Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v max, is found to correlate extremely well with the shortest Cu–O distance.v max increases at an impressive rate of sim20 cm–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu2+–O2– distance in square-planar CuO4 complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a ldquotitrationrdquo procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa2Cu3O7–d structure such as LaCaBaCu3O7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La2(Ca, Sr)Cu2O6. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.

Chemical probes into the active centre of a heme thiolate monoxygenase

Linalool-8-monoxygenase, a typical bacterial P-450 heme thiolase, shows a high degree of substrate specificity towards linalool. The active site of the pure enzyme has been probed with a large number of substrate analogues with systematic alterations or conformational variations in the linalool molecule. The comparison of three parameters, the mo→mos conversion of the enzyme as a result of substrate binding monitored at 392 nm, theK D of the analogues giving information about energies of association and the relative turnover as substrate have given information about the space-filling characteristics of the substrates in the enzyme cleft, the number of contacts the molecules make with the respective domains of the enzyme and the distance of the site undergoing hydroxylation from the oxygen site, respectively. The data permit the conclusion that linalool makes contact with the enzyme by hydrogen bonding with the hydroxyl group as well through hydrophobic association with all the eight carbons carrying hydrogen in the molecules.

Sonochemical synthesis of Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta of similar to 4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe3+ ion in CeO2, lattice oxygen is activated and 33% Fe substituted CeO2 i.e. Ce0.67Fe0.33O1.835 reversibly releases 0.31O] up to 600 degrees C which is higher or comparable to the oxygen storage capacity of CeO2-ZrO2 based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd2+/0(0.89 V) and Fe3+/2+ (0.77 V) with Ce4+/3+ (1.61 V), Pd ion accelerates the electron transfer from Fe2+ to Ce4+ in Ce0.65Fe0.33Pd0.02O1.815, making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce0.65Fe0.33Pd0.02O1.815 is found to be as low as 38 kJ mol(-1). Ce0.67Fe0.33O1.835 and Ce0.65Fe0.33Pd0.02O1.815 have also shown high activity for the water gas shift reaction. CO conversion to CO2 is 100% H-2 specific with these catalysts and conversion rate was found to be as high 27.2 mu moles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce0.65Fe0.33Pd0.02O1.815.

Binding of active site directed ligands to phospholipase A2: Implications on the molecular constraints and catalytic mechanism

Molecular constraints for the localization of active site directed ligands (competitive inhibitors and substrates) in the active site of phospholipase A2 (PLA2) are characterized. Structure activity relationships with known inhibitors suggest that the head : group interactions dominate the selectivity as well as a substantial part of the affinity. The ab initio fitting of the amide ligands in the active site was carried out to characterize the head group interactions. Based on a systematic coordinate space search, formamide is docked with known experimental constraints such as coordination of the carbonyl group to Ca2+ and hydrogen bond between amide nitrogen and ND1 of His48. An optimal position for a bound water molecule is identified and its significance for the catalytic mechanism is postulated. Unlike the traditional ''pseudo-triad'' mechanism, the ''Ca-coordinatedoxyanion'' mechanism proposed here invokes activation of the catalytic water to form the oxyanion in the coordination sphere of calcium. As it attacks the carbonyl carbon of the ester, a near-tetrahedral intermediate is formed. As the second proton of the catalytic water is abstracted by the ester oxygen, its reorientation and simultaneous cleavage form hydrogen bond with ND1 of His48. In this mechanism of esterolysis, a catalytic role for the water co-ordinated to Ca2+ is recognised.

Electrocatalysis and redox behavior of Pt(2+) ion in CeO(2) and Ce(0.85)Ti(0.15)O(2): XPS evidence of participation of lattice oxygen for high activity

Electronic states of CeO(2), Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) , and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) is active toward these reactions compared with CeO(2) alone. Higher electrocatalytic activity of Pt(2+) ions in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) compared with the same amount of Pt(0) in Pt/C is attributed to Pt(2+) ion interaction with CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) does not suffer from CO poisoning effect unlike Pt(0) in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO(2). Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.

A Single-Stage Water-Gas Shift Reaction over Highly Active and Stable Si- and Al-Substituted Pt/CeO2 Catalysts

Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d catalysts were synthesized by using a low-temperature sonochemical method and characterized by using XRD, TEM, XPS, FTIR, and BET surface analyzer. The catalytic activities of these compounds were investigated for the watergas shift reaction in the temperature range of 140-440 degrees C. The substitution of Si in Ce0.98Pt0.02O2-d increased the releasing capacity of lattice oxygen, whereas the substitution of Al decreased the reducibility of Ce0.98Pt0.02O2-d, as evidenced by hydrogen temperature-programmed reduction studies. However, both the catalysts showed a considerable improvement in terms of activity and stability compared to Ce0.98Pt0.02O2-d. The combined activity measurement and characterization results suggest that the increase in the oxygen vacancy, which acts as a dissociation center for water, is the primary reason for the improvement in the activity of modified Ce0.98Pt0.02O2-d. Both the catalysts are 100?% selective toward H2 production, and approximately 99?% conversion of CO to CO2 was observed at 260 and 270 degrees C for Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d, respectively. These catalysts do not deactivate during the daily startup/shutdown operations and are sustainable even after prolonged reaction. Notably, these catalysts do not require any pretreatment or activation during startup/shutdown operations.

