Tripodal Bile Acid Architectures Based on a Triarylphosphine Oxide Core Obtained by Copper-Catalysed 1,3]-Dipolar Cycloaddition: Synthesis and Preliminary Aggregation Studies

We report the synthesis and aggregation behaviour of new water-soluble, bile acid derived tripodal architectures based on a core derived from triphenylphosphine oxide. We employed the well-established copper-catalysed 1,3]-dipolar cycloaddition (CuAAC) for the construction of these tripodal molecules. The aggregation behaviour of these molecules in aqueous media was studied by different analytical methods such as dye solubilisation, dynamic light scattering, NMR and AFM. These molecular architectures also offer an additional advantage in aiding understanding of the influence of the nature of the bile acid backbone and of the configuration at the steroid C-3 position in these architectures; to the best of our knowledge this has not been reported in the literature. The unique gelation properties of the -derivatives were explained through molecular modelling studies and the mechanical behaviour of these gels was studied by rheology experiments.

Electrical switching, SET-RESET, and Raman scattering studies on Ge15Te80-xIn5Agx glasses

Bulk Ge15Te85-xIn5Agx glasses are shown to exhibit electrical switching with switching/threshold voltages in the range of 70-120V for a sample thickness of 0.3 mm. Further, the samples exhibit threshold or memory behavior depending on the ON state current. The compositional studies confirm the presence of an intermediate phase in the range 8 <= x <= 16, revealed earlier by thermal studies. Further, SET-RESET studies have been performed by these glasses using a triangular pulse of 6 mA amplitude (for SET) and 21 mA amplitude (for RESET). Raman studies of the samples after the SET and RESET operations reveal that the SET state is a crystalline phase which is obtained by thermal annealing and the RESET state is the glassy state, similar to the as-quenched samples. It is interesting to note that the samples in the intermediate phase, especially compositions at x = 10, 12, and 14 withstand more set-reset cycles. This indicates compositions in the intermediate phase are better suited for phase change memory applications. (C) 2014 AIP Publishing LLC.

Optical, photo-acoustic and electrical switching studies of amorphous GeS2 thin films

This paper reports optical, photo-acoustic and electrical switching investigations of GeS2 amorphous thin films of different thicknesses, deposited on glass substrates in vacuum. The Tauc parameter (B (1/2)) and Urbach energy (E (U)) have been determined from the transmittance spectra, to understand the changes in structural disorder; it is found that B (1/2) increases whereas E (U) decreases as the thickness of the films increases. Based on the results, it is suggested that bond re-arrangement, i.e. transformation from homopolar bonds to heteropolar bonds, takes place with increase in thickness. The thermal diffusivity values of GeS2 thin films also show the presence of a chemically ordered network in the GeS2 thin films. Further, it is found that these films exhibit memory-type electrical switching. The observed variation in the switching voltages has been understood on the basis of increase in chemical order.

Effect of silane functionalized alumina on poly(vinyl butyral) nanocomposite films: Thermal, mechanical, and moisture barrier studies

In this work, a hybrid-polymer nanocomposite film, based on polyvinyl butyral/amino-silane functionalized nano alumina, was fabricated by melt processing. The calcium degradation measurements suggest the functionalized nanocomposite films exhibit higher resistance towards moisture penetration as compared to the neat alumina loaded films. Thermal stability, mechanical strength, and contact angle studies of the composites were also conducted to evaluate the performance of the functionalized alumina loaded films. These nanocomposite films were encapsulated over Al/P3HT/ITO Schottky structured device. The changes observed in the current density of the devices to the applied voltage before and after accelerated aging conditions are presented. The nanocomposite with functionalized alumina films exhibits 50% change in current density, which is superior to that attained with neat and non-functionalized films. POLYM. COMPOS., 35:1426-1435, 2014. (c) 2013 Society of Plastics Engineers

Structural, thermal and quantum chemical studies of p-coumaric and caffeic acids

Two hydroxycinnamic acids viz., p-coumaric, and caffeic acids have been extracted and purified from Parthenium hysterophorus, subsequently characterized by elemental analysis, FT-IR, NMR, single crystal X-ray crystallography. The optimized structures of these acids were calculated in terms of density functional theory by Gaussian 09. The validation of experimental and theoretically obtained data for structural parameters such as bond lengths and bond angles has have been carried out to analyze the statistical significance by curve fitting analysis and the values of correlation coefficient found to be 0.985, 0.992, and 0.984, 0.975 in p-coumaric, and caffeic acids, respectively. The calculated HOMO and LUMO energies show the eventual charge transfer interaction within the molecule. Thermal studies were also carried out by thermogravimetry (TG), differential thermogravimetric analysis (DTA), and derivative thermogravimetry (DTG). (C) 2014 Elsevier B.V. All rights reserved.

