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.     

MAS-NMR study of lithium zinc silicate glasses and glass-ceramics with various ZnO content

Lithium zinc silicate glasses of composition (mol%): 17.5Li₂O-(72−x)SiO₂-xZnO−5.1Na₂O−1.3P₂O₅−4.1B₂O₃, 5.5?x?17.7, were prepared by conventional melt-quenched technique and converted to glass-ceramic by controlled crystallization process. ²⁹Si and ³¹P MAS-NMR was used to characterize the structure of both glass and glass-ceramic samples. Despite the complex glass composition, Q², Q³ and Q⁴ sites are identified from ²⁹Si MAS-NMR, which relative intensities are found to vary with the ZnO content, indicating a network depolymerization by ZnO. Moreover, well separated Q³ and Q⁴ resonances for low ZnO content indicates the occurrence of phase separation. From ³¹P MAS-NMR, it is seen that phosphorus is mainly present in the form of ortho-(Q⁰) and pyro-phosphate (Q¹) structural units and variation of ZnO content did not have much effect on these resonances, which provides an additional evidence for phase separation in the glass. On conversion to glass-ceramics, lithium disilicate (Li₂Si₂O₅), lithium zinc ortho-silicate (Li₃Zn_0.5SiO₄), tridymite (SiO₂) and cristobalite (SiO₂) were identified as major silicate crystalline phases. Using ²⁹Si MAS-NMR, quantification of these silicate crystalline phases is carried out and correlated with the ZnO content in the glass-ceramics samples. In addition, ³¹P spectra unambiguously revealed the presence of crystalline Li₃PO₄ and (Na,Li)₃PO₄ in the glass-ceramics.     

Cd2+-induced conformational change of a synthetic metallopeptide: slow metal binding followed by a slower conformational change

A two-stranded alpha-helical coiled coil was prepared having a Cys 4 metal-binding site within its hydrophobic interior. The addition of Cd2+ results in the incorporation of 2 equiv of metal ion, which is accompanied by a conformational change of the peptide, as observed by circular dichroism (CD) spectroscopy. Isothermal titration calorimetry (ITC) shows that the addition of Cd2+ is accompanied by two thermodynamic events. A comparison of the time dependence of the ITC behavior with those of the UV absorption and CD behavior allows the assignment of these events to a preliminary endothermic metal-binding step followed by a slower exothermic conformational change.     

Simulation of Fibrillation of PC/LCP/Kevlar Blends and Its Characterizations

Kevlar fiber was fluorinated and oxy-fluorinated directly in presence of undiluted fluorine and fluorine gas mixture and processed with Polycarbonate and LCP at 320 °C under 20 rpm in a twin-screw extruder. The composites were then injection molded into dumbbell shaped specimens under different conditions like various mold temperatures, injection temperatures, injection speeds and mold filling rates. Various physico-chemical characterizations have been performed under definite processing parameter. Orientation of fibers under different injection parameters was evaluated using mold flow simulation technique. Most injection molded or extruded structures however, exhibit non-uniform fiber orientation across the final parts, with a diverging variety of different local fiber orientation states. Distinct skin and core regions were observed in the injection molded parts and it has also been found out that fiber orientation is different in skin and core region for both unmodified and modified derivative, which affects the flow behavior. Processing parameters significantly affect the fiber orientation pattern in the skin and core region for all blended materials. It is worth mentioning that the maximum fiber orientation occurred during the extrusion process at the wall but different extent of fiber orientation is observed during the injection molding depending on the shape of the dumbbell specimen. This fibrillation has been corroborated by the SEM study in both the skin and core region.     

Fractal model of polymer electrolyte to investigate influence of high energy irradiation in molecular distribution and molar mass average

Ionics - The present work is completely based on the theoretical investigation i.e. computer simulated study of the effect of gamma irradiation on the molecular weight distribution and the molar...     

Application of Multivariate Curve Resolution–Alternate Least Square Technique on Extracting Pure Spectral Components from Multiple Emitting Systems: a Case Study

