Raman spectroscopy and DFT calculations of para-coumaric acid and its deprotonated species

An electronic and vibrational spectroscopic analysis of p-coumaric acid (HCou) and its deprotonated species was performed by UV-vis and Raman, respectively, and the results were supported by density functional theory (OFT) calculations. Electronic UV-vis spectral data of HCou solutions show that the deprotonation of the carboxyl group (Cou(-)) leads to a blue shift of the lowest energy electronic transition in comparison to the neutral species, whereas the subsequent deprotonation of the phenolic moiety (Cou(2-)) carries out to a more delocalized chromophore. The DFT geometric parameters calculations suggest that the variation in the electronic delocalization for the three organic species is due to different contribution of a quinoid structure that is significantly distorted in the case of Cou(2-). The Raman data of HCou and its sodium salts show that the main spectral features that allow to differentiate the three organic species are those involving the styrene nu(C=C)(sty) vibration at 1600cm(-1) region. Even though the Raman spectra of the sodium salts of Cou(-) and Cou(2-) anions show subtle differences, the appearing of a band at ca. 1598cm(-1) in the Na(2)Cou spectrum, assigned to a mode involving the carboxylate asymmetric stretching, nu(as)(COO), and the styrene stretching, nu(C=C)(sty), is quite characteristic, as confirmed by the theoretical Raman spectrum. Considering that p-coumaric acid is an archetypical phenolic compound with several biological activities that essentially depend upon the medium pH, Raman spectroscopy results reported in this work can provide a proper way to characterize such important phytochemical compound in different protonation states. In order to complement the characterization of the sodium salts, X-ray diffraction (XRD) and thermal analysis were performed. (C) 2011 Elsevier B.V. All rights reserved.

Ionization of chlorophyll-c(2) in liquid methanol

The ionization of chlorophyll-c(2) in liquid methanol was investigated by a sequential quantum mechanical/Monte Carlo approach. Focus was placed on the determination of the first ionization energy of chlorophyll-c(2). The results show that the first vertical ionization energy (IE) is red-shifted by 0.47 +/- 0.24 eV relative to the gas-phase value. The red-shift of the chlorophyll-c(2) IE in the liquid phase can be explained by Mg center dot center dot center dot OH hydrogen bonding and long-ranged electrostatic interactions in solution. The ionization threshold for chlorophyll-c2 in liquid methanol is close to 6 eV. (C) 2012 Elsevier B.V. All rights reserved.

On the Deactivation Mechanisms of Adenine-Thymine Base Pair

In this contribution, the multiconfigurational second-order perturbation theory method based on a complete active space reference wave function (CASSCF/CASPT2) is applied to study all possible single and double proton/hydrogen transfers between the nucleobases in the adenine-thymine (AT) base pair, analyzing the role of excited states with different nature [localized (LE) and charge transfer (CT)] and considering concerted as well as step-wise mechanisms. According to the findings, once the lowest excited states, localized in adenine, are populated during UV irradiation of the Watson-Crick base pair, the proton transfer in the N-O bridge does not require high energy in order to populate a CT state. The latter state will immediately relax toward a crossing with the ground state, which will funnel the system to either the canonical structure or the imino-enol tautomer. The base pair is also capable of repairing itself easily since the imino-enol species is unstable to thermal conversion.

Boron site preference in ternary Ta and Nb boron suicides

X-ray single crystal (XSC) and neutron powder diffraction data (NPD) were used to elucidate boron site preference for five ternary phases. Ta3Si1-xBx (x=0.112(4)) crystallizes with the Ti3P-type (space group P4(2)/n) with B-atoms sharing the 8g site with Si atoms. Ta5Si3-x (x=0.03(1); Cr5B3- type) crystallizes with space group 14/mcm, exhibiting a small amount of vacancies on the 4 alpha site. Both, Ta-5(Si1-xBx)(3), X=0.568(3), and Nb-5(Si1-xBx)(3), x=0.59(2), are part of solid solutions of M5Si3 with Cr5B3-type into the ternary M-Si-B systems (M=Nb or Ta) with B replacing Si on the 8h site. The D8(8)-phase in the Nb-Si-B system crystallizes with the Ti5Ga4-type revealing the formula Nb5Si3B1-x (x=0.292(3)) with B partially filling the voids in the 2b site of the Mn5Si3 parent type. (C) 2012 Elsevier Inc. All rights reserved.

