Comparison of aromatic NH···π, OH···π, and CH···π interactions of alanine using MP2, CCSD, and DFT methods

A comparison of the performance of various density functional methods including long‐range corrected and dispersion corrected methods [MPW1PW91, B3LYP, B3PW91, B97‐D, B1B95, MPWB1K, M06‐2X, SVWN5, ωB97XD, long‐range correction (LC)‐ωPBE, and CAM‐B3LYP using 6‐31+G(d,p) basis set] in the study of CH···π, OH···π, and NH···π interactions were done using weak complexes of neutral (A) and cationic (A⁺) forms of alanine with benzene by taking the Møller–Plesset (MP2)/6‐31+G(d,p) results as the reference. Further, the binding energies of the neutral alanine–benzene complexes were assessed at coupled cluster (CCSD)/6‐31G(d,p) method. Analysis of the molecular geometries and interaction energies at density functional theory (DFT), MP2, CCSD methods and CCSD(T) single point level reveal that MP2 is the best overall performer for noncovalent interactions giving accuracy close to CCSD method. MPWB1K fared better in interaction energy calculations than other DFT methods. In the case of M06‐2X, SVWN5, and the dispersion corrected B97‐D, the interaction energies are significantly overrated for neutral systems compared to other methods. However, for cationic systems, B97‐D yields structures and interaction energies similar to MP2 and MPWB1K methods. Among the long‐range corrected methods, LC‐ωPBE and CAM‐B3LYP methods show close agreement with MP2 values while ωB97XD energies are notably higher than MP2 values. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010     

Investigations on multiply charged nuclei of the primary cosmic radiation near the geomagnetic equator using nuclear emulsions

The charge spectrum obtained from measurements made on tracks of 1329 nuclei of the cosmic radiation of Z?6 and E?7·5 GeV/n has been studied in detail using emulsion stacks exposed over Hyderabad, India (cut off rigidity=16·8 GV) at a depth of 6·8 g/cm² of air for 7¼ hrs. This spectrum has been compared with that available for nuclei of E≥1·5 GeV/n. Within the limits of experimental errors, no dependence of the flux values or ratios of intensities with energy are noticed. This result has important implications on the origin and history of the cosmic radiation. Integral energy spectra of M and H-nuclei have been derived making use of the flux values at the two locations; the spectra thus derived have the least errors associated with these.     

Intensity clamping and re-focusing of intense femtosecond laser pulses in nitrogen molecular gas

We present results of measurements of fluorescence spectra due to the interaction of a Ti:sapphire laser pulse with N₂ molecules at different gas pressures and pulse energies. The analysis of the data together with the results of numerical simulations, using a propagation model, reveal signatures of the phenomena of intensity clamping and of re-focusing of the laser pulse at high gas pressure. The laser pulse energy for intensity clamping as a function of the gas pressure is determined. Received: 21 May 2001 / Revised version: 10 July 2001 / Published online: 19 September 2001     

Facile preparation of a cellulose microfibers–exfoliated graphite composite: a robust sensor for determining dopamine in biological samples

A simple and robust dopamine (DA) sensor was developed using a cellulose microfibers (CMF)–exfoliated graphite composite-modified screen-printed carbon electrode (SPCE) for the first time. The graphite-CMF composite was prepared by sonication of pristine graphite in CMF solution and was characterized by high-resolution scanning electron microscopy, Fourier transform, infrared, and Raman spectroscopy. The cyclic voltammetry results reveal that the graphite-CMF composite modified SPCE has superior electrocatalytic activity against oxidation of dopamine than SPCE modified with pristine graphite and CMF. The presence of large edge plane defects on exfoliated graphite and abundant oxygen functional groups of CMF enhance electrocatalytic activity and decrease potential to oxidize DA. Differential pulse voltammetry was used to quantify DA using the graphite-CMF composite-modified SPCE and demonstrated a linear response for DA detection in the range of 0.06–134.5 µM. The sensor shows a detection limit at 10 nM with an appropriate sensitivity and displays appropriate recovery of DA in human serum samples with good repeatability. Sensor selectivity is demonstrated in the presence of 50-fold concentrations of potentially active interfering compounds including ascorbic acid, uric acid, and dihydroxybenzene isomers.     

Thermal Decomposition of Strontium Iron Citrate

The citrate precursor method has been used to synthesise ultrafine SrFe₁₂O¹⁹. The thermal decomposition of citrate precursor SrFe₁₂O₆ (C₆H₆O₇)₁₃ was investigated by TG, DTG and DTA techniques, gas and chemical analyses. The citrate precursor on decomposition in static air atmosphere yields pure and stoichiometric SrFe₁₂O₁₉. The decomposition consists of three major steps, the formation of acetone dicarboxylate complex occurs around 165°C. The citrate groups are completely destroyed in the temperature range 195–315°C resulting in the formation of complex carbonate with the evolution of acetone and CO₂ gas. The decomposition of carbonate results in the formation of ultrafine SrFe₁₂O₁₉ below 550°C with the evolution of CO₂ gas. The ultrafine particles are observed as platelet clusters having crystallite size 13 nm and surface area 76.4 m² g^?1. The citrate precursor and the decomposed products were characterised by IR, NMR, XRD, SEM and surface area measurements.     

