Many-body energy decomposition of hydrogen-bonded glycine clusters in gas-phase

A detailed analysis of the many-body contribution to the interaction energies of the gas-phase hydrogen-bonded glycine clusters, (Gly)(N), N = 1-4 is presented. The energetics of the hydrogen-bonded dimer, trimer and tetramer complexes have been analyzed using density-functional theory. The magnitude of the two-through four-body energy terms have been calculated and compared. The relaxation energy and the two-body energy terms are the principal contributors to the total binding energy. Four-body contribution is negligible. However, the three-body contribution is found to be sizable and the formation of the cyclic glycine trimer presents geometric strains that make it less favorable. (C) 2010 Elsevier B.V. All rights reserved.

Compressible Sherrington-Kirkpatrick spin-glass model

We introduce a Sherrington-Kirkpatrick spin-glass model with the addition of elastic degrees of freedom. The problem is formulated in terms of an effective four-spin Hamiltonian in the pressure ensemble, which can be treated by the replica method. In the replica-symmetric approximation, we analyze the pressure-temperature phase diagram, and obtain expressions for the critical boundaries between the disordered and the ordered (spin-glass and ferromagnetic) phases. The second-order para-ferromagnetic border ends at a tricritical point, beyond which the transition becomes discontinuous. We use these results to make contact with the temperature-concentration phase diagrams of mixtures of hydrogen-bonded crystals.

2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, a hydrogen-bonded organic quasi-1D ferromagnet

The title radical (F4BlmNN) is a stable nitronylnitroxide that forms hydrogen-bonded NH center dot center dot center dot ON chains in the solid state. The chains assemble the F4BlmNN molecules to form stacked contacts between the radical groups, in a geometry that is expected to exhibit ferromagnetic (FM) exchange based on spin polarization (SP) models. The experimental magnetic susceptibility of F4BlmNN confirms the expectation, showing 1-D Heisenberg chain FM exchange behavior over 1.8-300 K with an intrachain exchange constant Of J(chain)/k = +22 K. At lower temperatures, ac magnetic susceptibility and variable field heat capacity measurements show that F4BlmNN acts as a quasi-1-D ferromagnet. The dominant ferromagnetic exchange interaction is attributable to overlap between spin orbitals of molecules within the hydrogen-bonded chains, consistent with the SP model expectations. The chains appear to be antiferromagnetically exchange coupled, giving cusps in the ac susceptibility and zero field heat capacity at lower temperatures. The results indicate that the sample orders magnetically at about 0.7 K. The magnetic heat capacity ordering cusp shifts to lower temperatures as external magnetic field increases, consistent with forming a bulk antiferromagnetic phase below a Neel temperature of T-N(0) = 0.72 K, with a critical field of H-c approximate to 1800 Oe. The interchain exchange is estimated to be zJ/k congruent to (-)0.1 K.

Influence of interlayer tunneling on the quantized Hall phases in intentionally disordered multilayer structures

Stability of the quantized Hall phases is studied in weakly coupled multilayers as a function of the interlayer correlations controlled by the interlayer tunneling and by the random variation of the well thicknesses. A strong enough interlayer disorder destroys the symmetry responsible for the quantization of the Hall conductivity, resulting in the breakdown of the quantum Hall effect. A clear difference between the dimensionalities of the metallic and insulating quantum Hall phases is demonstrated. The sharpness of the quantized Hall steps obtained in the coupled multilayers with different degrees of randomization was found consistent with the calculated interlayer tunneling energies. The observed width of the transition between the quantized Hall states in random multilayers is explained in terms of the local fluctuations of the electron density.