Metal based photosensitizers of tetradentate Schiff base: Promising role in anti-tumor activity through singlet oxygen generation mechanism

In the present investigation, a Schiff base N'(1),N'(3)-bis(Z)-(2-hydroxynapthyl)methylidene]benzene-1,3-dicarbod ihydrazide (L-1) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized as novel photosensitizing agents for photodynamic therapy (PDT). The interaction of these complexes with calf thymus DNA (CT DNA) has been explored using absorption, thermal denaturation and viscometric studies. The experimental results revealed that Co(II) and Ni(II) complexes on binding to CT DNA imply a covalent mode, most possibly involving guanine N7 nitrogen of DNA, with an intrinsic binding constant K-b of 4.5 x 10(4) M-1 and 4.2 x 10(4) M-1, respectively. However, interestingly, the Cu(II) complex is involved in the surface binding to minor groove via phosphate backbone of DNA double helix with an intrinsic binding constant K-b of 5.7 x 10(4) M-1. The Co(II), Ni(II) and Cu(II) complexes are active in cleaving supercoiled (SC) pUC19 DNA on photoexposure to UV-visible light of 365 nm, through O-1(2) generation with quantum yields of 0.28, 0.25 and 0.30, respectively. Further, these complexes are cytotoxic in A549 lung cancer cells, showing an enhancement of cytotoxicity upon light irradiation. (C) 2013 Elsevier B.V. All rights reserved.

High Catalytic Activity of Amorphous Ir-Pi for Oxygen Evolution Reaction

Large-scale production of hydrogen gas by water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER) at the anode. The development of a highly active and stable catalyst for OER is a challenging task. Electrochemically prepared amorphous metal-based catalysts have gained wide attention after the recent discovery of a cnbalt-phosphate (Co-Pi) catalyst: Herein, an amorphous iridium-phosphate (Ir-Pi) is investigated as an oxygen evolution catalyst. The catalyst is prepared by the anodic polarization of carbon paper electrodes in neutral phosphate buffer solutions containing IrCl3. The Ir-Pi film deposited on the substrate has significant amounts of phosphate and It centers in an oxidation state higher than +4. Phosphate plays a significant role in the deposition of the catalyst and also in its activity toward OER. The onset potential of OER on the Ir-Pi is about 150 mV lower in comparison with the Co-Pi under identical experimental conditions. Thus, Ir-Pi is a promising catalyst for electrochemical oxidation of water.

Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.

Study of the processes occurring when sputtering YBa2Cu3O7-x in pure oxygen

The sputter deposition of YBa2Cu3O7-x in a de-diode was performed in pure oxygen medium and an optical spectroscopic study of the resultant discharge revealed strong emissions from both metal atoms and oxygen ions. Emission intensities were studied in pressure range from 0.5 to 3 mbar, with substrate temperatures from 150 to 850 degrees C. Raising the substrate temperature to 850 degrees C increased the number of positive ions and excited neutral atoms. Raising the pressure decreased the emission intensities of excited neutral and ionic species. The results have been compared with those obtained from Langmuir probe measurements. The rise in emission intensities of excited neutrals and ions with temperature suggested the possibility of chemically enhanced physical sputtering of YBa2Cu3O7-x. The effect of process conditions on film composition and quality is also discussed.

The role of lysine-41 in RNase A catalysis - A quantum chemical study on the active site ligand complex

Several mechanisms have been proposed to explain the action of enzymes at the atomic level. Among them, the recent proposals involving short hydrogen bonds as a step in catalysis by Gerlt and Gassman [1] and proton transfer through low barrier hydrogen bonds (LBHBs) [2, 3] have attracted attention. There are several limitations to experimentally testing such hypotheses, Recent developments in computational methods facilitate the study of active site-ligand complexes to high levels of accuracy, Our previous studies, which involved the docking of the dinucleotide substrate UpA to the active site of RNase A [4, 5], enabled us to obtain a realistic model of the ligand-bound active site of RNase A. From these studies, based on empirical potential functions, we were able to obtain the molecular dynamics averaged coordinates of RNase A, bound to the ligand UpA. A quantum mechanical study is required to investigate the catalytic process which involves the cleavage and formation of covalent bonds. In the present study, we have investigated the strengths of some of the hydrogen bonds between the active site residues of RNase A and UpA at the ab initio quantum chemical level using the molecular dynamics averaged coordinates as the starting point. The 49 atom system and other model systems were optimized at the 3-21G level and the energies of the optimized systems were obtained at the 6-31G* level. The results clearly indicate the strengthening of hydrogen bonds between neutral residues due to the presence of charged species at appropriate positions. Such a strengthening manifests itself in the form of short hydrogen bonds and a low barrier for proton transfer. In the present study, the proton transfer between the 2'-OH of ribose (from the substrate) and the imidazole group from the H12 of RNase A is influenced by K41, which plays a crucial role in strengthening the neutral hydrogen bond, reducing the barrier for proton transfer.

