ADVANCED ENGINEERING MATERIALS, Issue 12 2006
E. Clouet
This study illustrates how a quantitative multiscale modelling of the precipitation kinetics can be performed. Using a very limited number of experimental data and ab-initio calculations, we built for the Al-Zr-Sc alloy an atomic model from which mesoscopic quantities like the interface free energy or the nucleation free energy could be deduced. For the two binary Al-Zr and Al-Sc alloys, it was shown that a good agreement can be obtained between the KMC simulations, different mesoscopic models (CD and CNT) and experimental data. For the ternary alloy, CNT could be extended leading to predictions of an increase of the nucleation rate in agreement with atomic simulations and with experimental data. [source]

Conditioning polymers in today's shampoo formulations , efficacy, mechanism and test methods

INTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 1 2000
Hössel
Synopsis Today's shampoo formulations are beyond the stage of pure cleansing of the hair. Additional benefits are expected, e.g. conditioning, smoothing of the hair surface, improvement of combability and lather creaminess. Cationic polymers play an important role in providing many of those features. Therefore, within the last few years their use in shampoos has increased greatly. In the only last two decades, shampoo designation has gradually changed from ,2-in-1' to ,3-in-1' and then to ,multifunctional', as at present. The consumer demands products which live up to their promises. Modern shampoos contain a wide variety of ingredients such as co-surfactants, vitamins and pro-vitamins, protein derivatives, silicones, natural-based plant extracts and other ,active ingredients', but there is still a need for conditioning polymers. The specific objective of this study is to assess the conditioning efficacy of cationic polymers and to investigate their mechanisms in a shampoo system. The investigations were carried out on formulations that contained sodium lauryl ether sulphate and different cationic polymers, e.g. Polyquaternium 7, 10, 11, cationic guar gum and Luviquat Care (Polyquaternium 44), a new branched copolymer of vinylpyrrolidone (VP) and quaternized vinylimidazolium salts (QVI). We used test methods relevant to the applications in question, such as combing force measurements, the feel of the hair and the creaminess of the lather, to assess the efficacy. Atomic force microscopy and electrokinetics (streaming potential) were used to detect polymer residues on treated hair. All the polymers under investigation improved the overall performance of the shampoo formulations. This was demonstrated by means of combing force measurements, sensorial tests and analytical methods, namely zeta potential measurement and atomic force microscopy. Polyquaternium 44 exhibited the best conditioning properties on wet hair without sacrificing removability or absence of build-up. The latter are the most striking weaknesses of cationic Guar Gum-based polymers. Polyquaternium 10 can also be removed from the hair after rinsing with anionic surfactant but it does not perform as well as Polyquaternium 44 in the fields of wet combability and sensorial criteria such as lather creaminess and feel of the hair. We postulate that the outstanding properties of Polyquaternium 44 as a conditioning agent for shampoos are due to its tailor-made ,branched' structure. There is a clear correlation between the molecular weight and the efficacy of the new copolymers of VP and QVI. Only cationic polymers with a very high molecular weight are effective as conditioners in shampoos based on anionic surfactants. Surprisingly, they do not have to have a high cationic charge. On the basis of all our results, our postulation is that the polymer residue which is responsible for conditioning does not form a flat layer on the hair. Rather, the polymer residue adsorbs with the few cationic moieties, while the uncharged part of the polymer forms loops, which are orientated away from the hair and which are responsible for the reduced friction between hairs. Résumé Les formulations actuelles de shampoing font plus qu'un simple nettoyage des cheveux. On en attend un intérêt supplémentaire, par exemple après-shampoing, lissage de la surface du cheveu, amélioration de la coiffabilité et aspect crémeux du savon. Les polymères cationiques jouent un rôle important dans l'apport de nombre de ces caractéristiques. Par conséquent, ces quelques dernières années leur utilisation a considérablement augmenté dans les shampoings. Dans les seules deux dernières décades, l'appellation du shampoing est progressivement passée de "2 en 1"à"3 en 1" puis ensuite à"multifonctionnel", comme actuellement. Le consommateur recherche des produits qui tiennent leurs promesses. Les shampoings modernes contiennent une grande diversité d'ingrédients tels que des co-tensioactifs, des vitamines et des provitamines, des dérivés de protéines, des silicones, des extraits à base de plantes naturelles et autres "ingrédients actifs", mais il existe toujours un besoin pour des polymères d'après shampoing. L'objectif spécifique de cette étude est d'évaluer l'efficacité comme après-shampoing de polymères cationiques et de rechercher leurs mécanismes dans le système de shampoing. Les recherches ont été menées sur des formulations qui contiennent du sulfate de lauryl éther sodium et différents polymères cationiques, par exemple du Polyquaternium 7, 10, 11, de la gomme de guar cationique et du Luviquat Care (Polyquaternium 44), un nouveau copolymère ramifié de vinylpyrrolidone (VP) et de sels quaternaires de vinylimidazolium (QVI). Nous avons utilisé les procédés de contrôle appropriées aux applications en question, tels que les mesures de force de coiffage, le toucher du cheveu et l'aspect crémeux du savon, pour évaluer l'efficacité. La microscopie atomique et l'électrocinétique (potentiel d'écoulement) ont été utilisées pour détecter les résidus de polymère sur le cheveu traité. Tous les polymères étudiés améliorent le comportement global des formulations de shampoing. Ceci est démontré au moyen des mesures de force de coiffage, des tests sensoriels et des méthodes analytiques, en l'occurrence la mesure du potentiel zêta et la microscopie atomique. Le Polyquaternium 44 présente les meilleures propriétés d'après-shampoing sur cheveu mouillé sans diminuer sa capacité d'élimination ou l'absence d'accumulation. Ces dernières sont les faiblesses les plus frappantes des polymères à base de gomme de guar cationique. Le Polyquaternium 10 peut aussi être éliminé du cheveu après rinçage avec un tensioactif anionique mais il ne se comporte pas aussi bien que le Polyquaternium 44 dans les domaines de la coiffabilitéà l'état mouillé et des critères sensoriels tels que l'aspect crémeux du savon et du toucher du cheveu. Nous supposons que les propriétés exceptionnelles du Polyquaternium 44 comme agent après-shampoing pour shampoings sont dues à sa structure "ramifiée" conçue sur mesure. Il existe une corrélation claire entre le poids moléculaire et l'efficacité des nouveaux copolymères de VP et QVI. Seuls les polymères cationiques avec un poids moléculaire très élevé sont efficaces comme après shampoings dans des shampoings à base de tensioactifs anioniques. Etonnamment, ils n'ont pas besoin d'avoir une charge cationique élevée. Sur la base de tous nos résultats, notre hypothèse est que le fragment de polymère qui est responsable du traitement ne forme pas une couche plate sur le cheveu. Le fragment de polymère adsorbe plutôt les quelques fragments cationiques, tandis que la partie non chargée du polymère forme des boucles, qui sont orientées à l'extérieur du cheveu et qui sont responsables de la friction réduite entre les cheveux. [source]

