Synthesis,biological evaluation,and molecular docking study of pyridine clubbed 1,3,4-oxadiazoles as potential antituberculars

A series of pyridine clubbed 1,3,4-oxadiazole derivatives were efficiently synthesized, characterized by standard spectral techniques and evaluated for their in vitro antitubercular activity against Mycobacterium tuberculosis (MTB) H₃₇Ra and Mycobacterium bovis BCG in active and dormant state using an established methods. Compounds 5a, 5m, and 5t were identified as the most active compounds against MTB. Molecular docking was performed against MTB enoyl-ACP (CoA) reductase (FabI/ENR/InhA) enzyme to predict the binding modes and affinity. The theoretical predictions from molecular docking could establish a link between the observed biological activity and the binding affinity shedding light into specific bonded and non-bonded interactions influencing the activity. The active compounds were studied for cytotoxicity against three cell lines and were found to be non-cytotoxic. Specificity of these compounds was checked by screening them for their antibacterial activity against four bacterial strains.     

Benzoylation of polyphenylene oxide: Characterization and gas permeability investigations

Benzoylation of polyphenylene oxide (PPO) was carried out with aromatic acid chlorides bearing specific groups at para-position (H, methyl, Br, Cl and nitro), which differ in their polarity and bulk. The reaction conditions were optimized individually to get the high degree of substitution. These materials were characterized for thermal as well as other physical properties that are known to affect the gas permeation. In a series investigated, the nitrobenzoyl substitution on PPO resulted in the highest increase in glass transition temperature and the lowest thermal stability. An estimation of the packing density parameters—fractional free volume by density measurement and the d-spacing by X-ray diffraction analysis showed an increase in the packing density. The gas permeability was found to decrease in all the cases of benzoylation. The helium and oxygen based selectivities were increased, while CO₂ based selectivities were decreased. The unusual trend observed in the gas permeation properties is explained on the basis of nature of substituent and the degree of substitution.     

A host-guest optical sensor for aliphatic amines based on lipophilic cyclodextrin

A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10^–6 to 8.0 × 10^–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery. Received: 21 November 1999 / Revised: 10 January 2000 / Accepted: 15 January 2000     

Density functional theory study of ω phase in steel with varied alloying elements

The presence of a long-abandoned hexagonal omega (ω) phase in steel samples is recently gaining momentum owing to the advances in transmission electron microscopy (TEM) measurements, even though it is already reported in other transition-metal alloys. The stabilization of this metastable phase is mainly investigated in presence of C, even though the formation of the ω phase is attributed to the combined effect of many factors, one among which is the enrichment of solute elements such as Al, Mn, Si, C, and Cr in the nanometer-sized regimes. The present study investigates the effect of the above alloying elements in ω-Fe using density functional theory (DFT) calculations. It is seen that the magnetic states of the atoms play a major role in the stability of ω-Fe. Cohesive energy calculations show that the alloying elements affect the energetics and stabilization of ω-Fe. Further, density of states calculations reveal the variation in d-band occupancy in the presence of alloying elements, which in turn affects the cohesive energy. Phonon band structure calculations show that only ω-Fe with substitutional C shows positive frequencies and hence possess thermodynamic stability. Finally, we confirm the existence of ω-Fe using TEM measurements of a steel sample containing the same alloying elements. Our results can shed light on the stabilization of the ω in other transition-metal alloys as well, in the presence of minor alloying elements.     

Accelerated convergence of molecular free energy via superposition approximation-based reference states

The free energy of a molecular system can, at least in principle, be computed by thermodynamic perturbation from a reference system whose free energy is known. The convergence of such a calculation depends critically on the conformational overlap between the reference and the physical systems. One approach to defining a suitable reference system is to construct it from the one-dimensional marginal probability distribution functions (PDFs) of internal coordinates observed in a molecular simulation. However, the conformational overlap of this reference system tends to decline steeply with increasing dimensionality, due to the neglect of correlations among the coordinates. Here, we test a reference system that can account for pairwise correlations among the internal coordinates, as captured by their two-dimensional marginal PDFs derived from a molecular simulation. Incorporating pairwise correlations in the reference system is found to dramatically improve the convergence of the free energy estimates relative to the first-order reference system, due to increased conformational overlap with the physical distribution.     

