Synergistic Effect of Mo plus Cu Codoping on the Photocatalytic Behavior of Metastable TiO2 Solid Solutions

Codoping with Cu and Mo is shown to have a synergistic effect on the photocatalytic activity of TiO2. The enhancement in activity is observed only if the synthesis route results in TiO2 in which (Cu, Mo) codopants are forced into the TiO2 lattice. Using X-ray photoelectron spectroscopy, Cu and Mo are shown to be present in the +2 and +6 oxidation states, respectively. A systematic study of the ternary system shows that TiO2 containing 6 mol % CuO and 1.5 mol % MoO3 is the most active ternary composition. Ab initio calculations show that codoping of TiO2 using (Mo, Cu) introduces levels above the valence band, and below the conduction band, resulting in a significant reduction in the band gap (similar to 0.8 eV). However, codoping also introduces deep defect states, which can have a deleterious impact on photoactivity. This helps rationalize the narrow compositional window over which the enhancement in photocatalytic activity is observed.

A new tungsten-free gamma-gamma ` Co-Al-Mo-Nb-based superalloy

We present the first report of a tungsten-free cobalt-based superalloy having a composition Co-10Al-5Mo-2Nb. The alloy is strengthened by cuboidal precipitates of metastable Co-3(Al,Mo,Nb) distributed throughout the microstructure. The precipitates are coherent with the face-centred cubic gamma-Co matrix and possess ordered Ll(2) structure. The microstructure is identical to the popular gamma-gamma' type nickel-based superalloys and that of recently reported Co-Al-W-based alloys. Being tungsten free, the reported alloy has higher specific proof stress compared to existing cobalt-based superalloys. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Jacalin-carbohydrate interactions: distortion of the ligand molecule as a determinant of affinity

Jacalin is among the most thoroughly studied lectins. Its carbohydrate-binding site has also been well characterized. It has been postulated that the lower affinity of beta-galactosides for jacalin compared with beta-galactosides is caused by steric interactions of the substituents in the former with the protein. This issue has been explored energetically and structurally using different appropriate carbohydrate complexes of jacalin. It turns out that the earlier postulation is not correct. The interactions of the substituent with the binding site remain essentially the same irrespective of the anomeric nature of the substitution. This is achieved through a distortion of the sugar ring in beta-galactosides. The difference in energy, and therefore in affinity, is caused by a distortion of the sugar ring in beta-galactosides. The elucidation of this unprecedented distortion of the ligand as a strategy for modulating affinity is of general interest. The crystal structures also provide a rationale for the relative affinities of the different carbohydrate ligands for jacalin.

Remarkable enhancement in hydrogen storage on free-standing Ti3B and BC3 supported Ti-3 clusters

Hydrogen storage capacity of Tin-1B (n = 3-7) clusters is studied and compared with that of the pristine Ti-n (n = 3-7), using density functional theory (DFT) based calculations. Among these clusters, Ti3B shows the most significant enhancement in the storage capacity by adsorbing 12 H-2, out of which three are dissociated and the other nine are stored as dihydrogen via Kubas-interaction. The best storage in Ti3B is owed to a large charge transfer from Ti to B along with the largest distance of Ti empty d-states above the Fermi level, which is a distinct feature of this particular cluster. Furthermore, the effect of substrates on the storage capacity of Ti3B was assessed by calculating the number of adsorbed H-2 on Ti-3 cluster anchored onto B atoms in the B-doped graphene, BC3, and BN substrates. Similar to free-standing Ti3B, Ti-3 anchored onto boron atom in BC3, stores nine di-hydrogen via Kubas interaction, at the same time eliminating the total number of non-useful dissociated hydrogen. Gibbs energy of adsorption as a function of H-2 partial pressure, indicated that at 250 K and 300 K the di-hydrogens on Ti-3@BC3 adsorb and desorb at ambient pressures. Importantly, Ti-3@BC3 avoids the clustering, hence meeting the criteria for efficient and reversible hydrogen storage media. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

IR spectroscopy as a probe for C-H center dot center dot center dot X hydrogen bonded supramolecular synthons