A general treatment of geometric phases and dynamical invariants

Based only on the parallel-transport condition, we present a general method to compute Abelian or non-Abelian geometric phases acquired by the basis states of pure or mixed density operators, which also holds for nonadiabatic and noncyclic evolution. Two interesting features of the non-Abelian geometric phase obtained by our method stand out: i) it is a generalization of Wilczek and Zee`s non-Abelian holonomy, in that it describes nonadiabatic evolution where the basis states are parallelly transported between distinct degenerate subspaces, and ii) the non-Abelian character of our geometric phase relies on the transitional evolution of the basis states, even in the nondegenerate case. We apply our formalism to a two-level system evolving nonadiabatically under spontaneous decay to emphasize the non- Abelian nature of the geometric phase induced by the reservoir. We also show, through the generalized invariant theory, that our general approach encompasses previous results in the literature. Copyright (c) EPLA, 2008.

Structural and thermodynamic analysis of thrombin:suramin interaction in solution and crystal phases

Suramin is a hexasulfonated naphthylurea which has been recently characterized as a non-competitive inhibitor of human alpha-thrombin activity over fibrinogen, although its binding site and mode of interaction with the enzyme remain elusive. Here, we determined two X-ray structure of the thrombin: suramin complex, refined at 2.4 angstrom resolution. While a single thrombin: suramin complex was found in the asymmetric unit cell of the crystal, some of the crystallographic contacts with symmetrically related molecules are mediated by both the enzyme and the ligand. Molecular dynamics simulations with the 1:1 complex demonstrate a large rearrangement of suramin in the complex, but with the protein scaffold and the more extensive protein-ligand regions keep unchanged. Small-angle X-ray scattering measurements at high micromolar concentration demonstrate a suramin-induced dimerization of the enzyme. These data indicating a dissimilar binding mode in the monomeric and oligomeric states, with a monomeric, 1:1 complex to be more likely to exist at the thrombin physiological, nanomolar concentration range. Collectively, close understanding on the structural basis for interaction is given which might establish a basis for design of suramin analogues targeting thrombin. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Nitric oxide sensing by cytochrome c bonded to a conducting polymer modified glassy carbon electrode

A nitric oxide biosensor based on cytochrome c (an heme protein) covalently immobilized to poly(5-amino-1-naphthol) by using cyanuric chloride as a bridge was developed. The immobilization was studied by cyclic voltammetry and quartz crystal microbalance. The nitric oxide detection as a function of poly(5-amino-1-naphthol) amount was recorded, and the best result was obtained with the electrode prepared by 70 cycles. The sensitivity and detection limit were 0.015 mu A cm(-2)/mu mol L(-1) and 2.85 mu mol L(-1), respectively. (C) 2009 Elsevier B.V. All rights reserved.

FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

HPLC-DAD methodology for the quantification of organic acids, furans and polyphenols by direct injection of wine samples

This article proposes a simple and sensitive HPLC method with photo-diode array detection for the analysis of organic acids, monomeric polyphenols and furanic compounds in wine samples by direct injection. The chromatographic separation of 8 organic acids, 2 furans and 22 phenolic compounds was carried out with a buffered solution (pH 2.70) and acetonitrile as mobile phases and a difunctionally bonded C18 stationary phase, Atlantis dC18 (250 4.6 mm, 5mm) column. The elution was performed in 12 min for the organic acids and in 60 min for the phenolic compounds, including phenolic acids, stilbenes and flavonoids. Target compounds were detected at 210 nm (organic acids, flavan-3-ols and benzoic acids), 254 nm (ellagic acid), 280 nm (furans and cinnamic acid), 315 nm (hydroxycinnamic acids and trans-resveratrol) and 360 nm (flavonoids). The RSD for the repeatability test (n55) of peak area and retention times were below 3.1 and 0.3%, respectively, for phenolics and below 1.0 and 0.2% for organic acids. The RSDs expressing the reproducibility of the method were higher than for the repeatability results but all below 9.0%. Method accuracy was evaluated by the recovery results, with averaged values between 80 and 104% for polyphenols and 97–105% for organic acids. The calibration curves, obtained by triplicate injection of standard solutions, showed good linearity with regression coefficients higher than 0.9982 for polyphenols and 0.9997 for organic acids. The LOD was in the range of 0.07–0.49 mg/L for polyphenols (cinnamic and gallic acids, respectively) and 0.001–0.046 g/L for organic acids (oxalic and lactic acids, respectively). The method was successfully used to measure and assess the polyphenolic fingerprint and organic acids profile of red, white, rose ´ and fortified wines.