Solid state electrochemical reaction in photocells made using conducting polyaniline and sensitized with methylene blue

The effect of small concentration of methylene blue (MB) on photocurrents was studied in solid state photoelectrochemical cells fabricated using conducting polyaniline (PANI) coated electrodes sandwiched with a solid polymer electrolyte, viz. poly(vinyl alcohol) (PVA) with phosphoric acid. These exhibit good photoresponse to visible light (maximum photosensitivity factor of the order of 10). The current-voltage (I-V) characteristics in such cells reveal that the charge transport is ohmic. Also, an electrochemical reaction (motion of Cl^– from SPE+MB to PANI) is observed at 1.2–1.3 V, which gives rise to a sudden increase of current at this particular voltage. The presence of illumination enhances this electrochemical reaction. The combined effect, i.e. ohmic charge transport and an electrochemical reaction, is observed in the I-V characteristics. Along with the dye concentration, the photosensitivity is observed to be field/voltage dependent. The sensitization effects are due to lowering of the potential barrier formed at the PANI/SPE+MB interface under illumination. Electronic Publication     

In situ radiation measurement and estimation of U/Th ratio to reflect on the uranium bearing potential zone in metamorphic rocks of Mahendragarh district, Haryana

Gross gamma radiation survey was carried out using Nal(Tl) scintillator based portable gamma ray spectrometer (PGRS) around areas of Gaonri, Dholera, Pachnota and Meghot in Mahendragarh district, Haryana. Geologically the area forms part of north Delhi fold belt comprising calc-silicate, quartz biotite schist, impure marble, quartzite and pegmatite rocks. Equivalent uranium (eU₃O₈) concentration in ppm was estimated in situ on a regular grid pattern of 500 m (E-W) × 1000 m (N-S) and grab samples were collected at grid locations for analyzing in the laboratory for estimating the contents of eU₃O_s Ra_eq, ThO₂ and %K. A comparison with the laboratory analysed grab samples for eU₃0₈ data and in situ radiation measurements shows a good match of the two sets of data. The in situ measurements indicate higher concentration of eU₃O₈ in Chapra Bibipur in northeastern most corners, Maghot area in central part, Gaonri in western part and Pachnota in southwestern part of the study area. As index to uranium favorability, U(Ra_eq)-Th contour map (prepared using Surfer software with Krieging interpolation method for this grid size) based on the data on grab samples was generated which show three major clusters of relatively high U-Th ratio. The blocks delineated are enriched in sodic mineral albite which support albite hosted uranium mineralization potential in metamorphic rocks in Haryana.      

Crystallization studies of isotactic polypropylene containing nanostructured polyhedral oligomeric silsesquioxane molecules under quiescent and shear conditions

Crystallization studies at quiescent and shear states in isotactic polypropylene (iPP) containing nanostructured polyhedral oligomeric silsesquioxane (POSS) molecules were performed with in situ small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC). DSC was used to characterize the quiescent crystallization behavior. It was observed that the addition of POSS molecules increased the crystallization rate of iPP under both isothermal and nonisothermal conditions, which suggests that POSS crystals act as nucleating agents. Furthermore, the crystallization rate was significantly reduced at a POSS concentration of 30 wt %, which suggests a retarded growth mechanism due to the molecular dispersion of POSS in the matrix. In situ SAXS was used to study the behavior of shear‐induced crystallization at temperatures of 140, 145, and 150 °C in samples with POSS concentrations of 10, 20, and 30 wt %. The SAXS patterns showed scattering maxima along the shear direction, which corresponded to a lamellar structure developed perpendicularly to the flow direction. The crystallization half‐time was calculated from the total scattered intensity of the SAXS image. The oriented fraction, defined as the fraction of scattered intensity from the oriented component to the total scattered intensity, was also calculated. The addition of POSS significantly increased the crystallization rate during shear compared with the rate for the neat polymer without POSS. We postulate that although POSS crystals have a limited role in shear‐induced crystallization, molecularly dispersed POSS molecules behave as weak crosslinkers in polymer melts and increase the relaxation time of iPP chains after shear. Therefore, the overall orientation of the polymer chains is improved and a faster crystallization rate is obtained with the addition of POSS. Moreover, higher POSS concentrations resulted in faster crystallization rates during shear. The addition of POSS decreased the average long‐period value of crystallized iPP after shear, which indicates that iPP nuclei are probably initiated in large numbers near molecularly dispersed POSS molecules. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2727–2739, 2001