Multiple emitting components in a fluorophoric system often produce complicated emission spectra. Extracting the individual spectral information from the composite spectra is important in order to comprehend the photophysical processes occurring in the multifluorophoric systems. Although the combination of Principal Component Analysis and Multivariate Curve Resolution-Alternate Least Square (PCA/MCR-ALS) technique is a well-known approach for curve deconvolution, its applicability in the spectral deconvolution of vibronically and electronically mixed up emitting systems as well as systems merged up with multiple electronic bands without a priori knowledge of the individual emitting species, is not properly studied. The present work highlights the strength of PCA/MCR-ALS in retrieving pure spectral information from the set of complex spectra arising out of the regular variation of causative factors that result in the variation of spectral composition. The retrieval of the emission bands utilizing the PCA/MCR-ALS technique has been made without having a priori information of the emitting species present in the multifluorophoric systems and the resolved spectra correspond well with the fluorescence spectra of the individual chemical species. The common curve fitting methods such as Gaussian and Lorentzian techniques have been found to be unsuccessful in providing meaningful photophysical information through the retrieved spectra. A comparative study of the curve fitting techniques MCR-ALS, Gaussian and Lorentzian in a set of complicated emission spectra of (i) pyrene and its excimer, (ii) pyrene and its excimer in presence of benzo[a]pyrene, and (iii) fisetin in bile salt medium is presented herein in details.     

Polynomially based multi-projection methods for Fredholm integral equations of the second kind

In this paper, we propose a multi-projection and iterated multi-projection methods for Fredholm integral equations of the second kind with a smooth kernel using polynomial bases. We obtain super-convergence rates for the approximate solutions, more precisely, we prove that in M-Galerkin and M-collocation methods not only iterative solution approximates the exact solution u in the supremum norm with the order of convergence n^-4k, but also the derivatives of approximate the corresponding derivatives of u in the supremum norm with the same order of convergence, n being the degree of polynomial approximation and k being the smoothness of the kernel.     

A unique twisted rod-like pattern due to π-π stacking induced host-guest self-assembly

Here, we reported a unique twisted rod-like nano-architecture of as-synthesized 4-fluorocinnmaoyl chloride derived polynorbornene (PNORCNF) on the addition of 1-pyrenemethanol (PM) as a sensing probe. A significant change in the PNORCNF/PM microenvironment's polarity was observed with increasing PM concentration keeping the solvent (THF) unaltered. The change in polarity could be well documented with the morphological changes of the PNORCNF/PM system. We proposed π-π interaction between PM and cinnamoyl moiety of PNORCNF for this type of well-controlled hierarchical self-aggregation.     

Microstructural analysis of neutron-irradiation induced changes in polyester fibre studied using EPMA

Electron microscopy is an important characterization technique for the study of textile fibre as it gives more information on fabric wear, nature of fibre fracture, chemical degradation, abrasion, fatigue and many others. Electron Probe Micro Analyzer (EPMA) micrographs of virgin and some neutron-irradiated samples (graphite coated) are discussed. The filament diameter, D, of virgin PET fibre obtained from EPMA study was 12.5 μn. The surface topography of single filament distinctly reveals the core and sheath parts of the filament. The core diameter of the virgin fibre was estimated to be 1.43 μm. The fibre irradiated at fluence 1 × 10¹² n/cm² shows radiation induced sphere like polymer balls or spherulites of diameter 2.27 μm in the expanded core region. Due to irradiation, the sheath area crosslinks with expanded core region, which may be responsible for increase of strength and hardness of the polymer materials. Moreover, the micrograph at 3000 X magnifications clearly shows that there is no preferred orientation of the polymer in any direction confirming the isotropic nature of the sample.      

Identification of Putative Vaccine and Drug Targets against the Methicillin-Resistant Staphylococcus aureus by Reverse Vaccinology and Subtractive Genomics Approaches

Methicillin-resistant Staphylococcus aureus (MRSA) is an opportunistic pathogen and responsible for causing life-threatening infections. The emergence of hypervirulent and multidrug-resistant (MDR) S. aureus strains led to challenging issues in antibiotic therapy. Consequently, the morbidity and mortality rates caused by S. aureus infections have a substantial impact on health concerns. The current worldwide prevalence of MRSA infections highlights the need for long-lasting preventive measures and strategies. Unfortunately, effective measures are limited. In this study, we focus on the identification of vaccine candidates and drug target proteins against the 16 strains of MRSA using reverse vaccinology and subtractive genomics approaches. Using the reverse vaccinology approach, 4 putative antigenic proteins were identified; among these, PrsA and EssA proteins were found to be more promising vaccine candidates. We applied a molecular docking approach of selected 8 drug target proteins with the drug-like molecules, revealing that the ZINC4235426 as potential drug molecule with favorable interactions with the target active site residues of 5 drug target proteins viz., biotin protein ligase, HPr kinase/phosphorylase, thymidylate kinase, UDP-N-acetylmuramoyl-L-alanyl-D-glutamate-L-lysine ligase, and pantothenate synthetase. Thus, the identified proteins can be used for further rational drug or vaccine design to identify novel therapeutic agents for the treatment of multidrug-resistant staphylococcal infection.