Weak hydrogen bonds of the type C-H center dot center dot center dot X (X: N, O, S and halogens) have evoked considerable interest over the years, especially in the context of crystal engineering. However, association patterns of weak hydrogen bonds are generally difficult to characterize, and yet the identification of such patterns is of interest, especially in high throughput work or where single crystal X-ray analysis is difficult or impossible. To obtain structural information on such assemblies, we describe here a five step IR spectroscopic method that identifies supramolecular synthons in weak hydrogen bonded dimer assemblies, bifurcated systems, and p-electron mediated synthons. The synthons studied here contain C-H groups as hydrogen bond donors. The method involves: (i) identifying simple compounds/cocrystals/salts that contain the hydrogen bonded dimer synthon of interest or linear hydrogen bonded assemblies between the same functionalities; (ii) scanning infrared (IR) spectra of the compounds; (iii) identifying characteristic spectral differences between dimer and linear; (iv) assigning identified bands as marker bands for identification of the supramolecular synthon, and finally (v) identifying synthons in compounds whose crystal structures are not known. The method has been effectively implemented for assemblies involving dimer/linear weak hydrogen bonds in nitrobenzenes (C-H center dot center dot center dot O-NO), nitro-dimethylamino compounds (NMe2 center dot center dot center dot O2N), chalcones (C-H center dot center dot center dot O=C), benzonitriles (C-H center dot center dot center dot N C) and fluorobenzoic acids (C-H center dot center dot center dot F-C). Two other special cases of C-H center dot center dot center dot pi and N-H center dot center dot center dot pi synthons were studied in which the band shape of the C-H stretch in hydrocarbons and the N-H deformation in aminobenzenes was examined.

Synthesis and electrocatalytic properties of manganese dioxide for non-enzymatic hydrogen peroxide sensing

Manganese dioxide nanoparticles were synthesized by chemical reduction route at different growth temperatures of 40 degrees C, 80 degrees C, 100 degrees C and were characterized using X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Cyclic Voltammetry (CV) and chronoamperometry (CA) analysis. FESEM results show that on increasing growth temperature the morphology changes from clusters into mixture of rods and flakes. XPS analysis reveals the formation of MnO2. Then these particles were immobilized on Pt electrode. A platinum (Pt) electrode modified with low dimensional MnO2 was investigated as a chronoamperometric (CA) sensor for hydrogen peroxide sensing (H2O2). The sample prepared at 100 degrees C shows good electrocatalytic ability for H2O2 sensing when compared with the samples prepared at 40 degrees C and 80 degrees C. At an operating potential of 0.3 V vs. Ag/AgCl catalytic oxidation of the analyte is measured for chronoamperometric (CA) monitoring. The CA signals are linearly proportional to the concentration of H2O2. It is also found that the morphology of the nanostructure plays a vital role in the detection of H2O2. (C) 2014 Elsevier Ltd. All rights reserved.

Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation

Here, we report the clean and facile synthesis of Pt and Pd nanoparticles decorated on reduced graphene oxide (rGO) by the simultaneous reduction of graphene oxide (GO) and the metal ions in Mg/acid medium. As-generated Pt and Pd nanoparticles serve as a heterogeneous catalyst for the further reduction of the rGO by the hydrogen spill-over process. The C/O ratio is much higher as compared to the rGO obtained by the reduction of GO by only Mg/acid. Overall, the process is rapid, facile and green that does not require any toxic chemical agent or any rigorous chemical reactions. We perform the catalytic reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP) at room temperature by Pd@rGO and Pt@rGO. The reduction is complete within 35 s for Pd@rGO and 60 s for Pt@rGO when 50 mu g of hybrid catalyst is used for 0.5 ml of 1 mM of 4-NP. In case of ethanol oxidation, the current density for Pd@rGO is comparable to commercial Pt/C but is doubled for Pt@rGO. Overall, both structures show highly stable catalytic activity compared to commercial Pt/C. (C) 2014 Elsevier B.V. All rights reserved.

Three centered hydrogen bonds of the type C=O...H(N)...X-C in diphenyloxamide derivatives involving halogens and a rotating CF3 group: NMR, QTAIM, NCI and NBO studies

The existence of three centered C=O...H(N)...X-C hydrogen bonds (H-bonds) involving organic fluorine and other halogens in diphenyloxamide derivatives has been explored by NMR spectroscopy and quantum theoretical studies. The three centered H-bond with the participation of a rotating CF3 group and the F...H-N intramolecular hydrogen bonds, a rare observation of its kind in organofluorine compounds, has been detected. It is also unambiguously established by a number of one and two dimensional NMR experiments, such as temperature perturbation, solvent titration, N-15-H-1 HSQC, and F-19-H-1 HOESY, and is also confirmed by theoretical calculations, such as quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO) and non-covalent interaction (NCI).