Antiproliferative and tumor inhibitory studies of 2,3 disubstituted 4-thiazolidinone derivatives

4-Thiazolidinone derivatives were synthesized using T3P (R)-DMSO media as a cyclodehydrating agent. All the molecules were tested for their cytotoxicity against leukemic cell lines. The compound 3-(4-bromophenyl)-2-(4-(dimethylamino)phenyl)thiazolidin-4-one (4e) with electron donating substituent at para position of phenyl ring displayed considerable cytotoxicity against Reh and Nalm6 cells with an IC50 value of 11.9 and 13.5 mu M, respectively. Furthermore, the compound 4e tested for tumor regression studies induced by EAC in Swiss albino mouse. Both in vitro and in vivo results suggested significant antiproliferative activity of compound 4e in Reh cells and mouse tumor tissue treated with compound 4e showed multifocal areas of necrosis and numerous number of apoptotic cells. (C) 2015 Elsevier Ltd. All rights reserved.

Synthesis, ABTS-Radical Scavenging Activity, and Antiproliferative and Molecular Docking Studies of Novel Pyrrolo1,2-a]quinoline Derivatives

A new 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS)-radical scavenging and antiproliferative agents of pyrrolo1,2-a]quinoline derivatives have been synthesized. An efficient method for the synthesis of 14 novel diversified pyrrolo1,2-a]quinoline derivatives has been described using 4-(1,3-dioxolan-2-yl)quinoline and different phenacyl bromides in acetone and followed by reacting with different acetylenes in dimethylformamide/K2CO3. The structure of the newly synthesized compounds was determined by infrared, H-1 NMR, C-13 NMR, mass spectrometry, and elemental analysis. The in vitro antioxidant activity revealed that among all the tested compounds 5n exhibited maximum scavenging activity with ABTS. Compound 5b has showed good antiproliferative activity as an inhibitor of epidermal growth factor receptor (EGFR) tyrosine kinase.

Differential binding of ppGpp and pppGpp to E-coli RNA polymerase: photo-labeling and mass spectral studies

(p) ppGpp, a secondary messenger, is induced under stress and shows pleiotropic response. It binds to RNA polymerase and regulates transcription in Escherichia coli. More than 25 years have passed since the first discovery was made on the direct interaction of ppGpp with E. coli RNA polymerase. Several lines of evidence suggest different modes of ppGpp binding to the enzyme. Earlier cross-linking experiments suggested that the beta-subunit of RNA polymerase is the preferred site for ppGpp, whereas recent crystallographic studies pinpoint the interface of beta'/omega-subunits as the site of action. With an aim to validate the binding domain and to follow whether tetra-and pentaphosphate guanosines have different location on RNA polymerase, this work was initiated. RNA polymerase was photo-labeled with 8-azido-ppGpp/8-azido-pppGpp, and the product was digested with trypsin and subjected to mass spectrometry analysis. We observed three new peptides in the trypsin digest of the RNA polymerase labeled with 8-azido-ppGpp, of which two peptides correspond to the same pocket on beta'-subunit as predicted by X-ray structural analysis, whereas the third peptide was mapped on the beta-subunit. In the case of 8-azido-pppGpp-labeled RNA polymerase, we have found only one cross-linked peptide from the beta'-subunit. However, we were unable to identify any binding site of pppGpp on the beta-subunit. Interestingly, we observed that pppGpp at high concentration competes out ppGpp bound to RNA polymerase more efficiently, whereas ppGpp cannot titrate out pppGpp. The competition between tetraphosphate guanosine and pentaphosphate guanosine for E. coli RNA polymerase was followed by gel-based assay as well as by a new method known as DRaCALA assay.

Docking, molecular dynamics and QM/MM studies to delineate the mode of binding of CucurbitacinE to F-actin

CucurbitacinE (CurE) has been known to bind covalently to F-actin and inhibit depolymerization. However, the mode of binding of CurE to F-actin and the consequent changes in the F-actin dynamics have not been studied. Through quantum mechanical/molecular mechanical (QM/MM) and density function theory (DFT) simulations after the molecular dynamics (MD) simulations of the docked complex of F-actin and CurE, a detailed transition state (TS) model for the Michael reaction is proposed. The TS model shows nucleophilic attack of the sulphur of Cys257 at the beta-carbon of Michael Acceptor of CurE producing an enol intermediate that forms a covalent bond with CurE. The MD results show a clear difference between the structure of the F-actin in free form and F-actin complexed with CurE. CurE affects the conformation of the nucleotide binding pocket increasing the binding affinity between F-actin and ADP, which in turn could affect the nucleotide exchange. CurE binding also limits the correlated displacement of the relatively flexible domain 1 of F-actin causing the protein to retain a flat structure and to transform into a stable ``tense'' state. This structural transition could inhibit depolymerization of F-actin. In conclusion, CurE allosterically modulates ADP and stabilizes F-actin structure, thereby affecting nucleotide exchange and depolymerization of F-actin. (C) 2015 Elsevier Inc. All rights reserved.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

