Computational insight towards the binding affinity and participation of aliphatic unsaturated sidearms of aza-18-crown-6 extractants for Sr2+ encapsulation in different solvent medium.

CONTEXT: Macrocyclic extractants capture cations in solution phase; therefore, their structures and energetics in different solvents are worth investigating. In this computational research work, the optimized geometry of three aza-18-crown-6 extractants (1-3) has been obtained in suitable solvent mediums to work out the influence of the solvation on their binding affinity with Sr2+. The designed macrocyclic extractants are remarkable as the N-substituted side chain bears the rarely examined simple aliphatic unsaturated double and triple bond. All significant structural perturbations of the macro ring wherein Sr2+ binds are examined. Prediction of the auxiliary effect of the simple aliphatic unsaturated side arm on the binding of Sr2+ through solvent competition or cation-pi interaction is undertaken. The binding affinity of the complex formed in the solvent and gas phases is calculated. Results obtained in this study favor the utilization of solvents of low dielectric constant (CHCl3 and DCM) for effective binding of Sr2+ ions by the extractants. METHOD: All DFT calculations were performed using the Gaussian 09 program. The optimized geometries and their structural features were visualized by GaussView. Density functional calculation involving B3LYP functional and LANL2DZ basis set was employed to obtain optimized geometry and energy of the extractants and their Sr2+ complex. The solvation effects were considered by employing the calculations with the polarized continuum model (PCM). The computational method's reliability was assured by comparing the optimized structure with that of X-ray reported structure of a similar type of complex.

Physicochemical, scavenging and anti-proliferative analyses of polysaccharides extracted from psyllium (Plantago ovata Forssk) husk and seeds.

Polysaccharides extracted from seeds and husk of psyllium were characterized for different physicochemical characteristics, and bioactivities. Extracted polysaccharides are comprised of d-xylose, l-arabinose, d-glucose, d-galactose, and l-rhamnose. Crude husk-polysaccharide was crystalline, whereas rest was amorphous in nature. Husk-polysaccharide was structurally stable, and purified fractions were thermostable. Crude polysaccharides were irregular in shape with non-porous smooth-surface, however purified husk-polysaccharides showed some porosity, and fibrous nature. Husk-polysaccharide showed higher viscosity compared to seed-polysaccharide, but viscosity decreased with the purification. Crude polysaccharides contained hydrogel-like behavior compared to corresponding purified fractions. The purified fractions of seed-polysaccharide showed the utmost antioxidant and scavenging activities with a half-maximal effective concentration of 347.40 ±â€¯1.79 and 362.72 ±â€¯2.75 µg, respectively. Crude seed-polysaccharide showed about 34% anti-proliferation on Huh-7, whereas its purified fractions showed 42% anti-proliferation on HeLa cell line. The study confirms that psyllium polysaccharides are potential natural antioxidant and anti-carcinogenic agent; however a detailed study is needed to explore psyllium for nutraceutical applications.

Association of non-tuberculous mycobacteria with Mycobacterium leprae in environment of leprosy endemic regions in India.

Non-tuberculous mycobacteria (NTM) are environmental mycobacteria found ubiquitously in nature. The present study was conducted to find out the presence of various species of NTM in leprosy endemic region along with Mycobacterium (M) leprae. Water and wet soil samples from the periphery of ponds used by the community were collected from districts of Purulia of West Bengal and Champa of Chhattisgarh, India. Samples were processed and decontaminated followed by culturing on Lowenstein Jensen (LJ) media. Polymerase chain reaction (PCR) was performed using 16S rRNA gene target of mycobacteria and species was confirmed by sequencing method. Indirect immune-fluorescent staining of M. leprae from soil was performed using M. leprae-PGL-1 rabbit polyclonal antibody. The phylogenetic tree was constructed by using MEGA-X software. From 380 soil samples 86 NTM were isolated, out of which 34(40%) isolates were rapid growing mycobacteria (RGM) and 52(60%) isolates were slow growing mycobacteria (SGM). Seventy-seven NTM isolates were obtained from 250 water samples, out of which 35(45%) were RGM and 42(55%) were SGM. Amongst all the RGM, we isolated M. porcinum, M. psychrotolerans, M. alsenase, M. arabiense and M. asiaticum from Indian environmental samples. M. fortuitum was the most commonly isolated species of all RGM. Out of all SGM, M. holsaticum, M. yongonense, M. seoulense, M. szulgai, M. europaeum, M. simiae and M. chimaera were isolated for the first time from Indian environment. M. intracellulare was the commonest of all isolated SGM. Presence of M. leprae was confirmed by indirect immunofluorescent microcopy and PCR method from the same environmental samples. Phylogenetic tree was showing a close association between these NTMs and M. leprae in these samples. Several NTM species of pathogenic and nonpathogenic in nature along with M. leprae were isolated from soil and pond water samples from leprosy endemic regions and these might be playing a role in causing disease and maintaining leprosy endemicity in India.