Targeting Mycobacterium tuberculosis Topoisomerase I by Small-Molecule Inhibitors

We describe inhibition of Mycobacterium tuberculosis topoisomerase I (MttopoI), an essential mycobacterial enzyme, by two related compounds, imipramine and norclomipramine, of which imipramine is clinically used as an antidepressant. These molecules showed growth inhibition of both Mycobacterium smegmatis and Mycobacterium tuberculosis cells. The mechanism of action of these two molecules was investigated by analyzing the individual steps of the topoisomerase I (topoI) reaction cycle. The compounds stimulated cleavage, thereby perturbing the cleavage-religation equilibrium. Consequently, these molecules inhibited the growth of the cells overexpressing topoI at a low MIC. Docking of the molecules on the MttopoI model suggested that they bind near the metal binding site of the enzyme. The DNA relaxation activity of the metal binding mutants harboring mutations in the DxDxE motif was differentially affected by the molecules, suggesting that the metal coordinating residues contribute to the interaction of the enzyme with the drug. Taken together, the results highlight the potential of these small molecules, which poison the Mycobacterium tuberculosis and Mycobacterium smegmatis topoisomerase I, as leads for the development of improved molecules to combat mycobacterial infections. Moreover, targeting metal coordination in topoisomerases might be a general strategy to develop new lead molecules.

Effects of hydrogen bonding on amide-proton chemical shift anisotropy in a proline-containing model peptide

Longitudinal relaxation due to cross-correlation between dipolar ((HN-1H alpha)-H-1) and amide-proton chemical shift anisotropy (H-1(N) CSA) has been measured in a model tripeptide Piv-(L)Pro-(L)Pro-(L)Phe-OMe. The peptide bond across diproline segment is known to undergo cis/trans isomerization and only in the cis form does the lone Phe amide-proton become involved in intramolecular hydrogen bonding. The strength of the cross correlated relaxation interference is found to be significantly different between cis and trans forms, and this difference is shown as an influence of intramolecular hydrogen bonding on the amide-proton CSA. (C) 2015 Elsevier B.V. All rights reserved.

Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol

The gas-phase infrared spectra of 1,2-ED and 1,4-BD have been, recorded at three different temperatures using a multipass gas cell of 6 m optical path length. DFT calculation has also been carried out using 6-311++G** and aug-cc-pVDZ basis sets to look for the existence of intramolecular hydrogen bonding, in them from the red shift and infrared absorption intensity enhancement of the bonded O-H band compared to that of the free O-H hand. Equilibrium population analysis With 10 conformers of 1,2-ED and 1,4-BD at experimental temperatures were-carried out for the reconstruction of the Observed vibrational spectra at that temperature,using standard statistical relationships. The most abundant conformer at experimental temperatures, was identified. In 1,2-ED a red shift of 45 cm(-1) in the intramolecularly interacting O-H stretching vibrational band position and no significant intensity enhancement compared to that of-the free O-H have been observed. On the contrary, in one of the hydrogen bonded conformers of 1,4-BD, a 124 cm(-1) red shift in the O-H stretching frequency and 8.5 times-intensity enhancement for the ``bonded'' O-H compared to that of the ``free'' O-H is seen. On the basis of this comparative study, we have concluded that strong intramolecular hydrogen bonding exists in 1,4-BD. But there appears, to be weak intramolecular hydrogen bonding in 1,2-ED at temperatures of 303, 313, and 323 Km the gas phase We have found that most stable hydrogen-bonded conformers of 1,4-BD are less populated than some of the non-hydrogen-bonded conformers. Even for the 1,4-BD, the relative population of the g'GG'Gt conformer, which has a strong intramolecular,hydrogen bond, is less than what is predicted. Perhaps the intramolecular hydrogen bond plays a less Significant role in the relative stability,of the various Conformers than what has been predicted from calculations and prevails in the literature.