Vanadium Catalysis in Bromoperoxidation Reaction

Peroxidative bromination of phenol red to its tetrabromo derivative, bromophenol blue, required vanadate in addition to H2O2 when carried out in the pH range of 5-7. Excess H2O2, with ratio of H2O2:vanadate of 2:1 and above, prevented the reaction. Diperoxovanadate, known to be formed in such reaction mixtures, was ineffective by itself and needed uncomplexed vanadate (V-v) or vanadyl (V-iv) to support bromination. Bromide-assisted reduction of the excess vanadate to vanadyl appeared to be an essential secondary reaction. In the absence of phenol red oxygen was released, and concomitantly bromide was oxidized to a form competent to brominate phenol red added after termination of oxygen release. These findings indicated participation of reactions leading to an intermediate derived from vanadyl and diperoxovanadate, previously described from this laboratory (Arch. Biochem. Biophys. 316, 319-326, 1995). Continuous bromination of phenol red occurred when glucose oxidase-glucose system was used as a source of continuous flow of H2O2. A scheme of reactions involving peroxovanadates (mono-, di-, mu-, and bromo-) is proposed for the formation and utilization of an active brominating species and for the recycling of the product, mono-peroxovanadate, by H2O2, which explains the catalytic role of vanadium in the bromoperoxidation reaction.

High Oxygen Storage Capacity and High Rates of CO Oxidation and NO Reduction Catalytic Properties of Ce1-xSnxO2 and Ce0.78Sn0.2Pd0.02O2-delta

Ce1-xSnxO2 (x = 0.1-0.5) solid solution and its Pd substituted analogue have been prepared by a single step solution combustion method using tin oxalate precursor. The compounds were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and H-2/temperature programmed redution (TPR) studies. The cubic fluorite structure remained intact up to 50% of Sri substitution in CeO2, and the compounds were stable up to 700 C. Oxygen storage capacity of Ce1-xSnxO2 was found to be much higher than that of Ce1-xZrxO2 due to accessible Ce4+/Ce3+ and Sn4+/Sn2+ redox couples at temperatures between 200 and 400 C. Pd 21 ions in Ce0.78Sn0.2Pd0.02O2-delta are highly ionic, and the lattice oxygen of this catalyst is highly labile, leading to low temperature CO to CO2 conversion. The rate of CO oxidation was 2 mu mol g(-1) s(-1) at 50 degrees C. NO reduction by CO with 70% N-2 selectivity was observed at similar to 200 degrees C and 100% N-2 selectivity below 260 degrees C with 1000-5000 ppm NO. Thus, Pd2+ ion substituted Ce1-xSnxO2 is a superior catalyst compared to Pd2+ ions in CeO2, Ce1-xZrxO2, and Ce1-xTixO2 for low temperature exhaust applications due to the involvement of the Sn2+/Sn4+ redox couple along with Pd2+/Pd-0 and Ce4+/Ce3+ couples.

Hyperexpression of biologically active human chorionic gonadotropin using the methylotropic yeast, Pichia pastoris

Human chorionic gonadotropin (hCG), a heterodimeric glycoprotein hormone, is composed of an alpha subunit noncovalentlv associated with the hormone-specific beta subunit. The objective of the present study was recombinant expression of properly folded, biologically active hCG and its subunits using an expression system that could be used for structure-function studies while providing adequate quantities of the hormone for immunocontraceptive studies. We report here expression of biologically active hCG and its subunits using a yeast expression system, Pichia pastoris. The recombinant hGG alpha and hCG beta subunits were secreted into the medium and the levels of expression achieved at shake culture level were 24 and 2.7-3 mg/l secretory medium respectively. Go-expression of both subunits in the same cell resulted in secretion of heterodimeric hGG into the medium. The pichia-expressed hCG was immunologically similar to the native hormone, capable of binding to the LH receptors and stimulating a biological response in vitro. Surprisingly, the maximal response obtained was twice that obtained with the native hGG. The le level of expression of hCG achieved was 12-16 mg/l secretory medium and is expected to increase several-fold in a fermenter. Thus the Pichia expression system is capable of hyperexpressing properly folded, biologically active hGG and is suitable for structure-function studies of the hormone.