DFT calculations on the electronic structures of BiOX (X = F, Cl, Br, I) photocatalysts with and without semicore Bi 5d states

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2009
Wen Lai Huang
Abstract The electronic structures of BiOX (X = F, Cl, Br, I) photocatalysts have been calculated with and without Bi 5d states using the experimental lattice parameters, via the plane-wave pseudopotential method based on density functional theory (DFT). BiOF exhibits a direct band gap of 3.22 or 3.12 eV corresponding to the adoption of Bi 5d states or not. The indirect band gaps of BiOCl, BiOBr, and BiOI are 2.80, 2.36, and 1.75 eV, respectively, if calculated with Bi 5d states, whereas the absence of Bi 5d states reduces them to 2.59, 2.13, and 1.53 eV successively. The calculated gap characteristics and the falling trend of gap width with the increasing X atomic number agree with the experimental results, despite the common DFT underestimation of gap values. The shapes of valence-band tops and conduction-band bottoms are almost independent of the involvement of Bi 5d states. The indirect characteristic becomes more remarkable, and the conduction-band bottom flattens in the sequence of BiOCl, BiOBr, and BiOI. Both O 2p and X np (n = 2, 3, 4, and 5 for X = F, Cl, Br, and I, respectively) states dominate the valence bands, whereas Bi 6p states contribute the most to the conduction bands. With the growing X atomic number, the localized X np states shift closer toward the valence-band tops, and the valence and conduction bandwidths evolve in opposite trends. Atomic and bond populations have also been explored to elucidate the atomic interactions, along with the spatial distribution of orbital density. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009 [source]

