Intralamellar structural modifications related to the proton exchanging in K(4)Nb(6)O(17) layered phase

Basic structural aspects about the layered hexaniobate of K(4)Nb(6)O(17) composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K(4)Nb(6)O(17) and H(2)K(2)Nb(6)O(17)center dot H(2)O show significant modifications in the 950-800 cm(-1) region (Nb-O stretching mode of highly distorted NbO(6) octahedra). The band at 900 cm(-1) shifts to 940 cm(-1) after the replacement of K(+) ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H(2)K(2)Nb(6)O(17) was dehydrated: the relative intensity of the band at 940 cm(-1) decreases and new bands seems to be present at about 860-890 cm(-1). The H(+) ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H(+) ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials. 2009 Elsevier Ltd. All rights reserved.

Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

The effect of ultra-low proton concentration on the electrocatalytic reduction of nitrate over platinum

The electrocatalytic reduction of NO3- (aq) over platinum has been investigated in sulfuric acid solutions with proton concentrations between 1 mM and 50 mM. Cyclic voltammetry indicates that for [H+] < 10 mM, NO3- (aq) is reduced in two distinct regions of potential: one reduction peak occurs at approximately 0.1 V vs. RHE and one occurs at -0.13 V vs. RHE. This second reduction peak has never before been observed, and is not present for proton concentrations >10 mM, where hydrogen electroreduction prevails below 0.0 V vs. RHE. Chronoamperometry shows that the kinetics of the two reduction peaks are distinct, suggesting that the two reduction peaks may correspond to the evolution of different products. Results are discussed in the context of tuning the product selectivity of the electrocatalytic reduction of NO3- (aq). (C) 2007 Elsevier B.V. All rights reserved.

Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode

We report in this paper the occurrence of potential oscillations in a proton exchange membrane fuel cell (PEMFC) with a Pd-Pt/C anode, fed with H(2)/100 ppm CO, and operated at 30 degrees C. We demonstrate that the use of Pd-Pt/C anode enables the emergence of dynamic instabilities in a PEMFC. Oscillations are characterized by the presence of very high oscillation amplitude, ca. 0.8 V. which is almost twice that observed in a PEMFC with a Pt-Ru/C anode under similar conditions. The effects of the H(2)/CO flow rate and cell current density on the oscillatory dynamics were investigated and the mechanism rationalized in terms of the CO oxidation and adsorption processes. We also discuss the fundamental aspects concerning the operation of a PEMFC under oscillatory regime in terms of the benefit resulting from the higher average power output. (c) 2010 Elsevier B.V. All rights reserved.

Multimilligram enantioresolution of sulfoxide proton pump inhibitors by liquid chromatography on polysaccharide-based chiral stationary phase

The enantiomers of sulfoxide proton pump inhibitors - omeprazole, lansoprazole, rabeprazole and Ro 18-5364 - were enantiomerically separated by liquid chromatography at multimilligram scale on a poly saccharide-based chiral stationary phase using normal and polar organic conditions as mobile phase. The values of the recovery and production rate were significant for each enantiomer; better results were achieved using a solid-phase injection system. However, this system was applied just for the enantionteric separation of omeprazole to demonstrate the applicability of this injection mode at milligram scale. The chiroptical characterization of the compounds was performed using a polarimeter and a circular dichroism detector. The higher enantiomeric purity obtained for the isolated enantiomers suggests that the methods here described should be considered as a simple and rapid way to obtain enantiomeric pure standards for analytical purpose. (C) 2007 Elsevier B.V. All rights reserved.

A theoretical analysis on the intramolecular proton transfer of alpha-alanine in an aqueous medium

Intramolecular proton transfer from oxygen to nitrogen atoms in the alpha-alanine amino acid has been studied by ab initio methods at the HF/6-31G*, HF/6-31 ++ G** and MP2/6-31 ++ G** levels of calculation including the solvent effects by means of self-consistent reaction field theory. An analysis of the results based on the natural bond orbital charges shows that the transition structure presents an imbalance in the sense that the charge shift lags behind the proton transfer and that the bond formation is always in advance with respect to the bond cleavage. All calculation levels show that the barrier height associated with the conformational change on alpha-alanine is larger than the proton transfer process. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Grand unification and proton stability near the Peccei-Quinn scale

We show that in an SU(2)circle timesU(1) model with a Dine-Fischler-Srednicki-like invisible axion it is possible to obtain (i) the convergence of the three gauge coupling constants at an energy scale near the Peccei-Quinn scale; (ii) the correct value for sin(2)theta<^>(W)(M-Z); (iii) the stabilization of the proton by the cyclic Z(13)circle timesZ(3) symmetries which also stabilize the axion as a solution to the strong CP problem. Concerning the convergence of the three coupling constants and the prediction of the weak mixing angle at the Z peak, this model is as good as the minimal supersymmetric standard model with mu(SUSY)=M-Z. We also consider the standard model with six and seven Higgs doublets. The main calculations were done in the 1-loop approximation but we briefly consider the 2-loop contributions.