Facile synthesis of TMS-protected trifluoromethylated alcohols using trifluoromethyltrimethylsilane (TMSCF3) and various nucleophilic catalysts in DMF

Organofluorine compounds are becoming increasingly important in different fields, such as material science, agro chemistry, and the pharmaceutical industry. Nucleophilic trifluoromethylation is one of the widely used methods to incorporate a trifluoromethyl moiety into organic molecules. We have carried out extensive studies to develop varieties of easily accessible nucleophilic catalysts to promote such reactions. TMS-protected trifluoromethylated alcohols were prepared from both aldehydes and ketones in excellent yields using catalytic amount of amine N-oxide. Carbonate and phosphate salts also showed efficient catalytic activity toward this reaction. These reactions were highly solvent dependent, and DMF was found to be the most suitable one among the various solvents studied. All these reactions proceeded under very mild conditions, giving clean products and avoiding the use of any fluoride initiators or expensive catalysts, and extremely water-free conditions. The mechanism for the reaction is discussed in detail. DFT calculations were performed on the possible reaction intermediates using the Gaussian 03 program at B3LYP/6-311+G* level to support the proposed mechanism.     

Energy‐induced polymorphic changes in poly(vinylidene fluoride): How ultrasonication results in polymer with predominantly γ phase

Self‐polarized poly(vinylidene fluoride) (PVDF) films were prepared via solution crystallization technique wherein the polymorphism of the films was controlled from α phase (>85%) to γ phase (>90%) by varying the time of ultrasonication. On increasing ultrasonication time up to 60 min, γ phase crystallites were found to be self‐aligned in the matrix while an equal proportion of α and γ phases coexist in the PVDF films ultrasonicated for 120 min. The phase conversion as well as inversion was evident from Fourier transform infrared, X‐ray diffraction, and differential scanning calorimetry analyses. Microscopic images of films ultrasonicated for 60 min showed a scrolled lamellar morphology while those sonicated for 120 min showed mixture of scrolled lamellar and spherulitic morphology. With the help of computational studies, it is explained that a large amount of energy is required for transforming trans‐gauche‐trans‐gauche into trans‐trans‐trans‐gauche conformation which is provided by ultrasonication. The mechanism of γ phase formation is proposed based on the experimental and theoretical approaches. Our studies show that just by tuning the time of ultrasonication, PVDF films with various morphologies can be processed; either one with predominantly electroactive γ phase with superior electrical properties or one with equal proportion of α and γ phases with superior mechanical properties. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 40–50     

Role of structural water molecule in HIV protease-inhibitor complexes: a QM/MM study

Structural water molecule 301 found at the interface of HIV protease-inhibitor complexes function as a hydrogen bond (H-bond) donor to carbonyl groups of the inhibitor as well as H-bond acceptor to amide/amine groups of the flap region of the protease. In this study, six systems of HIV protease-inhibitor complexes were analyzed, which have the presence of this "conserved" structural water molecule using a two-layer QM/MM ONIOM method. The combination of QM/MM and QM method enabled the calculation of strain energies of the bound ligands as well as the determination of their binding energies in the ligand-water and ligand-water-protease complexes. Although the ligand experiences considerable strain in the protein bound structure, the H-bond interactions through the structural water overcomes this strain effect to give a net stability in the range of 16-24 kcal/mol. For instance, in 1HIV system, the strain energy of the ligand was 12.2 kcal/mol, whereas the binding energy associated with the structural water molecule was 20.8 kcal/mol. In most of the cases, the calculated binding energy of structural water molecule showed the same trend as that of the experimental binding free energy values. Further, the classical MD simulations carried out on 1HVL system with and without structural water 301 showed that this conserved water molecule enhances the H-bond dynamics occurring at the Asp-bound active site region of the protease-inhibitor system, and therefore it will have a direct influence on the mechanism of drug action.     

Size quantization effect in GaAs nanocrystals

GaAs nanocrystals have been synthesized by an electrochemical route from the acidic solutions of metallic gallium and arsenic oxide. Structural analysis by transmission electron microscopy (TEM), reveales the presence of orthorhombic phase, in contrast to the usual cubic phase of bulk GaAs. Well separated GaAs nanocrystals having sizes in the range of 7 to 15 nm are identified in the TEM micrograph. Optical absorption shows a strong excitonic absorption band on account of quantum size effect associated with GaAs nanocrystals. Photoluminescence, recorded at 300 K under ultraviolet excitation (369 nm), shows the HOMO-LUMO transition band as well as the red shifted bands. Micro-Raman analysis shows a phonon mode centered at 250 cm⁻¹ associated with a point defect.     

Piperidinium 3‐[(4‐hydroxy‐5,7‐di­methyl‐2‐oxo‐2H‐chromen‐3‐yl)­phenyl­methyl]‐5,7‐di­methyl‐2‐oxo‐2H‐chromen‐4‐olate

In the title salt, C₅H₁₂N⁺·C₂₉H₂₃O₆^?, both benzo­pyran systems are planar. Intermolecular N—H?O hydrogen bonds and a short O—H?O intramolecular hydrogen bond are observed in the structure.