Study of CuO/CeO2 catalyst with for preferential CO oxidation reaction in hydrogen-rich feed (PROX-CO)

The CuO/CeO2 system was investigated as a catalyst for preferential CO oxidation reaction in hydrogen-rich feed (PROX-CO). The catalysts were prepared by deposition-precipitation (DEP) and co-precipitation (COP) methods and the catalytic performance reveals that the preparation method influences the properties of solids prepared, where a direct consequence is the difference in behavior of the catalysts in the PROX-CO reaction. A high specific area and a better dispersion of the metallic phase were obtained in the catalyst prepared by co-precipitation. The redox properties during the reaction were reported by measures of temperature programmed reduction (TPR), OSC measurements and X-ray absorption near edge structure (XANES-TPR) in situ showed the relationship between the preparation method, the physicochemical characteristics and redox properties in the PROX-CO reaction. By this means, the good dispersion of CuO and the best oxygen capacity are the response of the high performance of CuO/CeO2-COP catalysts for the PROX-CO reaction. Crown Copyright (c) 2012 Published by Elsevier B.V. All rights reserved.

Synthesis and Solar Cell Application of New Alternating Donor-Acceptor Copolymers Based on Variable Units of Fluorene, Thiophene, and Phenylene

A new series of donor acceptor copolymers were synthesized via the Witting route and applied as an active layer in organic thin-films solar cells. These copolymers are composed of fluorene thiophene and phenylene thiophene units. The ratio between those was systematically varied, and copolymers containing 0%, 50%, and 75% of phenylene thiophene were characterized and evaluated when used in photovoltaic devices. The copolymers' composition, photophysical, electrical, and morphological properties are addressed and correlated with device performance. The 50% copolymer ratio was found to be the best copolymer of the series, yielding a power conversion efficiency (PCE) under air mass (AM) 1.5 conditions of 2.4% in the bilayer heterojunction with the C-60 molecule. Aiming at flexible electronics applications, solutions based on the heterojunction of this copolymer with PCBM (6,6-phenyl-C-61-butyric acid methyl ester) were also successfully deposited using an inkjet printing method and used as an active layer in solar cells.

Conformational preferences for some 3-(4 '-substituted phenylsulfonyl)-1-methyl-2-piperidones through spectroscopic and theoretical studies

The analysis of the infrared (IR) carbonyl band of some 3-(4'-substituted phenylsulfonyl)-1-methyl-2-piperidones 1-5 bearing as substituents: OMe 1, Me 2, H 3, Cl 4 and NO2 5, supported by B3LY13/6-31G(d,p) calculations along with NBO analysis (for 1, 3 and 5) and X-ray diffraction (for 5), indicated the existence of three stable conformations i.e. quasi-axial (q-ax), syn-clinal (s-cl) and quasi-equatorial (q-eq). In the gas phase, the q-ax conformer is calculated as the most stable (ca. 88%) and the least polar, the s-cl conformer is less stable (ca. 12%) but more polar, and the q-eq conformer is the least stable (ca. 1%) and the most polar of the three conformers evaluated. The sum of the most important orbital interactions from NBO analysis and the trend of the electrostatic interactions accounts for the relative populations as well as for the v(CO) frequencies of the q-ax. s-cl and q-eq conformers calculated in the gas phase. The unique IR v(CO) band in CCl4 may be ascribed to the most stable q-ax conformer. The more intense (60%) high frequency doublet component in CHCl3 may be assigned to the summing up of the least stable q-eq and the less stable s-cl conformers, as their frequencies are almost coincident. The occurrence of only a single v(CO) band in both CH2Cl2 and CH3CN supports the fact that the v(CO) band of the two more polar conformers appear as a single band. Additional support to this rationalization is given by the single point PCM method, which showed a progressive increase of the q-eq + s-cl/q-ax population ratio going from the gas phase to CCl4, to CHCl3, to CH2Cl2 and to CN3CN. X-ray single crystal analysis of 5 indicates that this compound displays a quasi-axial geometry with respect to the [O=C-CH-S] moiety, and that the 2-piperidone ring assumes a slightly distorted half-chair conformation. In the crystal packing, molecules of 5 are arranged into supramolecular layers linked through C-H center dot center dot center dot O interactions along with it pi center dot center dot center dot pi interactions between adjacent benzene rings. (C) 2012 Elsevier B.V. All rights reserved.

