DRIFTS studies on CO and NO adsorption and NO plus CO reaction over Pd2+-substituted CeO2 and Ce0.75Sn0.25O2 catalysts

Sequential adsorption of CO and NO as well as equimolar NO + CO reaction with variation of temperature over Pd2+ ion-substituted CeO2 and Ce0.75Sn0.25O2 supports has been studied by DRIFTS technique. The results are compared with 2 at.% Pd/Al2O3 containing Pd-0. Both linear and bridging Pd-0-CO bands are observed over 2 at.% Pd/Al2O3. But, band positions are shifted to higher frequencies in Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts that could be associated with Pd delta+-CO species. In contrast, a Pd2+-CO band at 2160 cm(-1) is observed upon CO adsorption over Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts pre-adsorbed with NO and a Pd+-CO band at 2120 cm(-1) is slowly developed on Ce(0.73)Srl(0.25)Pd(0.02)O(2-delta) over time. An intense linear Pd-0-NO band at 1750 cm(-1) found upon NO exposure to CO pre-adsorbed 2 at.% Pd/Al2O3 indicates molecular adsorption of NO. On the other hand, a weak Pd2+-NO band at 1850 cm(-1) is noticed after NO exposure to Ce0.98Pd0.02O2-delta catalyst pre-adsorbed with CO indicating dissociative adsorption of NO which is crucial for NO reduction. Pd-0-NO band is initially formed over CO pre-adsorbed Ce0.73Sn0.25Pd0.02O2-delta which is red-shifted over time along with formation of Pd2+-NO band. Several intense bands related to nitrates and nitrites are observed after exposure of NO to fresh as well as CO pre-adsorbed Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts. Ramping the temperature in a DRIFTS cell upon NO and CO adsorption shows the formation of N2O and NCO surface species, and N2O-formation temperature is comparable with the reaction done in a reactor.

Highly regioselective C2-alkenylation of indoles using the N-benzoyl directing group: an efficient Ru-catalyzed coupling reaction

A highly regioselective alkenylation of indole at the C2-position has been achieved using the Ru(II) catalyst by employing a directing group strategy. This strategy offers rare selectivity for the alkenylation N-benzoylindole at the C-2 position in the presence of the more active C3- and C7-position of indole and the ortho-positions of the benzoyl protecting group. A simple deprotection of the benzoyl group has also been exemplified, and the resulting product serves as a useful synthon for natural product syntheses.

A pseudobinary approach to study interdiffusion and the Kirkendall effect in multicomponent systems

Interdiffusion studies become increasingly difficult to perform with the increasing number of elements in a system. It is rather easy to calculate the interdiffusion coefficients for all the compositions in the interdiffusion zone in a binary system. The intrinsic diffusion coefficients can be calculated for the composition of Kirkendall marker plane in a binary system. In a ternary system, however, the interdiffusion coefficients can only be calculated for the composition where composition profiles from two different diffusion couples intersect. Intrinsic diffusion coefficients are possible to calculate when the Kirkendall markers are also present at that composition, which is a condition that is generally difficult to satisfy. In a quaternary system, the composition profiles for three different diffusion couples must intersect at one particular composition to calculate the diffusion parameters, which is a condition that is almost impossible to satisfy. To avoid these complications in a multicomponent system, the average interdiffusion coefficients are calculated. I propose a method of calculating the intrinsic diffusion coefficients and the variation in the interdiffusion coefficients for multicomponent systems. This method can be used for a single diffusion couple in a multicomponent pseudobinary system. The compositions of the end members of a diffusion couple should be selected such that only two elements diffuse into the interdiffusion zone. A few hypothetical diffusion couples are considered in order to validate and explain our method. Various sources of error in the calculations are also discussed.

Unprecedented formation of a 14-membered dihydropyran macrocycle via sequential olefin cross metathesis-intramolecular hetero Diels-Alder reaction

Formation of a 2,3-dihydro-4H-pyran containing 14-membered macrocycle by sequential olefin cross metathesis and a highly regiospecific hetero Diels-Alder reaction was observed in the reaction of a hydroxydienone derived from tartaric acid with Grubbs' second generation catalyst. It was found that the free alcohol in the hydroxyenone led to the macrocycle formation, while protection of the hydroxy group formed the ring closing metathesis product. (C) 2013 Elsevier Ltd. All rights reserved.

