Supramolecular Arrangement and DFT analysis of Zinc(II) Schiff Bases: An Insight towards the Influence of Compartmental Ligands on Binding Interaction with Protein

We report, for the first time, a detailed crystallographic study of the supramolecular arrangement for a set of zinc(II) Schiff base complexes containing the ligand 2,6-bis((E)-((2-(dimethylamino)ethyl)imino)methyl)-4-R-phenol], where R=methyl/tert-butyl/chloro. The supramolecular study acts as a pre-screening tool for selecting the compartmental ligand R of the Schiff base for effective binding with a targeted protein, bovine serum albumin (BSA). The most stable hexagonal arrangement of the complex [Zn − Me] (R=Me) stabilises the ligand with the highest FMO energy gap (ΔE=4.22 eV) and lowest number of conformations during binding with BSA. In contrast, formation of unstable 3D columnar vertebra for [Zn − Cl] (R=Cl) tend to activate the system with lowest FMO gap (3.75 eV) with highest spontaneity factor in molecular docking. Molecular docking analyses reported in terms of 2D LigPlot+ identified site A, a cleft of domains IB, IIIA and IIIB, as the most probable protein binding site of BSA. Arg144, Glu424, Ser428, Ile455 and Lys114 form the most probable interactions irrespective of the type of compartmental ligands R of the Schiff base whereas Arg185, Glu519, His145, Ile522 act as the differentiating residues with ΔG=−7.3 kcal mol⁻¹.     

Calibration and optimization of alpha-beta separation procedures for determination of radium/radon in single- and two-phase liquid scintillation systems

Liquid scintillation alpha beta discrimination technique based on pulse shape analysis (PSA) was evaluated for determination of ²²⁶Ra and ²²²Rn in water samples. In view of the significance of calibration, for the reliable and precise determination of ²²⁶Ra and ²²²Rn concentrations in water samples, calibration procedures were standardized for single and two phase systems using Quantulus 1220 liquid scintillation counter. PSA optimization and efficiency calibrations were performed using ²²⁶Ra standard rather than conventionally used pure alpha and beta standards and substantiated by measuring the activity concentrations of ²²⁶Ra and ²²²Rn in the spiked water samples.     

Measurement of soil/dust arsenic by gas phase chemiluminescence

A gas phase chemiluminescence (GPCL)-based method for trace measurement of arsenic has been recently described for the measurement of arsenic in water. The principle is based on the reduction of inorganic As to AsH₃ at a controlled pH (the choice of pH governs whether only As(III) or all inorganic As is converted) and the reaction of AsH₃ with O₃ to produce chemiluminescence (Idowu et al., Anal. Chem. 78 (2006) 7088-7097). The same general principle has also been used in postcolumn reaction detection of As, where As species are separated chromatographically, then converted into inorganic As by passing through a UV photochemical reactor followed by AsH₃ generation and CL reaction with ozone (Idowu and Dasgupta, Anal. Chem. 79 (2007) 9197-9204). In the present paper we describe the measurement of As in different soil and dust samples by serial extraction with water, citric acid, sulfuric acid and nitric acid. We also compare parallel measurements for total As by induction coupled plasma mass spectrometry (ICP-MS). As(V) was the only species found in our samples. Because of chloride interference of isobaric ArCl⁺ ICP-MS analyses could only be carried out by standard addition; these results were highly correlated with direct GPCL and LC-GPCL results (r² = 0.9935 and 1.0000, respectively). The limit of detection (LOD) in the extracts was 0.36 μg/L by direct GPCL compared to 0.1 μg/L by ICP-MS. In sulfuric acid-based extracts, the LC-GPCL method provided LODs inferior to those previously observed for water-based standards and were 2.6, 1.3, 6.7, and 6.4 μg/L for As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA), respectively.     

Thermal hysteresis of some important physical properties of nanoparticles

Gold nanoparticles show thermal hysteresis with properties such as surface plasmon absorption, conductivity, and zeta potential. The direction of the incremental change in plasmon peak position and its extinction depend on the nature of surface conjugation. The thermal profile of a surface plasmon resonance spectrum for nanoparticles may serve as a signature for the associated small molecule or macromolecule on which it is seeded. The thermal responses of zeta potential and conductivity profile are found to be independent of the surface conjugation with the later being subjected to a phase transition phenomenon as revealed by a temperature criticality.     

Chromatographic peak resolution using Microsoft Excel Solver. The merit of time shifting input arrays

Resolution of overlapped chromatographic peaks is generally accomplished by modeling the peaks as Gaussian or modified Gaussian functions. It is possible, even preferable, to use actual single analyte input responses for this purpose and a nonlinear least squares minimization routine such as that provided by Microsoft Excel Solver can then provide the resolution. In practice, the quality of the results obtained varies greatly due to small shifts in retention time. I show here that such deconvolution can be considerably improved if one or more of the response arrays are iteratively shifted in time.     

Isobaric metabolite interferences and the requirement for close examination of raw data in addition to stringent chromatographic separations in liquid chromatography/tandem mass spectrometric analysis of drugs in biological matrix

In addition to matrix effects, common interferences observed in liquid chromatography/tandem mass spectrometry (LC/MS/MS) analyses can be caused by the response of drug-related metabolites to the multiple reaction monitoring (MRM) channel of a given drug, as a result of in-source reactions or decomposition of either phase I or II metabolites. However, it has been largely ignored that, for some drugs, metabolism can lead to the formation of isobaric or isomeric metabolites that exhibit the same MRM transitions as parent drugs. The present study describes two examples demonstrating that interference caused by isobaric or isomeric metabolites is a practical issue in analyzing biological samples by LC/MS/MS. In the first case, two sequential metabolic reactions, demethylation followed by oxidation of a primary alcohol moiety to a carboxylic acid, produced an isobaric metabolite that exhibits a MRM transition identical to the parent drug. Because the drug compound was rapidly metabolized in rats and completely disappeared in plasma samples, the isobaric metabolite appeared as a single peak in the total ion current (TIC) trace and could easily be quantified as the drug since it was eluted at a retention time very close to that of the drug in a 12-min LC run. In the second example, metabolism via the ring-opening of a substituted isoxazole moiety led to the formation of an isomeric product that showed an almost identical collision-induced dissociation (CID) MS spectrum as the original drug. Because two components were co-eluted, the isomeric product could be mistakenly quantified and reported by data processing software as the parent drug if the TIC trace was not carefully inspected. Nowadays, all LC/MS data are processed by computer software in a highly automated fashion, and some analysts may spend much less time to visually examine raw TIC traces than they used to do. Two examples described in this article remind us that quality data require both adequate chromatographic separations and close examination of raw data in LC/MS/MS analyses of drugs in biological matrix.     

Comparison of radiometric and non-radiometric methods for uranium determination in groundwater of Punjab,India

Uranium in groundwater samples collected from Punjab state, India was determined using radiometric methods (extractive liquid scintillation and Cerenkov counting). Experimental conditions were optimized by studying the effect of sample pH, quenching and amount of extracting agent added to the scintillation cocktail on recovery of uranium. To ensure the accuracy of results, both radiometric methods were compared with non radiometric method such as adsorptive stripping voltammetry and found to be very good agreement. The distinct advantage of proposed radiometric methods is almost 100 % effective especially extractive liquid scintillation for simultaneous measurement of alpha and beta emitting radionuclides with fast and simple sample preparation.