Single-Step Synthesis of Magnesium-Doped Lithium Manganese Oxide Nanosorbent and Their Polymer Composite Beads for Selective Heavy Metal Removal.

Magnesium-doped lithium manganese oxide nanosorbent is prepared by a single-step solid-state method and characterized with appropriate analytical techniques, adsorption kinetic model, and isotherms. Competitive and noncompetitive adsorption studies are performed for a range of heavy metal ions. Prepared nanosorbent has shown explicit selectivity for various heavy metal ions and no remarkable influence of coexisting common interfering ions (Na+, K+, Mg2+, and Ca2+), which generally coexist with all natural sources of water, contaminated water, and industrial waste. To achieve easy handling of an adsorbent, polysulfone-nanosorbent (PS-nanosorbent) composite beads are prepared, and their competitive heavy metal removal performance is determined. Competitive adsorption and regeneration studies have shown that PS-nanosorbent beads can be employed for selective heavy metal removal and reuse for multiple cycles.

Enhanced Electrochemical Performance of Stable SPES/SPANI Composite Polymer Electrolyte Membranes by Enriched Ionic Nanochannels.

Herein, we present the results of sulfonated polyaniline (SPANI) and sulfonated poly(ether sulfone) (SPES) composite polymer electrolyte membranes. The membranes are established for high-temperature proton conductivity and methanol permeability to render their applicability. Composite membranes have been prepared by modifying the SPES matrix with different concentrations of SPANI (e.g., 1, 2, 5, 10, and 20 wt %). Structural and thermomechanical characterizations have been performed using the transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analyzer techniques. Physicochemical and electrochemical properties have been evaluated by water uptake, ion-exchange capacity, dimensional stability, and proton conductivity. Methanol permeability experiment was carried out to analyze the compatibility of prepared membranes toward direct methanol fuel cell application and found the lowest methanol permeability for PAS-5. Also, the membranes reveal excellent thermal, mechanical, and physicochemical properties for their application toward high-temperature electromembrane processes.

Spontaneous Formation of Multiarchitecture Vesicles of [C8mim]Br + [Na]DBS in Aqueous Medium: Synergic Interplay of Electrostatic, Hydrophobic, and π-π Stacking Interactions.

A mixture of a cationic surface active ionic liquid, [C8mim]Br and anionic surfactant, [Na]DBS has been shown to form unilamellar vesicles in water over an exceptionally wide mole fraction range of [C8mim]Br (x1 = 0.2 to 0.8). Formation of vesicles has been evidenced from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) imaging. Cryo-TEM imaging of an equimolar mixture showed multiarchitectural unilamellar vesicles (spherical, tubular, and ribbon). Such complex architectures were earlier reported for Janus dendrimers of different structures (Science, 2010, 328, 1014). The synergism between oppositely charged single chain surfactants to form bilayer structures has been explained based on the evidence of π-π stacking interaction from 2D NOESY measurements, Coulombic interactions from zeta potential measurements and magnitude of interaction parameter from the critical aggregation concentration. The aggregation concentrations were measured from tensiometry and fluorescence using pyrene as a polarity probe. The phase behavior at different mixture compositions has been revealed from turbidity measurements and visual inspection. Hydrodynamic radii of self-assembled structures in the bulk solution phase were measured from dynamic light scattering. Vesicles formed have been explored as delivery vehicles for proteins using bovine serum albumin (BSA) as model.

Sodium bromide induced micelle to vesicle transitions of newly synthesized anionic surface active ionic liquids based on dodecylbenzenesulfonate.