Classification of states in S0(8) proton-neutron pairing model

lsoscalar (T = 0) plus isovector (T = 1) pairing Hamiltonian in LS-coupling. which is important for heavy N = Z nuclei, is solvable in terms of a SO(8) Lie algebra for three special values of the mixing parameter that measures the competition between the T = 0 aid T = 1 pairing. The SO(8) algebra is generated, amongst others, by the S = 1, T = 0 and S = 0, T = 1 pair creation and annihilation operators and corresponding to the three values of the mixing parameter, there are three chains of subalgebras: SO(8) superset of SOST (6) superset of SOS(3) circle times SOT(3), SO(8) superset of [SOS(5) superset of SOS(3)] circle times SOT(3) and SO(8) superset of [SOT(5) superset of SOT(3)] circle times SOS(3). Shell model Lie algebras, with only particle number conserving generators, that are complementary to these three chains of subalgebras are identified and they are used in the classification of states for a given number of nucleons. The classification problem is solved explicitly tor states with SO(8) seniority nu = 0, 1, 2, 3 and 4. Using them, hand structures in isospin space are identified for states with nu = 0, 1, 2 and 3. (c) 2005 Elsevier B.V. All rights reserved.

The Fulling-Davies-Unruh effect is mandatory: the proton's testimony

We discuss the decay of accelerated protons and illustrate how the Fulling-Davies-Unruh effect is indeed mandatory to maintain the consistency of standard Quantum Field Theory. The confidence level of the Fulling-Davies-Unruh effect must be the same as that of Quantum Field Theory itself.

Search for excited muons in p(p)over-bar collisions at root s=1.96 TeV

We present the results of a search for the production of an excited state of the muon, mu(*), in proton antiproton collisions at root s =1.96 TeV. The data have been collected with the D0 experiment at the Fermilab Tevatron Collider and correspond to an integrated luminosity of approximately 380 pb(-1). We search for mu(*) in the process p (p) over bar ->mu(*)mu, with the mu(*) subsequently decaying to a muon plus photon. No excess above the standard model expectation is observed in data. Interpreting our data in the context of a model that describes mu(*) production by four-fermion contact interactions and mu(*) decay via electroweak processes, we set a 95% confidence level production cross section upper limit ranging from 0.057 to 0.112 pb, depending on the mass of the excited muon. Choosing the scale for contact interactions to be Lambda=1 TeV, excited muon masses below 618 GeV are excluded.

Study of W boson production in PbPb and pp collisions at root s(NN)=2.76 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Charm Production in Antiproton-Proton Annihilation

We study the production of charmed mesons (D) and baryons (Lambda(c)) in antiproton- proton ((p) over barp) annihilation close to their respective production thresholds. The elementary charm production process is described by either baryon/ meson exchange or by quark/ gluon dynamics. Effects of the interactions in the initial and final states are taken into account rigorously. The calculations are performed in close analogy to our earlier study on (p) over bar -> (Lambda) over bar Lambda and (p) over barp (K) over bar K by connecting the processes via SU(4) flavor symmetry. Our predictions for the (Lambda) over bar (c)Lambda(c) production cross section are in the order of 1 to 7 mb, i. e. a factor of around 10-70 smaller than the corresponding cross sections for (Lambda) over bar Lambda However, they are 100 to 1000 times larger than predictions of other model calculations in the literature. on the other hand, the resulting cross sections for (D) over barD production are found to be in the order of 10(-2) - 10(-1)mu b and they turned out to be comparable to those obtained in other studies.

Search for flavor changing neutral currents via quark-gluon couplings in single top quark production using 2.3 fb(-1) of p(p)over-bar collisions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Measurement of the ratio of the 3-jet to 2-jet cross sections in pp collisions at root s=7 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)