Suspended core-shell Pt-PtOx nanostructure for ultrasensitive hydrogen gas sensor

High sensitivity gas sensors are typically realized using metal catalysts and nanostructured materials, utilizing non-conventional synthesis and processing techniques, incompatible with on-chip integration of sensor arrays. In this work, we report a new device architecture, suspended core-shell Pt-PtOx nanostructure that is fully CMOS-compatible. The device consists of a metal gate core, embedded within a partially suspended semiconductor shell with source and drain contacts in the anchored region. The reduced work function in suspended region, coupled with builtin electric field of metal-semiconductor junction, enables the modulation of drain current, due to room temperature Redox reactions on exposure to gas. The device architecture is validated using Pt-PtO2 suspended nanostructure for sensing H-2 down to 200 ppb under room temperature. By exploiting catalytic activity of PtO2, in conjunction with its p-type semiconducting behavior, we demonstrate about two orders of magnitude improvement in sensitivity and limit of detection, compared to the sensors reported in recent literature. Pt thin film, deposited on SiO2, is lithographically patterned and converted into suspended Pt-PtO2 sensor, in a single step isotropic SiO2 etching. An optimum design space for the sensor is elucidated with the initial Pt film thickness ranging between 10 nm and 30 nm, for low power (< 5 mu W), room temperature operation. (C) 2015 AIP Publishing LLC.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl center dot center dot center dot N halogen-bonded clusters following vertical ionization

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation-and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH2, CF3, and COOH substituents) molecules paired with NH3 (referred as ACl:NH3 complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation-and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31+G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl center dot center dot center dot NH3 complex, the hole is predicted to migrate from the NH3-end to the ClCN-end of the NCCl center dot center dot center dot NH3 complex in approximately 0.5 fs on the D-0 cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H2NCl:NH3, F3CCl:NH3, and HOOCCl:NH3, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH3 and HOCl:NH3 complexes do not exhibit any charge migration following vertical ionization to the D-0 cation state, pointing to interesting halogen bond strength-dependent charge migration. (C) 2015 AIP Publishing LLC.

Hydrogen-induced mechanical properties of amorphous silicon thin films

Mechanical properties of thin films such as residual stress and hardness are of paramount importance from the device fabrication point of view. Intrinsic stress in sputtered films can be tensile or compressive as decided by the number density and the energy of the plasma species striking the growing film. In the presence of hydrogen we analyzed the applicability of idealized stress reversal curve for amorphous silicon thin films deposited by DC, pulsed DC (PDC) and RF sputtering. We are successfully able to correlate the microstructure with the stress reversal and hardness. We observed a stress reversal from compressive to tensile with hydrogen incorporation. It was found that unlike in idealized stress reversal curve case, though the energy of plasma species is less in DC plasma, DC deposited films exhibit more compressive stress, followed by PDC and RF deposited films. A tendency towards tensile stress from compressive stress was observed at similar to 13, 18 and 23 at%H for DC, PDC and RF deposited films respectively, which is in exact agreement with the vacancy to void transition in the films. Regardless of the sputtering power mode, the hardness of a-Si:H films is found to be maximum at C-H similar to 10 at%H. Enhancement in hardness with C-H (up to C-H similar to 10 at%H) is attributed to increase of Si-H bonds. Beyond C-H similar to 10 at%H, hardness starts falling. (C) 2015 Elsevier Ltd. All rights reserved.

Effects of heat exchanger design on the performance of a solid state hydrogen storage device

Heat exchanger design plays a significant role in the performance of solid state hydrogen storage device. In the present study, a cylindrical hydrogen storage device with an embedded annular heat exchanger tube with radial circular copper fins, is considered. A 3-D mathematical model of the storage device is developed to investigate the sorption performance of metal hydride (MH). A prototype of the device is fabricated for 1 kg of MH alloy, LaNi5, and tested at constant supply pressure of hydrogen, validating the simulation results. Absorption characteristics of storage device have been examined by varying different operating parameters such as hydrogen supply pressure and cooling fluid temperature and velocity. Absorption process is completed in 18 min when these parameters are 15 bar, 298 K and 1 m/s respectively. A study of geometric parameters of copper fins (such as perforation, number and thickness of fin) has been carried out to investigate their effects on absorption process. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.