Dodecylbenezenesulfonate-based anionic surface active ionic liquids (DBS-ILs) paired with onium cations, n-butyltrimethylammonium ([N1114]), 1-butyl-3-methylimidazolium ([C4mim]), and N-butylpyridinium ([C4Py]) have been synthesized. DBS-ILs were found to be highly surface active having critical micelle concentration (CMC) lower than that of their conventional analogue sodium dodecylbenezenesulfonate ([Na][DBS]). The CMC values of DBS-ILs were determined from surface tension (ST) and isothermal titration calorimetry (ITC). DBS-ILs formed micelles predominantly in the aqueous medium, and unlike [Na]DBS, the micelles of DBS-ILs could be transformed into vesicles with the addition of sodium bromide (NaBr). Micelle to vesicle transitions (MVTs) were evidenced from dynamic light scattering (DLS), turbidity, proton nuclear magnetic resonance ((1)H NMR), and cryo-TEM techniques. Thermodynamics of aggregation was investigated from ITC which indicated that the aggregation process is primarily driven by the entropy factor. The formation of a vesicle upon addition of NaBr has been accounted to the increased electrostatic interactions between the less hydrated sulfonate headgroup and the more populated bigger sized counterions along with the favored cation-π or π-π interactions between them as evidenced from 2D-NOESY NMR experiments. The stimuli-responsive morphological transitions in the self-assembly of the reported anionic surface active ionic liquids (SAILs) will be useful for encapsulation and delivery of active (bio)molecules in the targeted biomedical applications.

Stabilization of microtubules by taxane diterpenoids: insight from docking and MD simulations.

Microtubules are formed from the molecules of tubulin, whose dynamics is important for many functions in a cell, the most dramatic of which is mitosis. Taxol is known to interact within a specific site on tubulin and also believed to block cell-cycle progression during mitosis by binding to and stabilizing microtubules. Along with the tremendous potential that taxol has shown as an anticancer drug, clinical problems exist with solubility, toxicity, and development of drug resistance. The crystal structure of taxane diterpenoids, namely, 10, 13-deacetyl-abeo-baccatin-IV (I), 5-acetyl-2-deacetoxydecinnamoyl-taxinine-0.29hydrate (II), 7, 9-dideacetyltaxayuntin (III), and Taxawallin-K (IV), are very similar to the taxol molecule. Considerable attention has been given to such molecules whose archetype is taxol but do not posses long aliphatic chains, to be developed as a substitute for taxol with fewer side effects. In the present work, the molecular docking of these taxane diterpenoids has been carried out with the tubulin alpha-beta dimer (1TUB) and refined microtubule structure (1JFF) using Glide-XP, in order to assess the potential of tubulin binding of these cytotoxic agents. Results show that all the ligands dock into the classical taxol binding site of tubulin. Taxol shows the best binding capabilities. On the basis of docking energy and interactions, apart from taxol, molecule II has a better tendency of binding with 1TUB while molecule I shows better binding capability with bovine tubulin 1JFF. To validate the binding capabilities, molecular dynamics (MD) simulations of the best docked complexes of ligands with 1JFF have been carried out for 15.0 ns using DESMOND. Average RMSD variations and time line study of interactions and contacts indicate that these complexes remain stable during the course of the dynamics. However, taxol and molecule II prevail over other taxoids.

Temperature-dependent solubility transition of Na2SO4 in water and the effect of NaCl therein: solution structures and salt water dynamics.

Dual, aqueous solubility behavior of Na2SO4 as a function of temperatures is still a natural enigma lying unresolved in the literature. The solubility of Na2SO4 increases up to 32.38 °C and decreases slightly thereafter at higher temperatures. We have thrown light on this phenomenon by analyzing the Na2SO4-water clusters (growth and stability) detected from temperature-dependent dynamic light scattering experiments, solution compressibility changes derived from the density and speed of sound measurements, and water structural changes/Na2SO4 (ion pair)-water interactions observed from the FT-IR and 2D DOSY (1)H NMR spectroscopic investigations. It has been observed that Na2SO4-water clusters grow with an increase in Na2SO4 concentration (until the solubility transition temperature) and then start decreasing afterward. An unusual decrease in cluster size and solution compressibility has been observed with the rise in temperature for the Na2SO4 saturated solutions below the solubility transition temperature, whereas an inverse pattern is followed thereafter. DOSY experiments have indicated different types of water cluster species in saturated solutions at different temperatures with varying self-diffusion coefficients. The effect of NaCl (5-15 wt %) on the solubility behavior of Na2SO4 at different temperatures has also been examined. The studies are important from both fundamental and industrial application points of view, for example, toward the clean separation of NaCl and Na2SO4 from the effluent streams of textile and tannery industries.

One pot synthesis of water-dispersible dehydroascorbic acid coated Fe3O4 nanoparticles under atmospheric air: blood cell compatibility and enhanced magnetic resonance imaging.