Adiabatic eigenfunction-based approach for coherent excitation transfer: An almost analytical treatment of the Fenna-Matthews-Olson complex

We suggest a method of studying coherence in finite-level systems coupled to the environment and use it for the Hamiltonian that has been used to describe the light-harvesting pigment-protein complex. The method works with the adiabatic states and transforms the Hamiltonian to a form in which the terms responsible for decoherence and population relaxation are separated out. Decoherence is then accounted for nonperturbatively and population relaxation using a Markovian master equation. Almost analytical results can be obtained for the seven-level system, and the calculations are very simple for systems with more levels. We apply the treatment to the seven-level system, and the results are in excellent agreement with the exact numerical results of Nalbach et al. Nalbach, Braun, and Thorwart, Phys. Rev. E 84, 041926 (2011)]. Our approach is able to account for decoherence and population relaxation separately. It is found that decoherence causes only damping of oscillations and does not lead to transfer to the reaction center. Population relaxation is necessary for efficient transfer to the reaction center, in agreement with earlier findings. Our results show that the transformation to the adiabatic basis followed by a Redfield type of approach leads to results in good agreement with exact simulation.

Naphthalene Carbohydrazone Based Dizinc(II) Chemosensor for a Pyrophosphate Ion and Its DNA Assessment Application in Polymerase Chain Reaction Products

A new naphthalene carbohydrazone based dizinc(II) complex has been synthesized and investigated to act as a highly selective fluorescence and visual sensor for a pyrophosphate ion with a quite low detection limit of 155 ppb; this has also been used to detect the pyrophosphate ion released from polymerase-chain-reaction.

Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring.

Platinum Ion-Doped TiO2: High Catalytic Activity of Pt2+ with Oxide Ion Vacancy in Ti1-x4+Ptx2+O2-x Compared to Pt4+ without Oxide Ion Vacancy in Ti1-x4+Ptx4+O2

Ti0.97Pt0.032+O1.97 and Ti0.97Pt0.034+O2 have been synthesized by a solution combustion method using alanine and glycine as the fuels, respectively. Both crystallize in anatase TiO2 structure with 15 nm average crystallite size. X-ray photoelectron spectroscopy (XPS) confirmed Pt ions are in the 2+ state in Ti0.97Pt0.03O1.97 (alanine) and 4+ state in Ti0.97Pt0.03O2 (glycine). The rate of CO oxidation occurring over Ti0.97Pt0.032+O1.97 (0.76 mu mol.g(-1).s(-1)) is similar to 10, times more than that over Ti0.97Pt0.034+O2 at 60 degrees C (0.08 mu mol.g(-1).s(-1)). A large shift in 100% hydrocarbons conversion to lower temperature was observed for Pt2+ ion-substituted TiO2 relative 10 that for Pt4+ ion-substituted TiO2. After reoxidation of the reduced compound by H-2 as well as CO, Pt ions are stabilized in mixed valences, 2+ and 4+ states. The role of oxide ion vacancy has been demonstrated by CO oxidation and H-2 + O-2 recombination reactions in the presence and absence of O-2. We analyze the activated lattice oxygens upon substitution of Pt2+ and Pt4+ ions in TiO2, using first-principles density functional theory (DFT) calculations with supercells of Ti31Pt1O63, Ti30Pt2O62, and Ti29Pt3O61 for Pt2+ ion substitution and Ti31Pt1O64, Ti30Pt2O62, and Ti29Pt3O61 for Pt4+ ion substitution in TiO2. We find that the local structure of Pt2+ ion has a distorted square planar geometry and that of Pt4+ ion has an octahedral geometry similar to that of Ti4+ ion in pure TiO2. The change in coordination of Pt2+ ion gives rise to weakly bonded oxygens, and these oxygens are involved in high rates of catalytic reaction. Thus, the high catalytic activity results from synergistic roles of Pt2+ ion and oxide ion vacancy and weakly bonded lattice oxygen.

Mechanistic Insights into a Non-Classical Diffusion Pathway for the Formation of Hollow Intermetallics: A Route to Multicomponent Hollow Structures

Hollow nanostructures are used for various applications including catalysis, sensing, and drug delivery. Methods based on the Kirkendall effect have been the most successful for obtaining hollow nanostructures of various multicomponent systems. The classical Kirkendall effect relies on the presence of a faster diffusing species in the core; the resultant imbalance in flux results in the formation of hollow structures. Here, an alternate non-Kirkendall mechanism that is operative for the formation of hollow single crystalline particles of intermetallic PtBi is demonstrated. The synthesis method involves sequential reduction of Pt and Bi salts in ethylene glycol under microwave irradiation. Detailed analysis of the reaction at various stages indicates that the formation of the intermetallic PtBi hollow nanoparticles occurs in steps. The mechanistic details are elucidated using control experiments. The use of microwave results in a very rapid synthesis of intermetallics PtBi that exhibits excellent electrocatalytic activity for formic acid oxidation reaction. The method presented can be extended to various multicomponent systems and is independent of the intrinsic diffusivities of the species involved.