Spin-glass state in nanoparticulate (La0.7Sr0.3MnO3)(1-x) (BaTiO3)(x) solid solutions: Experimental and density-functional studies

We report the transition from robust ferromagnetism to a spin- glass state in nanoparticulate La0.7Sr0.3MnO3 through solid solution with BaTiO3. The field- and temperature-dependent magnetization and the frequency-dependent ac magnetic susceptibility measurements strongly indicate the existence of a spin- glass state in the system, which is further confirmed from memory effect measurements. The breaking of long-range ordering into short-range magnetic domains is further investigated using density-functional calculations. We show that Ti ions remain magnetically inactive due to insufficient electron leakage from La0.7Sr0.3MnO3 to the otherwise unoccupied Ti-d states. This results in the absence of a Mn-Ti-Mn spin exchange interaction and hence the breaking of the long-range ordering. Total-energy calculations suggest that the segregation of nonmagnetic Ti ions leads to the formation of short-range ferromagnetic Mn domains.

Electrical conductivity and dielectric relaxation studies on microwave synthesized Na2SO4 center dot NaPO3 center dot MoO3 glasses

Electrical conductivity and dielectric relaxation studies on SO4 (2-) doped modified molybdo-phosphate glasses have been carried out over a wide range of composition, temperature and frequency. The d.c. conductivities which have been measured by both digital electrometer (four-probe method) and impedance analyser are comparable. The relaxation phenomenon has been rationalized using electrical modulus formalism. The use of modulus representation in dielectric relaxation studies has inherent advantages viz., experimental errors arising from the contributions of electrode-electrolyte interface capacitances are minimized. The relaxation observed in the present study is non-Debye type. The activation energies for relaxation were determined using imaginary parts of electrical modulus peaks which were close to those of the d.c. conductivity implying the involvement of similar energy barriers in both the processes. The enhanced conductivity in these glasses can be attributed to the migration of Na+, in expanded structures due to the introduction of SO4 (2-) ions.

Crustal Deformation and Seismic History Associated with the 2004 Indian Ocean Earthquake: A Perspective from the Andaman–Nicobar Islands

The Indian Ocean earthquake of 26 December 2004 led to significant ground deformation in the Andaman and Nicobar region, accounting for ~800 km of the rupture. Part of this article deals with coseismic changes along these islands, observable from coastal morphology, biological indicators, and Global Positioning System (GPS) data. Our studies indicate that the islands south of 10° N latitude coseismically subsided by 1–1.5 m, both on their eastern and western margins, whereas those to the north showed a mixed response. The western margin of the Middle Andaman emerged by >1 m, and the eastern margin submerged by the same amount. In the North Andaman, both western and eastern margins emerged by >1 m. We also assess the pattern of long-term deformation (uplift/subsidence) and attempt to reconstruct earthquake/tsunami history, with the available data. Geological evidence for past submergence includes dead mangrove vegetation dating to 740 ± 100 yr B.P., near Port Blair and peat layers at 2–4 m and 10–15 m depths observed in core samples from nearby locations. Preliminary paleoseismological/tsunami evidence from the Andaman and Nicobar region and from the east coast of India, suggest at least one predecessor for the 2004 earthquake 900–1000 years ago. The history of earthquakes, although incomplete at this stage, seems to imply that the 2004-type earthquakes are infrequent and follow variable intervals

The effect of pH on the unfolding pathway and stability of ribosome-inactivating protein abrin-II

The effect of pH on the unfolding pathway acid the stability of the toxic protein abrin-II have been studied by increasing denaturant concentrations of guanidine hydrochloride and by monitoring the change in 8,1-anilino naphthalene sulfonic acid (ANS) fluorescence upon binding to the hydrophobic sites of the protein. Intrinsic protein fluorescence, far and near UV-circular dichroism (CD) spectroscopy and ANS binding studies reveal that the unfolding of abrin-II occurs through two intermediates at pH 7.2 and one intermediate at pH 4.5. At pH 7.2, the two subunits A and B of abrin-II unfold sequentially. The native protein is more stable at pH 4.5 than at pH 7.2. However, the stability of the abrin-II A-subunit is not affected by a change in pH. These observations may assist in an understanding of the physiologically relevant transmembrane translocation of the toxin.