Water dispersible and biologically important molecule dehydroascorbic acid (DHA, capable to cross the blood brain barrier) coated Fe3O4 superparamagnetic nanoparticles having an average size of ∼6 nm were synthesized through one pot aqueous coprecipitation method under atmospheric air. An antioxidant ascorbic acid (AA) used in the synthesis oxidized itself to dehydroascorbic acid (DHA) to consume dissolved or available oxygen in reaction mixture which died away the oxidative impact of atmospheric air and formed DHA encapsulated the Fe3O4 nanoparticles which stabilized the Fe3O4 nanoparticles and significantly enhanced their colloidal solubility in water. Fe3O4 phase, superparamagnetic property, DHA coating and stable colloidal solubility in water were confirmed by means of XPS, VSM, IR and zeta potential analysis respectively. T1, T2 and T2(∗) weighted magnetic resonance imaging (MRI) and corresponding relaxivity (r1=0.416, r2=50.28 and r2(∗)=123.65 mM(-1) and r2/r1=120.86, r2(∗)r1=297.23) of colloidally dispersed DHA-coated nanoparticle water phantom revealed a strong contrast enhancement in T2 and T2(∗) weighted images. The compatibility of DHA-coated Fe3O4 nanoparticles toward human blood cells was examined by means of cell counting and cell morphological analysis with the use of optical microscope and scanning electron microscope imaging.

One-Pot Fabrication of RGO-Ag3 VO4 Nanocomposites by in situ Photoreduction using Different Sacrificial Agents: High Selectivity Toward Catechol Synthesis and Photodegradation Ability.

Weak photon absorption and fast carrier kinetics in graphene restrict its applications in photosensitive reactions. Such restrictions/limitations can be overcome by covalent coupling of another photosensitive nanostructure to graphene, forming graphene-semiconductor nanocomposites. Herein, we report one-pot synthesis of RGO-Ag3 VO4 nanocomposites using various sacrificial agents like ethanol, methanol, propanol and ethylene glycol (EG) under visible light illumination. The Raman spectral analysis and (13) C MAS NMR suggest ethanol to be the best sacrificial agent among those studied. Thermal analysis studies, further, confirm the stability of the synthesized nanocomposite with ethanol as sacrificial agent. In view of this, the activity toward dye degradation was focused over the composites prepared via ethanol as sacrificial agent. It was observed and proved that cationic dyes could be degraded quantitatively and swiftly compared to anionic dyes (37.79%) in 1.5 h. This suggests that the surface of the nanocomposites is anionic as partial reduction takes place during synthesis process. In case of mixed dye degradation process, it was noticed that the presence of cationic dye doubles the degradation of anionic dye. The activity of these synthesized nanocomposites is more than five-fold toward the phototransformation of phenol and photodegradation of textile dyes under visible light illumination.

New chemodosimetric probe for the specific detection of Hg2+ in physiological condition and its utilisation for cell imaging studies.

A dithiane derivative of BODIPY is synthesized. This new reagent could be used for the specific and instantaneous detection of Hg(2+) in physiological condition. This dithiane reagent reacts specifically with Hg(2+) to regenerate the parent BODIPY-aldehyde with consequential change in visually detectable optical responses and this provides the possibility of using this reagent as a colorimetric probe or as a fluorescent biomarker/imaging reagent. Further, non-covalent interactions could be utilized for formation of an inclusion complex with biologically benign ß-cyclodextrin for enhancing its solubility in aqueous environment and this included adduct could be used as a fluorescent marker and imaging reagent for Hg(2+). Uptake of Hg(2+) ions in live HeLa cells, exposed to a solution having Hg(2+) ion concentration as low as 2 ppb, could also be detected by confocal laser microscopic studies.

Temperature invariance of NaCl solubility in water: inferences from salt-water cluster behavior of NaCl, KCl, and NH4Cl.

The growth and stability of salt-water clusters have been experimentally studied in aqueous solutions of NaCl, KCl, and NH(4)Cl from dilute to near-saturation conditions employing dynamic light scattering and zeta potential measurements. In order to examine cluster stability, the changes in the cluster sizes were monitored as a function of temperature. Compared to the other cases, the average size of NaCl-water clusters remained almost constant over the studied temperature range of 20-70 °C. Information obtained from the temperature-dependent solution compressibility (determined from speed of sound and density measurements), multinuclear NMR ((1)H, (17)O, (35)Cl NMR), and FTIR were utilized to explain the cluster behavior. Comparison of NMR chemical shifts of saturated salt solutions with solid-state NMR data of pure salts, and evaluation of spectral modifications in the OH stretch region of saturated salt solutions as compared to that of pure water, provided important clues on ion pair-water interactions and water structure in the clusters. The high stability and temperature independence of the cluster sizes in aqueous NaCl shed light on the temperature invariance of its solubility.