Role of dicarboxylate linkers in Mn-III-salicylaldoximate based extended structures: synthesis, structures, and magnetic behavior

Four new oxo-centered Mn-III-salicylaldoximate triangle-based extended complexes (Mn6O2)-O-III(salox)(6)(EtOH)(4)(phda)](n)(saloxH(2))(n)(2H(2)O)(n) (1), (Mn6O2)-O-III(salox)(6)(MeOH)(5)(5-I-isoph)](n)(3MeOH)(n) (2), (Mn6O2)-O-III(salox)(6)(MeOH)(4)(H2O) (5-N-3-isoph)](n)(4MeOH)(n) (3) and (Mn3NaO)-Na-III(salox)(3)(MeOH)(4)(5-NO2-isoph)](n)(MeOH)(n) (H2O)(n) (4) salox=salicylaldoximate, phda=1,3-phenylenediacetate, isoph=isophthalate] have been synthesized under similar reaction conditions. Single crystal X-ray structures show that in 1, only one type of Mn-6 cluster is arranged in 1D, whereas in 2 and 3 there are two types of clusters, differing in the way the triangle units are joined and assembled. In complex4, however, the basic building structure is heteronuclear and based on Mn-3 units extended in 2D. Susceptibility measurements (dc and ac) over a wide range of temperatures and fields show that the complexes1, 2, and 3 behave as single molecule magnets (SMMs) with S=4ground state, while 4 is dominantly antiferromagnetic with a ground spin state S=2. Density functional theory calculations have been performed on model complexes to provide a qualitative theoretical interpretation for their overall magnetic behavior.

Glycidyl azide polymer crosslinked through triazoles by click chemistry: curing, mechanical and thermal properties

Glycidyl azide polymer (GAP) was cured through click chemistry by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3-dipolar cycloaddition reaction to form 1,2,3-triazole network. The properties of GAP-based triazole networks are compared with the urethane cured GAP-systems. The glass transition temperature (T-g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T-g in comparison to the GAP-urethane system (T-g-20 degrees C) and the networks exhibit biphasic transitions at 61 and 88 degrees C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)-based theoretical calculations implied marginal preference for 1,5-addition over 1,4-addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP-triazole and the mechanism of decomposition was elucidated using pyrolysis GC-MS studies. The higher heat of exothermic decomposition of triazole adduct (418kJmol(-1)) against that of azide (317kJmol(-1)) and better mechanical properties of the GAP-triazole renders it a better propellant binder than the GAP-urethane system.

A catalytic michael/horner-wadsworth-emmons cascade reaction for enantioselective synthesis of thiochromenes

A catalytic enantioselective sulfa-Michael/Horner-Wadsworth-Emmons reaction cascade has been developed, taking advantage of phosphonate as an electrophilic activator and a traceless binding site. Using a chiral bifunctional urea derivative as the catalyst, a variety of aryl and heteroaryl substituted thiochromenes was obtained in excellent yield with a high level of enantioselectivity.

Cross-Hetero-Dehydrogenative Coupling Reaction of Phosphites: A Catalytic Metal-Free Phosphorylation of Amines and Alcohols

Phosphorylation of amines, alcohols, and sulfoximines are accomplished using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions. This method provides an easy route for synthesizing a variety of phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates which are of biological importance.

Production of syngas from steam reforming and CO removal with water gas shift reaction over nanosized Zr0.95Ru0.05O2-delta solid solution

This study presents the synthesis, characterization, and kinetics of steam reforming of methane and water gas shift (WGS) reactions over highly active and coke resistant Zr0.93Ru0.05O2-delta. The catalyst showed high activity at low temperatures for both the reactions. For WGS reaction, 99% conversion of CO with 100% H-2 selectivity was observed below 290 degrees C. The detailed kinetic studies including influence of gas phase product species, effect of temperature and catalyst loading on the reaction rates have been investigated. For the reforming reaction, the rate of reaction is first order in CH4 concentration and independent of CO and H2O concentration. This indicates that the adsorptive dissociation of CH4 is the rate determining step. The catalyst also showed excellent coke resistance even under a stoichiometric steam/carbon ratio. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic nature of Ru species. The associative mechanism involving the surface formate as an intermediate was used to correlate experimental data. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Solvent-induced changes on the polarity of the triplet excited state of 2-chlorothioxanthone: From time-resolved absorption and resonance Raman spectroscopies

Solvent polarity has been known to influence the triplet state structure and reactivity. Here, we present our experimental and theoretical study on the effect of solvent on the lowest triplet excited state structure of 2-chlorothioxanthone (CTX). Time-resolved absorption (TA) spectroscopy has been employed to understand the triplet state electronic structure; whereas solvent-induced structural changes have been studied using time-resolved resonance Raman (TR3) spectroscopy. Both the DFT and TD-DFT calculations have been performed in the solution phase employing self-consistent reaction field implicit solvation model to support the experimental data. It has been observed that CO stretching frequencies of the excited triplet state are sensitive to the solvent polarity and increase with the increase in the solvent polarity. Both TA and TR3 studies reveal that specific solvent effect (H-bonding) is more pronounced in comparison to the nonspecific solvent effect. (C) 2013 Elsevier B.V. All rights reserved.