Dimeric 1,3-Phenylene-bis(piperazinyl benzimidazole)s: Synthesis and Structure-Activity Investigations on their Binding with Human Telomeric G-Quadruplex DNA and Telomerase Inhibition Properties

Ligand-induced stabilization of G-quadruplex structures formed by the human telomeric DNA is an active area of research. The compounds which stabilize the G-quadruplexes often lead to telomerase inhibition. Herein we present the results of interaction of new monomeric and dimeric ligands having 1,3-phenylene-bis(piperazinyl benzimidazole) unit with G-quadruplex DNA (G4DNA) formed by human telomeric repeat d(G(3)T(2)A)(3)G(3)]. These ligands efficiently stabilize the preformed G4DNA in the presence of 100 mM monovalent alkali metal ions. Also, the G4DNA formed in the presence of low concentrations of ligands in 100 mM K+ adopts a highly stable parallel-stranded conformation. The G-quadruplexes formed in the presence of the dimeric compound are more stable than that induced by the corresponding monomeric counterpart. The dimeric ligands having oligo-oxyethylene spacers provide much higher stability to the preformed G4DNA and also exert significantly higher telomerase inhibition activity. Computational aspects have also been discussed.

Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique

Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant ('a' and `c'), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 10(6) Omega-cm at higher temperature and 10(5) Omega-cm at lower temperature. (C) 2012 Elsevier Ltd. All rights reserved.

2,3-Unsaturated enoses. A Pummerer rearrangement route to sugar vinyl sulfides and synthesis of 3-deoxy-3-alkyl/arylsulfinyl pyranosides

A Pummerer rearrangement of 2,3-dideoxy-3-alkyl/arylsulfinyl-arabino-hexopyranosides is reported. Treatment of sulfinyl-arabino-hexopyranoside derivatives, obtained through oxidation of the corresponding thio-derivatives, with trifluoroacetic anhydride (TFAA)/pyridine led to a facile formation of 2,3-dideoxy-3-alkyl/arylthio-hex-2-enopyranosides. Upon conversion of sugar vinyl sulfides to vinyl sulfoxides, conjugate addition reactions were conducted with alkoxides, to afford 3-deoxy-3-alkyl/arylsulfinyl pyranosides, in the manno-configuration exclusively. Whereas the conjugate addition reaction did not proceed with ether protecting groups, ester protecting groups and free hydroxyl groups in the sugar vinyl sulfoxide permitted the reaction. (C) 2012 Elsevier Ltd. All rights reserved.

Structural and mechanistic investigations on Salmonella typhimurium acetate kinase (AckA): identification of a putative ligand binding pocket at the dimeric interface

Background: Bacteria such as Escherichia coli and Salmonella typhimurium can utilize acetate as the sole source of carbon and energy. Acetate kinase (AckA) and phosphotransacetylase (Pta), key enzymes of acetate utilization pathway, regulate flux of metabolites in glycolysis, gluconeogenesis, TCA cycle, glyoxylate bypass and fatty acid metabolism. Results: Here we report kinetic characterization of S. typhimurium AckA (StAckA) and structures of its unliganded (Form-I, 2.70 angstrom resolution) and citrate-bound (Form-II, 1.90 angstrom resolution) forms. The enzyme showed broad substrate specificity with k(cat)/K-m in the order of acetate > propionate > formate. Further, the K-m for acetyl-phosphate was significantly lower than for acetate and the enzyme could catalyze the reverse reaction (i.e. ATP synthesis) more efficiently. ATP and Mg2+ could be substituted by other nucleoside 5'-triphosphates (GTP, UTP and CTP) and divalent cations (Mn2+ and Co2+), respectively. Form-I StAckA represents the first structural report of an unliganded AckA. StAckA protomer consists of two domains with characteristic beta beta beta alpha beta alpha beta alpha topology of ASKHA superfamily of proteins. These domains adopt an intermediate conformation compared to that of open and closed forms of ligand-bound Methanosarcina thermophila AckA (MtAckA). Spectroscopic and structural analyses of StAckA further suggested occurrence of inter-domain motion upon ligand-binding. Unexpectedly, Form-II StAckA structure showed a drastic change in the conformation of residues 230-300 compared to that of Form-I. Further investigation revealed electron density corresponding to a citrate molecule in a pocket located at the dimeric interface of Form-II StAckA. Interestingly, a similar dimeric interface pocket lined with largely conserved residues could be identified in Form-I StAckA as well as in other enzymes homologous to AckA suggesting that ligand binding at this pocket may influence the function of these enzymes. Conclusions: The biochemical and structural characterization of StAckA reported here provides insights into the biochemical specificity, overall fold, thermal stability, molecular basis of ligand binding and inter-domain motion in AckA family of enzymes. Dramatic conformational differences observed between unliganded and citrate-bound forms of StAckA led to identification of a putative ligand-binding pocket at the dimeric interface of StAckA with implications for enzymatic function.