First principles simulations of F centers in cubic SrTiO3

PHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 1 2005
J. Carrasco
Abstract Atomic and electronic structure of regular and O-deficient SrTiO3 have been studied. Several types of first principles atomistic simulations: Hartree-Fock method, Density Functional Theory, and hybrid HF-DFT functionals, have been applied to periodic models that consider supercells of different sizes (ranging between 40 and 240 atoms). We confirm the ionic character of the Sr-O bonds and the high covalency of the Ti-O2 substructure. For the stoichiometric cubic crystal; the lattice constant and bulk modulus correctly reproduce the experimental data whereas the band gap is only properly obtained by the B3PW functional. The relaxed geometry around the F center shows a large expansion of the two nearest Ti ions. Moreover, the vacancy formation energy is extremely sensitive to the size and the shape of the supercell as well as the calculation method. The electronic density map indicates the redistribution of two electrons of the missing O atom between the vacancy and 3d atomic orbitals of the two nearest Ti ions, in contrast to the F centers in ionic oxides where the charge centroid does not change. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Analysis of Particle Pumping Using SOLDOR/NEUT2D Code in the JT-60U Tokamak

CONTRIBUTIONS TO PLASMA PHYSICS, Issue 1-3 2008
H. Kawashima
Abstract In order to understand the particle pumping on JT-60U, we analyze the roles of atomic and molecular processes using SOLDOR/NEUT2D code. A case of short strike point distance shows that most of neutrals produced on the targets go toward the exhaust slot directly. Whereas, neutrals are scattered in the spherically at random for the long distance case by collision processes and a few of them go toward the slot. It is clarified that the incident neutrals to the slot at low ne/high Te divertor plasma condition are dominated by atoms. Those at high ne/low Te condition are dominated by molecules due to elastic collision. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Silicon crystal growth from the melt: Analysis from atomic and macro scales

CRYSTAL RESEARCH AND TECHNOLOGY, Issue 4-5 2005
K. Kakimoto
Abstract The effect of impurity concentration on thermal conductivity of natural and isotope silicon by using equilibrium molecular dynamics simulation is investigated. It was found that the concentrations of the impurities such as boron, phosphor and arsene play an important role in the propagation of phonons in silicon crystals. It was also clarified that a mass difference of impurities and host crystals results in degradation of thermal conductivity of silicon. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Absorption of copper(II) by creosote bush (Larrea tridentata): Use of atomic and x-ray absorption spectroscopy

ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2001
Jorge Luis Gardea-Torresdey
Abstract Larrea tridentata (creosote bush), a common North American native desert shrub, exhibits the ability to take up copper(II) ions rapidly from solution. Following hydroponic studies, U.S. Environmental Protection Agency method 200.3 was used to digest the plant samples, and flame atomic absorption spectroscopy (FAAS) was used to determine the amount of copper taken up in different parts of the plant. The amount of copper(II) found within the roots, stems, and leaves was 13.8, 1.1, and 0.6 mg/g, respectively, after the creosote bush was exposed to a 63.5-ppm copper(II) solution for 48 h. When the plant was exposed to a 635-ppm copper(II) solution, the roots, stems, and leaves contained 35.0, 10.5, and 3.8 mg/g, respectively. In addition to FAAS analysis, x-ray microfluorescence (XRMF) analysis of the plant samples provided further confirmation of copper absorption by the various plant parts. X-ray absorption spectroscopy (XAS) elucidated the oxidation state of the copper absorbed by the plants. The copper(II) absorbed from solution remained as copper(II) bound to oxygen-containing ligands within the plant samples. The results of this study indicate that creosote bush may provide a useful and novel method of removing copper(II) from contaminated soils in an environmentally friendly manner. [source]