Structural and mechanical analysis for the optimization of PVD oxide coatings for protection against metal dusting

The evolution of the structure and properties of Cr/Cr oxide thin films deposited on HK40 steel substrates by reactive magnetron sputtering (RMS) was investigated and linked to their potential protective behavior against metal dusting. Deposition time, mode of oxygen feeding, and application of bias voltage were varied to assess their effect on the density, adhesion, and integrity of the films. All the films showed a very fine columnar microstructure and the presence of amorphous Cr oxide. Both, an increasing time and a constant oxygen flow during deposition led to the development of relatively low density films and mud-like cracking patterns. A graded oxygen flow resulted in films with fewer cracks, but a careful control of the oxygen flow is required to obtain films with a truly graded structure. The effect of the bias voltage was much more significant and beneficial. An increasing negative bias voltage resulted in the development of denser films with a transition to an almost crack-free structure and better adhesion. The amorphous oxide resulted in low values of hardness and Young's modulus. (C) 2012 Elsevier B.V. All rights reserved.

Molecular Dynamics Investigations of PRODAN in a DLPC Bilayer

Molecular dynamics computer simulations have been performed to identify preferred positions of the fluorescent probe PRODAN in a fully hydrated DLPC bilayer in the fluid phase. In addition to the intramolecular charge-transfer first vertical excited state, we considered different charge distributions for the electronic ground state of the PRODAN molecule by distinct atomic charge models corresponding to the probe molecule in vacuum as well as polarized in a weak and a strong dielectric solvent (cyclohexane and water). Independent on the charge distribution model of PRODAN, we observed a preferential orientation of this molecule in the bilayer with the dimethylamino group pointing toward the membrane's center and the carbonyl oxygen toward the membrane's interface. However, changing the charge distribution model of PRODAN, independent of its initial position in the equilibrated DLPC membrane, we observed different preferential positions. For the ground state representation without polarization and the in-cyclohexane polarization, the probe maintains its position close to the membrane's center. Considering the in-water polarization model, the probe approaches more of the polar headgroup region of the bilayer, with a strong structural correlation with the choline group, exposing its oxygen atom to water molecules. PRODAN's representation of the first vertical excited state with the in-water polarization also approaches the polar region of the membrane with the oxygen atom exposed to the bilayer's hydration shell. However, this model presents a stronger structural correlation with the phosphate groups than the ground state. Therefore, we conclude that the orientation of the PRODAN molecule inside the DLPC membrane is well-defined, but its position is very sensitive to the effect of the medium polarization included here by different models for the atomic charge distribution of the probe.

The nuclear electric quadrupole moment of hafnium from the molecular method

The molecular method is used to obtain nuclear electric quadrupole moment (NQM) values for hafnium through electric field gradients (EFGs) at this nucleus in HfO and HfS. Dirac-Coulomb calculations with the Coupled Cluster approach, DC-CCSD (T) and DC-CCSD-T, were carried out to achieve the most accurate estimates of these EFGs. Higher order corrections are also added. Hence, the most reliable values for 177Hf and 179Hf determined here are 3319(33) and 3750(37) mbarn, respectively, in nice accordance with the best currently accepted NQMs for this element. (C) 2012 Elsevier B.V. All rights reserved.