Small-Angle Neutron-Scattering Studies of Mixed Micellar Structures Made of Dimeric Surfactants Having Imidazolium and Ammonium Headgroups

Planar imidazolium cation based gemini surfactants 16-Im-n-Im-16], 2Br(-) (where n = 2, 3, 4, 5, 6, 8, 10, and 12), exhibit different morphologies and internal packing arrangements by adopting different supramolecular assemblies in aqueous media depending on their number of spacer methylene units (CH2)(n). Detailed measurements of the small-angle neutron-scattering (SANS) cross sections from different imidazolium-based surfactant micelles in aqueous media (D2O) are reported. The SANS data, containing the information of aggregation behavior of such surfactants in the molecular level, have been analyzed on the basis of the Hayter and Penfold model for the macro ion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the dimeric surfactant micelles. The characteristic changes in the SANS spectra of the dimeric surfactant with n = 4 due to variation of temperature have also been investigated. These data are then compared with the SANS characterization data of the corresponding gemini micelles containing tetrahedral ammonium ion based polar headgroups. The critical micellar concentration of each surfactant micelle (cmc) has been determined using pyrene as an extrinsic fluorescence probe. The variation of cmc as a function of spacer chain length has been explained in terms of conformational variation and progressive looping of the spacer into the micellar interior upon increasing the n values. Small-angle neutron-scattering (SANS) cross sections from different mixed micelles composed of surfactants with ammonium headgroups, 16-A(0), 16-Am-n-Am-16], 2Br(-) (where n = 4), 16-I-0, and 16-Im-n-Im-16], 2Br(-) (where n = 4), in aqueous media (D2O) have also been analyzed. The aggregate composition matches with that predicted from the ideal mixing model.

Pressure induced structural phase transformation in TiN: a first-principles study

Titanium nitride (TiN), which is widely used for hard coatings, reportedly undergoes a pressure-induced structural phase transformation, from a NaCl to a CsCl structure, at similar to 7 GPa. In this paper, we use first-principles calculations based on density functional theory with a generalized gradient approximation of the exchange correlation energy to determine the structural stability of this transformation. Our results show that the stress required for this structural transformation is substantially lower (by more than an order of magnitude) when it is deviatoric in nature vis-a-vis that under hydrostatic pressure. Local stability of the structure is assessed with phonon dispersion determined at different pressures, and we find that CsCl structure of TiN is expected to distort after the transformation. From the electronic structure calculations, we estimate the electrical conductivity of TiN in the CsCl structure to be about 5 times of that in NaCl structure, which should be observable experimentally. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4798591]

Ultrafast photoinduced enhancement of nonlinear optical response in 15-atom gold clusters on indium tin oxide conducting film

We show that the third order optical nonlinearity of 15-atom gold clusters is significantly enhanced when in contact with indium tin oxide (ITO) conducting film. Open and close aperture z-scan experiments together with non-degenerate pump-probe differential transmission experiments were done using 80 fs laser pulses centered at 395 nm and 790 nm on gold clusters encased inside cyclodextrin cavities. We show that two photon absorption coefficient is enhanced by an order of magnitude as compared to that when the clusters are on pristine glass plate. The enhancement for the nonlinear optical refraction coefficient is similar to 3 times. The photo-induced excited state absorption using pump-probe experiments at pump wavelength of 395 nm and probe at 790 nm also show an enhancement by an order of magnitude. These results attributed to the excited state energy transfer in the coupled gold cluster-ITO system are different from the enhancement seen so far in charge donor-acceptor complexes and nanoparticle-conjugate polymer composites.

Organogels from Dimeric Bile Acid Esters: In Situ Formation of Gold Nanoparticles

A new class of steroid dimers (bile acid derivatives) linked through ester functionalities were synthesized, which gelled various aromatic solvents. The organogels formed by the three dimeric ester molecules showed birefringent textures and fibrous nature by polarizing optical microscopy and scanning electron microscopy, respectively. A detailed rheological study was performed to estimate the mechanical strengths of two sets of organogels. In these systems, the storage modulus varied in the range of 0.8-3.5 X 10(4) at 1% w/v of the organogelators. The exponents of scaling of the storage modulus and yield stress of the two systems agreed well with those expected for viscoelastic soft colloidal gels with fibrillar flocs. The nanofibers in the organogel were utilized to engineer gold nanoparticles of different sizes and shapes and generate new gel-nanoparticle hybrid materials.