Laser-induced breakdown spectroscopy for soil diagnostics

EUROPEAN JOURNAL OF SOIL SCIENCE, Issue 2 2001
J. Bublitz
Summary Laser-optical measurements and fibre optics are potentially attractive tools for applications in soil science because of their great sensitivity and selectivity and their capabilities for on-line and in situ analysis. We have investigated laser-induced breakdown spectroscopy (LIBS) for the quantitative detection of metal ions on the surface of natural soil samples from two sites (Hohenschulen and Oderbruch, Germany). The LIBS technique allows the spatially resolved investigation of adsorption and desorption effects of ions in soil. A frequency doubled (532 nm) and Q-switched Nd:YAG laser with a pulse duration of 8 ns is focused on the soil surface and induces a plasma. Typical power densities are 150 mJ mm,2. The plasma emission is recorded in time and spectrally resolved by a gateable optical multichannel analyser (OMA). A delay time of about 500 ns between laser pulse and OMA gate was used to resolve single atomic and ionic spectral lines from the intense and spectrally broad light that is emitted by the plasma itself. The dependency of the LIBS signal of a single spectral line on the amount of water in the sample is investigated in detail. The results indicate that quenching of water in the plasma plume reduces the line intensities, while the interaction with aquatic colloids increases the intensity. The two processes compete with each other, and a non-linear correlation between measured line intensities and the amount of water in the sample is obtained. This is verified by a simple computer simulation and has to be taken into account for the quantitative interpretation of LIBS signals, e.g. when absolute concentrations are estimated. In the present investigation natural calcium concentrations <,2 ,g kg,1 were measured with the LIBS technique in the samples for the two test sites. In addition, measurements were made with dry and water-saturated BaCl2 mixed soil samples, and no significant difference in the detection limit for barium was obtained. [source]

Reversible Cluster Formation of Colloidal Nanospheres by Interparticle Photodimerization,

ADVANCED FUNCTIONAL MATERIALS, Issue 5 2004
X. Yuan
Abstract Crosslinked spherical nanoparticles based on trimethoxysilane monomers have been prepared by polycondensation in aqueous emulsion. These particles have been labeled chemically at their surface region with two different types of organic dye molecules (cinnamate, coumarin), which both are well known for their ability to undergo a reversible photodimerization if irradiated with light of a suitable wavelength. Upon irradiation of dilute solutions of these nanoparticles with UV light, the photodimerization of labels belonging to different colloidal nanoparticles caused the formation of large colloidal clusters consisting of chemically bound individual nanospheres. This process has been quantitatively investigated using light scattering and atomic force microscopy. Importantly, utilizing the reversibility of the photoreaction, the clusters could be broken up by irradiation of the sample with UV light of shorter wavelengths than the light used for their formation [source]

Polyimide Orientation Layers Prepared from Lyotropic Aromatic Poly(Amic Ethyl Ester)s,

ADVANCED FUNCTIONAL MATERIALS, Issue 5 2003
C. Neuber
Abstract The synthesis and characterization of liquid-crystalline precursor polymer solutions[1] for polyimides permit for the first time the preparation of bulk- and surface-oriented polyimide thin films from the nematic lyotropic state by shear. A special shearing technique was developed and optimized to orient viscous solutions into thin films with thicknesses below 100 nm. The films produced were thermally imidized and characterized by polarized light microscopy, as well as polarized FTIR and UV-vis spectroscopy before and after imidization. The dichroic ratios (DRs) before imidization were determined as 5 by FTIR, and 4.5 by UV-vis spectroscopies. After imidization the DRs increased to 14 and 7, respectively. The shear-oriented layers possess a surface profile in the form of striations, which was characterized by mechanical surface scanning and atomic force microscopy (AFM). The profile height was determined in the nanometer range in contrast to the profile distance in the micrometer range, thus the latter is a magnitude larger than the film thickness. To quantify and compare the orientation potential of the obtained orientation layers, cells with a liquid-crystalline host and a dichroic azo dye as guest were prepared. Interesting for this class of rod-like polyimides is that layers, which were cast from low concentration isotropic solutions and rubbed, exhibited an almost doubled DR of 15 compared to analogously prepared alignment layers based on commercial flexible polyimide systems (DR,=,8). [source]

Institute of Physics, CAS: (Adv. Mater.