Influence of Alloying Elements Upon the Solidification Interval of CA6NM Cast Martensitic Stainless Steel

The influence of different Cr and C contents upon the solidification interval of ASTM A352M-06 Grade CA6NM cast martensitic stainless steel has been investigated using computational thermodynamics, and checked against DTA measurements in samples taken from 13 large cast parts, in order to identify potential sources for improvement on the part castability. Calculation results suggest, indeed, that this would be the case for C: when its content increases from 0.018 to 0.044 wt.% C (within the allowed range in the alloy specification), the solidification intervals increases from 25 to 43 K, which suggests improved castability with decreasing C contents. DTA results, however, do not support this prediction, showing a fairly constant solidification interval around 23 K for all investigated samples. The results are discussed both regarding the impact in alloy processing and the fitness of the existing databases to reproduce experimental results in these limiting cases.

Investigation of the pore blockage of a Brazilian dolomite during the sulfation reaction

The influence of the temperature and reaction time on the sulfation process of a dolomite is investigated in this paper. The sulfation effectiveness was evaluated and correlated with changes in the physical characteristics of a Brazilian dolomite during the reactive process. Calcination and sulfation experiments were performed under isothermal conditions for dolomite samples with average particle sizes of 545 mu m at temperatures of 750 degrees C, 850 degrees C and 950 degrees C at different times of sulfation. Thermogravimetric tests were applied to establish the reactivity variation of the dolomite in function of the time in the sulfation reaction and evaluate the methodology of the samples preparation. Porosimetry tests were performed to study the pore blockage of dolomite during the sulfation reaction. The highest values of BET surface area were 25.55 m(2)/g, 29.55 m(2)/g and 12.62 m(2)/g for calcined samples and after their sulfation processes, conversions of 51.5%, 61.9% and 42.8% were obtained at 750 degrees C, 850 degrees C and 950 degrees C, respectively. Considering the process as a whole, the best fit was provided by a first-order exponential decay equation. Moreover, the results have shown that it is possible to quantify the decreasing in the dolomite reactivity for sulfur dioxide sorption and understand the changes in the behavior of the sulfation process of limestones when applied to technologies, as fluidized bed combustor, in which sulfur dioxide is present. (C) 2011 Elsevier B. V. All rights reserved.

Improving the catalytic activity of formate dehydrogenase from Candida boidinii by using magnetic nanoparticles

Formate dehydrogenase from Candida boidinii (FDH) was immobilized on three different magnetic supports: one composed by magnetite nanoparticles directly silanized with ARTS (aminopropyltriethoxysilane), i.e. MagNP-APTS: the second one containing a silica gel coated magnetite core which was further silanized with APTS (MagNP@SiO2-APTS), and the third one consisting of magnetite-APTS coated with Glyoxyl-Agarose (MagNP-Glyoxyl-Agarose). The catalytic activity of the three FDH systems was investigated as a function of pH and temperature. The silica gel coated nanoparticles provided the highest conversion rates; however, in terms of recycling, magnetite without the silica shell led to the most stable system. By using the enzyme tryptophan residues as internal fluorescence probes, the structure-activity behavior was investigated in the presence of the formate and NAD(+) substrates, revealing a rather contrasting behavior in the three cases. Because of its peculiar behavior, a direct interaction of the magnetic nanoparticles with the catalytic sites seems to be implicated in the case of MagNP-APTS. (C) 2012 Elsevier B.V. All rights reserved.

The T-2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb5Si3 (Cr5B3 structure type, D8(l), tl32, 14/mcm, No140, a=6.5767 angstrom, c=11.8967 angstrom) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. (C) 2012 Elsevier Inc. All rights reserved.

Self-Assembly of Poly(4-vynil-N-alkylpyridinium) Bromide onto Silica: Effect of Side-Chain Length on Structural Aspects at a Molecular Level

Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.