Preparation and characterisation of CoS2 nanomaterial in aqueous cationic surfactant medium of cetyltrimethylammonium bromide (CTAB)

Cobalt disulfide is an important nanomaterial in the field of material chemistry due to its interesting catalytic and electromagnetic properties. We herein report the simple solution phase preparation of nanoparticles of cobalt disulfide in micellar medium of cationic surfactant cetyltrimethylammonium bromide (CTAB) and also by way of capping with thiophenol. The product has been characterized using spectroscopic and electron microscopic and magnetic moment measurements. The presence of disulfide bond is clearly evident from the 480 cm⁻¹ peak in the infrared spectrum. The thiol passivated particles prepared in aqueous and ethanol medium has been found to have different compositions as observed from the ESIMS study.     

Redox responsive activity regulation in exceptionally stable supramolecular assembly and co-assembly of a protein

Supramolecular assembly of biomolecules/macromolecules stems from the desire to mimic complex biological structures and functions of living organisms. While DNA nanotechnology is already in an advanced stage, protein assembly is still in its infancy as it is a significantly difficult task due to their large molecular weight, conformational complexity and structural instability towards variation in temperature, pH or ionic strength. This article reports highly stable redox-responsive supramolecular assembly of a protein Bovine serum albumin (BSA) which is functionalized with a supramolecular structure directing unit (SSDU). The SSDU consists of a benzamide functionalized naphthalene-diimide (NDI) chromophore which is attached with the protein by a bio-reducible disulfide linker. The SSDU attached protein (NDI-BSA) exhibits spontaneous supramolecular assembly in water by off-set π-stacking among the NDI chromophores, leading to the formation of spherical nanoparticles (diameter: 150–200 nm). The same SSDU when connected with a small hydrophilic wedge (NDI-1) instead of the large globular protein, exhibits a different π-stacking mode with relatively less longitudinal displacement which results in a fibrillar network and hydrogelation. Supramolecular co-assembly of NDI-BSA and NDI-1 (3 : 7) produces similar π-stacking and an entangled 1D morphology. Both the spherical assembly of NDI-BSA or the fibrillar co-assembly of NDI-BSA + NDI-1 (3 : 7) provide sufficient thermal stability to the protein as its thermal denaturation could be completely surpassed while the secondary structure remained intact. However, the esterase like activity of the protein reduced significantly as a result of such supramolecular assembly indicating limited access by the substrate to the active site of the enzyme located in the confined environment. In the presence of glutathione (GSH), a biologically important tri-peptide, due to the cleavage of the disulfide bond, the protein became free and was released, resulting in fully regaining its enzymatic activity. Such supramolecular assembly provided excellent protection to the protein against enzymatic hydrolysis as the relative hydrolysis was estimated to be <30% for the co-assembled protein with respect to the free protein under identical conditions. Similar to bioactivity, the enzymatic hydrolysis also became prominent after GSH-treatment, confirming that the lack of hydrolysis in the supramolecularly assembled state is indeed related to the confinement of the protein in the nanostructure assembly.

Supramolecular structure directing unit regulated co-assembly of a protein produces a highly stable fibrillar nanostructure and glutathione responsive release of the protein in its active state.     

Pressure effects on diffusion in liquid ammonia : A simulation study using a combination of isobaric-isothermal and microcanonical molecular dynamics

The effects of pressure on translational and rotational diffusion in liquid ammonia are investigated by means of molecular dynamics simulations. Calculations are done at two different temperatures and at many different pressures by using a two-part protocol involving molecular dynamics in isobaric-isothermal ensemble in the first part and in microcanonical ensemble in the second part. Our results are analyzed in terms of pressure-induced changes in structural properties such as packing and hydrogen bond properties. Also, the present results of liquid ammonia are compared with corresponding results for other hydrogen bonded liquids that were reported in recent years.      

Synthesis and optical properties of triphenylene-based conjugated dendrons

Conjugated dendrons based on triphenylene building blocks have been synthesized. Such dendrons exhibit broader absorption wavelength range and higher absorption coefficients than their phenyl analogs. They also possess extended excited state lifetimes and high fluorescence quantum yields in dilute solutions. In the solid state, these dendrons are highly aggregated, resulting in significantly broadened and red-shifted emissions, whose decay transients depend strongly on the detection wavelength.     

