phenolic oxygen and the O(1) atom from the adjacent molecule. A pseudotetrahedral geometry has been suggested for Ph₃Sn(Umb). A distorted octahedral geometry around tin has been proposed for R₃Sn(Umb) · phen, in which umbelliferone anion acts as a monodentate ligand coordinating through phenolic oxygen O(7). The newly synthesized derivatives have been assayed for their anti-inflammatory, cardiovascular and anti-microbial activities. The average LD₅₀ values >1000 mg kg⁻¹ of these derivatives indicate their safety margin. Among all the compounds tested, Ph₃Sn(Umb) · phen has been found to show potent anti-inflammatory activity with low mammalian toxicity and mild hypotensive activity.     

A standard protocol for single nucleotide primer extension in the human genome using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Analysis of single nucleotide polymorphisms (SNPs) has become an increasingly important area of research, with numerous applications in medical genetics, population genetics, forensic science, and agricultural biotechnology. Large-scale SNP analyses require the development of methodologies that are economical, flexible, accurate and capable of automation. Primer extension in conjunction with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is currently emerging as a potential method for high-throughput SNP genotyping. We have evaluated a number of published primer extension methods and refined a simple and robust protocol to analyze human autosomal disease-causing mutations and population genetic markers on the Y-chromosome. Twelve different variant sites were examined, and homozygotes, heterozygotes and hemizygotes were accurately typed. A 100% concordance was observed between SNP genotypes obtained using the MALDI-TOFMS technique and alternative genotyping methods, such as restriction fragment length polymorphism (RFLP) assays and denaturing high-performance liquid chromatography (DHPLC). Since multiple polymorphisms can be detected in single reactions, the method provides a cost-effective approach for SNP analysis. The protocol is also extremely flexible (able to accommodate new markers) and can be adapted to a number of platforms without the use of commercial kits.     

X-ray scattering reveals ion clustering of dilute chromium species in molten chloride medium

Enhancing the solar energy storage and power delivery afforded by emerging molten salt-based technologies requires a fundamental understanding of the complex interplay between structure and dynamics of the ions in the high-temperature media. Here we report results from a comprehensive study integrating synchrotron X-ray scattering experiments, ab initio molecular dynamics simulations and rate theory concepts to investigate the behavior of dilute Cr³⁺ metal ions in a molten KCl–MgCl₂ salt. Our analysis of experimental results assisted by a hybrid transition state-Marcus theory model reveals unexpected clustering of chromium species leading to the formation of persistent octahedral Cr–Cr dimers in the high-temperature low Cr³⁺ concentration melt. Furthermore, our integrated approach shows that dynamical processes in the molten salt system are primarily governed by the charge density of the constituent ions, with Cr³⁺ exhibiting the slowest short-time dynamics. These findings challenge several assumptions regarding specific ionic interactions and transport in molten salts, where aggregation of dilute species is not statistically expected, particularly at high temperature.

Ion clustering of dilute chromium species was unexpectedly revealed in a high-temperature molten chloride salt, challenging several long-held assumptions regarding specific ionic interactions and transport in molten ionic media.     

The Kinetics and Mechanism of Ligand Substitution Reaction of Aquapentacyanoruthenate(II) with Nitroso-R-salt and α-Nitroso-β-Naphthol in Presence of Anionic Surfactant Micelle

The kinetics and mechanism of ligand substitution reaction of coordinated water in complex, [Ru(CN)₅H₂O]^3? by two incoming naphthalene substituted ligands [Lⁿ], that is, Lⁿ = nitroso-R-salt (NRS) and α-nitroso-β-naphthol (αNβN) have been studied spectrophotometrically by following an increase in absorbance at λ_max = 525 nm in aqueous medium in presence of anionic surfactant micelle, sodium dodecyl sulphate (SDS) at 25.0 ± 0.1°C as a function of pH, [nitro-R-salt], [α-nitroso-β-naphthol], [Ru(CN)₅H₂O^3?], [SDS] and ionic strength(I) under pseudo-first-order conditions by taking excess [L]. The values of pseudo-first-order rate constants (k_obs) were evaluated from the slope of ln(A_∞ ? A_t) versus time plots for each variation. Both systems were found to follow a dissociative mechanism (D), through the formation of an intermediate, [Ru(CN)₅]^3?. The activation parameters, that is, enthalpy of activation (ΔH^≠) and entropy of activation (ΔS^≠) were computed from the slope and intercept of ln(k_f/T) versus (1/T) plot, which support the proposed mechanistic scheme.     

Rapid Determination of Non-Steroidal Anti-Inflammatory Drugs in Urine Samples after In-Matrix Derivatization and Fabric Phase Sorptive Extraction-Gas Chromatography-Mass Spectrometry Analysis

Fabric phase sorptive extraction (FPSE) has become a popular sorptive-based microextraction technique for the rapid analysis of a wide variety of analytes in complex matrices. The present study describes a simple and green analytical protocol based on in-matrix methyl chloroformate (MCF) derivatization of non-steroidal anti-inflammatory (NSAID) drugs in urine samples followed by FPSE and gas chromatography-mass spectrometry (GC-MS) analysis. Use of MCF as derivatizing reagent saves substantial amounts of time, reagent and energy, and can be directly performed in aqueous samples without any sample pre-treatment. The derivatized analytes were extracted using sol–gel Carbowax 20M coated FPSE membrane and eluted in 0.5 mL of MeOH for GC-MS analysis. A chemometric design of experiment-based approach was utilized comprising a Placket–Burman design (PBD) and central composite design (CCD) for screening and optimization of significant variables of derivatization and FPSE protocol, respectively. Under optimized conditions, the proposed FPSE-GC-MS method exhibited good linearity in the range of 0.1–10 µg mL⁻¹ with coefficients of determination (R²) in the range of 0.998–0.999. The intra-day and inter-day precisions for the proposed method were lower than <7% and <10%, respectively. The developed method has been successfully applied to the determination of NSAIDs in urine samples of patients under their medication. Finally, the green character of the proposed method was evaluated using ComplexGAPI tool. The proposed method will pave the way for simper analysis of polar drugs by FPSE-GC-MS.     

Mobile interstitial model and mobile electron model of mechano-induced luminescence in coloured alkali halide crystals

A theoretical study is made on the mobile interstitial and mobile electron models of mechano-induced luminescence in coloured alkali halide crystals. Equations derived indicate that the mechanoluminescence intensity should depend on several factors like strain rate, applied stress, temperature, density of F-centres and volume of crystal. The equations also involve the efficiency and decay time of mechanoluminescence. Results of mobile interstitial and mobile electron models are compared with the experimental observations, which indicated that the latter is more suitable as compared to the former. From the temperature dependence of ML, the energy gaps between the dislocation band and ground state of F-centre is calculated which are 0.08, 0.072 and 0.09 eV for KCl, KBr and NaCl crystals, respectively. The theory predicts that the decay of ML intensity is related to the process of stress relaxation in crystals.