Sodium levels for Japanese quail at initial phases

The aim of this research was to determine the nutritional requirements of sodium for Japanese quail (Coturnix coturnix Japonica) during the periods of 1 to 21 d and 22 to 40 d of age, as well as to evaluate the residual effect on egg production and densitometry bone traits from 41 to 63 d. Two experiments were developed. Experiment 1: 360 Japanese quail were used, from 1 to 21 d of age. Treatments consisted of 5 sodium levels (0.06, 0.12, 0.18, 0.24, and 0.30%). Experiment 2: 240 Japanese quail were used, from 22 to 40 d. Treatments consisted of 5 sodium levels (0.04, 0.12, 0.20, 0.28, and 0.36%). In both experiments, weight gain, final weight, and feed conversion presented a quadratic trend, whereas water intake presented a linear trend. Treatments did not affect the densitometry of bone traits, although they presented a quadratic influence on tibia ash, calcium, and calcium: phosphorus ratio. Therefore, the nutritional requirement of sodium for Japanese quail from 1 to 21 d and from 22 to 40 d is 0.222% and 0.253%, respectively.

Basal temperature and thermal sum in phenological phases of nectarine and peach cultivars

O objetivo deste trabalho foi avaliar a temperatura basal, a soma térmica acumulada em diferentes fases fenológicas, a duração das fenofases, a produtividade e a sazonalidade do ciclo de uma cultivar de nectarina e de 14 cultivares de pêssego, entre 2006 e 2009. As fases fenológicas consideradas foram: poda-brotação; brotação-florescimento, da gema inchada até a flor aberta; florescimento-frutificação, da queda das pétalas até o fruto médio; e maturação. As temperaturas basais mínimas obtidas foram: poda-brotação, 8°C, independentemente das cultivares avaliadas; brotação-florescimento, 10°C, com exceção de 'Cascata 968', que necessitou de Tb de 8°C; florescimento-frutificação, 12°C, exceto 'Oro Azteca', que necessitou de Tb de 14°C; maturação, 14°C, com exceção de 'Sunblaze', 'Diamante Mejorado' e 'Precocinho', com Tb de 12°C. Para a maioria das cultivares, as temperaturas basais máximas foram de 30, 34, 34 e 28ºC, nas fases poda-brotação, brotação-florescimento, florescimento-frutificação e maturação, respectivamente. 'Turmalina', 'Marli' e 'Tropic Beauty' apresentaram produtividade média de 3.945,0, 3.969,3 e 3.954,0 kg ha-1, em 2009, respectivamente, enquanto a nectarineira 'Sunblaze' produziu em torno de 3.900 kg ha-1 em 2008 e 2009. As cultivares diferiram quanto ao ciclo total e quanto às somas térmicas acumuladas que variaram, respectivamente, de 245 dias e 1.881,4 graus-dia em 'Oro Azteca', a 144 dias e 1.455,7 graus-dia em 'Precocinho'.

Nucleation kinetics of crystalline phases from a kaolinitic body used in the processing of red ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrocatalysis of oxidation of hydrogen on platinum ordered intermetallic phases: Kinetic and mechanistic studies

An experimentally based kinetic and mechanistic study of the hydrogen oxidation reaction (HOR) on platinum and platinum ordered intermetallic materials in acid medium is presented. RDE kinetic data were re-evaluated and complemented by Tafel plots obtained from chronoamperometric measurements. Among the materials evaluated, PtSb and PtSn exhibited markedly improved kinetic current densities and exchange current densities, compared to Pt in the same experimental conditions. It is proposed that the intermetallic phase enhanced the adsorptive characteristic of the surface sites and, as a consequence, improved the kinetics of the adsorption steps (Tafel or Heyrovsky) of the mechanism involved. (c) 2006 Published by Elsevier B.V.

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.