Density dynamics in some quantum systems

The quantum domain behavior of classical nonintegrable systems is well‐understood by the implementation of quantum fluid dynamics and quantum theory of motion. These approaches properly explain the quantum analogs of the classical Kolmogorov–Arnold–Moser type transitions from regular to chaotic domain in different anharmonic oscillators. Field‐induced tunneling and chaotic ionization in Rydberg atoms are also analyzed with the help of these theories. Quantum fluid density functional theory may be used to understand different time‐dependent processes like ion‐atom/molecule collisions, atom‐field interactions, and so forth. Regioselectivity as well as confined atomic/molecular systems and their reactivity dynamics have also been explained. © 2013 Wiley Periodicals, Inc.     

New hockey stick compounds with a lateral methyl group showing nematic,synclinic and anticlinic smectic C phases

New hockey stick-shaped mesogens with a lateral methyl group inserted between the m-alkyloxy-chain and the azomethine connecting group, 4-(3-n-alkyloxy-2-methyl-phenyliminomethyl) phenyl-4-n-alkyloxycinnamates have been synthesised. The interesting feature of these hockey stick-shaped mesogens is the appearance of the nematic phase in addition to two polymorphic tilted smectic phases – the synclinic smectic C (SmC_s) and the anticlinic SmC_a phase. Physical characterisation of these mesogens has been carried out using polarising optical microscopy, differential scanning calorimetry, optical birefringence, X-ray diffraction (XRD), electro–optical and dielectric spectroscopy measurements. The SmC_s–SmC_a phase transition is accompanied by only a small calorimetric signal but causes a pronounced change in the optical textures. Orientational order parameters determined from the birefringence measurements have been compared with those estimated from XRD patterns. Dielectric measurements point to the formation of small ‘soft’ ferroelectric clusters responsible for a low frequency absorption range.     

Divergence in photoinduced electron transfer (PET) reactions: a useful strategy towards identifying route-selectivity in mixed ketones

The work utilized photoinduced electron transfer (PET) reactions to identify the preferred photoreaction route in molecules having juxtaposed α,β and β,γ-enones. Such process directly converted 2-hydroxyimino derivatives of 5-benzoylbicyclo[2.2.2]octenones to the corresponding bicyclo[3.2.1]octane derivatives. First evidence of Type B rearrangement in α,β-enones having acyl substitution at Cγ-position has been depicted in this work. In rigid mixed enones, this has been found to be generally the preferred photoreaction route.     

Emergent Scenario and Different Anisotropic Models

In this work, Emergent Universe scenario has been developed in general homogeneous anisotropic model and for the inhomogeneous LTB model. In the first case, it is assumed that the matter in the universe has two components—one is perfect fluid with barotropic equation of state p=ωρ (ω, a constant) and the other component is a real or phantom (or tachyonic) scalar field. In the second case, the universe is only filled with a perfect fluid and possibilities for the existence of emergent scenario has been examined.     

Biotechnological and Molecular Approaches for Vanillin Production: a Review

Vanillin is one of the most widely used flavoring agents in the world. As the annual world market demand of vanillin could not be met by natural extraction, chemical synthesis, or tissue culture technology, thus biotechnological approaches may be replacement routes to make production of bio-vanillin economically viable. This review’s main focus is to highlight significant aspects of biotechnology with emphasis on the production of vanillin from eugenol, isoeugenol, lignin, ferulic acid, sugars, phenolic stilbenes, vanillic acid, aromatic amino acids, and waste residues by applying fungi, bacteria, and plant cells. Production of biovanillin using GRAS lactic acid bacteria and metabolically engineered microorganisms, genetic organization of vanillin biosynthesis operons/gene cassettes and finally the stability of biovanillin generated through various biotechnological procedures are also critically reviewed in the later sections of the review.     

Characterization and electrical transport properties of polyaniline and multiwall carbon nanotube composites

Polyaniline/multiwalled carbon nanotube (PANI/MWNT) composites were prepared by in situ polymerization. Scanning electron microscope, X‐ray diffraction, Fourier transform infrared, Uv‐Visible spectroscopy, Fluorescence spectrophotometry were done to characterize the PANI/MWNT composites. Thermal stability was measured by thermogravimetry analysis. The thermal stability of PANI/MWNT composites becomes higher than PANI. Electrical transport properties of different PANI/MWNT composites were investigated in the temperature range 77 ≤ T ≤ 300 K with and without magnetic field up to 1 T. The dc resistivity of PANI/MWNT composites shows different behavior compared to the sample without MWNT. The room temperature dc magnetoconductivity of the samples is negative; however, its sign changes to positive by lowering the temperature, which has been explained by hopping type charge transport. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1767–1775, 2010