ADVANCED MATERIALS, Issue 45 2009
45/2009)
Founded in 1928, the Institute of Physics of the Chinese Academy of Sciences has become one of China's leading research institutions. In 2003, the Institute acquired the Beijing National Laboratory for Condensed Matter Physics, one of the first six national laboratories in China. Its current programs focus on condensed matter physics and its theory, optical physics, atomic and molecular physics, soft matter, plasma physics, and computational physics. [source]

Conditioning polymers in today's shampoo formulations , efficacy, mechanism and test methods

Comparison of second-order orbital-dependent DFT correlation functionals

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2008
Ireneusz Grabowski
Abstract The choice of the orbital-dependent second-order correlation functional plays the prime role in the description of the correlation effects in orbital-dependent DFT calculations. Using second-order perturbation theory we were able to derive the simplest orbital-dependent correlation functional, but even at this lowest correlation level, we had several possibilities to define it. Applications of different second-order correlation functionals for the atomic as well as molecular systems are presented. The ab initio DFT-type OEP2 functionals based on Møller-Plesset or semicanonical partitioning (OEP2-sc) are compared with those based on Epstein-Nesbet type partitioning, showing that the latter ones can fail in more difficult molecular problems, e.g., the Be dimer potential curve. We show that currently the best performing orbital-dependent second-order correlation functional is the OEP2-sc one. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source]

Natural bond orbital-based energy density analysis for correlated methods: Second-order Møller,Plesset perturbation and coupled-cluster singles and doubles

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2008
Yutaka Imamura
Abstract Natural bond orbital-based energy density analysis (NBO-EDA), which split energies into atomic and bonding contributions, is proposed for correlated methods such as coupled-cluster singles and doubles (CCSD) and second-order Møller,Plesset (MP2) perturbation. Applying NBO-EDA for CCSD and MP2 to ethylene and the Diels,Alder reaction, we are successful in obtaining useful knowledge regarding electron correlation of ,- and ,-type orbitals, and clarifying the difference of the reaction barriers and heat of reaction calculated by CCSD and MP2. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source]

Comparative study of electrostatic solvent response by RISM and PCM methods,

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2007
S. Chiodo
Abstract The solvent response on the solute is calculated by the reference interaction site model (RISM) and by the polarizable continuum model (PCM) methods. The linearized RISM technique is developed to treat free energies of atomic and polyatomic ions in water. An empirical repulsive bridge is used for the RISM calculations. The solvent electrostatic potential is approximated by a linear dependence on the solute atomic charges. For a series of monovalent polyatomic cations and anions, the method provides free energies deviating by few percent from the experimental data. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source]

Using an interval branch-and-bound algorithm in the Hartree,Fock method

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2005
Carlile C. Lavor
Abstract The Hartree,Fock (HF) method is widely used to obtain atomic and molecular electronic wave functions, based on the minimization of a functional of the energy. We propose to use a deterministic global optimization algorithm, based on a branch-and-bound method, that applies techniques of interval arithmetic. This algorithm is applied directly to the minimization of the energy expression derived from the HF method. The proposed approach was successfully applied to the ground state of He and Be atoms. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source]

Model density approach to the Kohn,Sham problem: Efficient extension of the density fitting technique