Comparison of ZnO films deposited on indium tin oxide and soda lime glass under identical conditions

ZnO films have been grown via a vapour phase transport (VPT) on soda lime glass (SLG) and indium-tin oxide (ITO) coated glass. ZnO film on ITO had traces of Zn and C which gives them a dark appearance while that appears yellowish-white on SLG. X-ray photoelectron spectroscopy studies confirm the traces of C in the form of C-O. The photoluminescence studies reveal a prominent green luminescence band for ZnO film on ITO. (C) 2013 Author(s).

Gibbs free energy of formation of rhodium sulfides

Using a solid-state electrochemical technique, thermodynamic properties of three sulfide phases (RhS0.882, Rh3S4, Rh2S3) in the binary system (Rh + S) are measured as a function of temperature over the range from (925 to 1275) K. Single crystal CaF2 is used as the electrolyte. The auxiliary electrode consisting of (CaS + CaF2) is designed in such a way that the sulfur chemical potential converts into an equivalent fluorine potential at each electrode. The sulfur potentials at the measuring electrodes are established by the mixtures of (Rh + RhS0.882), (RhS0.882 + Rh3S4) and (Rh3S4 + Rh2S3) respectively. A gas mixture (H-2 + H2S + Ar) of known composition fixes the sulfur potential at the reference electrode. A novel cell design with physical separation of rhodium sulfides in the measuring electrode from CaS in the auxiliary electrode is used to prevent interaction between the two sulfide phases. They equilibrate only via the gas phase in a hermetically sealed reference enclosure. Standard Gibbs energy changes for the following reactions are calculated from the electromotive force of three cells: 2.2667Rh (s) + S-2 (g) -> 2.2667RhS(0.882) (s), Delta(r)G degrees +/- 2330/(J . mol(-1)) = -288690 + 146.18 (T/K), 4.44RhS(0.882) (s) + S-2 (g) -> 1.48Rh(3)S(4) (s), Delta(r)G degrees +/- 2245/(J . mol(-1)) = -245596 + 164.31 (T/K), 4Rh(3)S(4) (s) + S-2 (g) -> 6Rh(2)S(3) (s), Delta(r)G degrees +/- 2490/(J . mol(-1)) = -230957 + 160: 03 (T/K). Standard entropy and enthalpy of formation of rhodium sulfides from elements in their normal standard states at T = 298.15 K are evaluated. (C) 2013 Elsevier Ltd. All rights reserved.

Effect of TiN particulate reinforcement on corrosive behaviour of aluminium 6061 composites in chloride medium

In the present investigation, the corrosive behaviour of Al 6061-TiN particulate composites prepared by liquid metallurgy has been studied in chloride medium using electroanalytical techniques such as Tafel, cyclic polarization and electrochemical impedance spectroscopy (EIS). Surface morphology of the sample electrodes was examined using scanning electron micrography and energy dispersive X-ray methods. X-ray diffraction technique was used to confirm inclusion of TiN particulates in the matrix alloy and identify the alloying elements and intermetallic compounds in the Al 6061 composites. Polarization studies indicate an increase in the corrosion resistance in composites compared to the matrix alloy. EIS study reveals that the polarization resistance (R (p)) increases with increase in TiN content in composites, thus confirming improved corrosion resistance in composites. The observed decrease in corrosion rate in the case of composites is due to decoupling between TiN particles and Al 6061 alloy. It is understood that after the initiation of corrosion, interfacial corrosion products may have decoupled the conducting ceramic TiN from Al 6061 matrix alloy thus eliminating the galvanic effect between them.

Enhanced electrochemical performance of graphene nanosheet thin film anode decorated with tin nanoparticles

Graphene nanosheet (GNS) was synthesized by using microwave plasma enhanced CVD on copper substrate and followed by evaporation of tin metal. Scanning and transmission electron microscopy show that nanosize Sn particles are well embedded into the GNS matrix. The composition, structure, and electrochemical properties were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), cyclic voltammetry (CV) and chrono-potentiometry. The first discharge capacity of as-deposited and annealed SnGNS obtained was 1551 mA h/g and 975 mA h/g, respectively. The anodes show excellent cyclic performance and coulombic efficiency.

Phase and Dimensionality of Tin Oxide at graphene nanosheet array and its Electrochemical performance as anode for Lithium Ion Battery

We incorporated tin oxide nanostructures into the graphene nanosheet matrix and observed that the phase of tin oxide varies with the morphology. The highest discharge capacity and coulumbic efficiency were obtained for SnO phase of nanoplates morphology. Platelet morphology of tin oxide shows more reversible capacity than the nanoparticle (SnO2 phase) tin oxide. The first discharge capacity obtained for SnO@GNS is 1393 and 950 mAh/g for SnO2@GNS electrode at a current density of 23 mu A/cm(2). A stable capacity of about 1022 and 715 mAh/g was achieved at a current rate of 23 mu A/cm(2) after 40 cycles for SnO@GNS and SnO2@GNS anodes, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.