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2005
Uwe Birkenheuer
Abstract We present a novel procedure for treating the exchange-correlation contributions in the Kohn,Sham procedure. The approach proposed is fully variational and closely related to the so-called "fitting functions" method for the Coulomb Hartree problem; in fact, the method consistently uses this auxiliary representation of the electron density to determine the exchange-correlation contributions. The exchange-correlation potential and its matrix elements in a basis set of localized (atomic) orbitals can be evaluated by reusing the three-center Coulomb integrals involving fitting functions, while the computational cost of the remaining numerical integration is significantly reduced and scales only linearly with the size of the auxiliary basis. We tested the approach extensively for a large set of atoms and small molecules as well as for transition-metal carbonyls and clusters, by comparing total energies, atomization energies, structure parameters, and vibrational frequencies at the local density approximation and generalized gradient approximation levels of theory. The method requires a sufficiently flexible auxiliary basis set. We propose a minimal extension of the conventional auxiliary basis set, which yields essentially the same accuracy for the quantities just mentioned as the standard approach. The new method allows one to achieve substantial savings compared with a fully numerical integration of the exchange-correlation contributions. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source]

HF,CC model for atoms and molecules,

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2002
E. Clementi
Abstract The Hartree,Fock,Clementi,Corongiu method (HF,CC) is revisited, aiming at an unified formulation for post-HF energy computations in atomic and molecular systems. For atomic systems new parameterizations of the HF,CC functional are proposed for the computation of atoms. The previous HF,CC molecular functional (Clementi, E.; Corongiu, G. Theochem 2001, 543, 39), revisited and recalibrated with a new optimization of the parameters, is tested with a sample of 131 molecules, including radicals, H-bond, and van der Waals systems. The atomization energy is decomposed into "HF classic" energy (the sum of the HF nuclear electron, HF kinetic, and HF Coulomb energies), "HF exchange" energy, and correlation energy; the latter is computed with a scaling functional with atomic, covalent, ionic, and van der Waals contributions. For the sample of 131 molecules, the computed HF,CC atomization energies have an average standard deviation of 1.89 kcal/mol. The atomic and molecular components of the correlation energy are decomposed into nuclear electron, kinetic, Coulomb, and exchange contributions; these decompositions characterize the HF,CC model and are used to explain the origin of the chemical bond. Computations on van der Waals systems show the validity of the HF,CC method also for long-range weak interactions. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 [source]

Immobilization of Porphyrinatocopper Nanoparticles onto Activated Multi-Walled Carbon Nanotubes and a Study of its Catalytic Activity as an Efficient Heterogeneous Catalyst for a Click Approach to the Three-Component Synthesis of 1,2,3-Triazoles in Water

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009
Hashem Sharghi
Abstract An efficient, regioselective, one-pot and two-step synthesis of ,-hydroxy 1,4-disubstituted 1,2,3-triazoles from a wide range of non-activated terminal alkynes and epoxides and sodium azide by way of a three-component click reaction using a catalytic amount of [meso -tetrakis(o -chlorophenyl)porphyrinato]copper(II) (5,mol%) in excellent isolated yields is described. The reactions were performed in water as a green solvent at ambient temperature without any additives. By performing two reaction steps in one pot and purifying only at the final step, this procedure excludes any interim purification of in situ generated organic azide intermediates, which significantly improves the overall yield and reduces the reaction time. To benefit from the recovery and reuse of the catalyst, a new heterogeneous catalyst was prepared by simple and successful impregnation of the catalyst onto activated multi-walled carbon nanotubes (AMWCNT). The heterogeneous catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic forced microscopy (AFM), and thermogravimetric (TG) analysis to estimate the amount of nitrogen adsorption, and Raman and FT-IR spectroscopy. Leaching experiments after ten successive cycles showed that the catalyst is most strongly anchored to the AMWCNT support. Mechanistically, porphyrinatocopper catalyzes each step of the reaction in different ways as a bifunctional catalyst including epoxide ring opening by azide delivery to epoxide, forming in situ generated 2-azido alcohols followed by activation of the CC triple bond of the starting terminal alkynes by forming a porphyrinatocopper-acetylide intermediate and thereby promoting the [3+2]-cycloaddition reaction as the key step to form the triazole framework. [source]

Copper Nanoparticles on Charcoal for Multicomponent Catalytic Synthesis of 1,2,3-Triazole Derivatives from Benzyl Halides or Alkyl Halides, Terminal Alkynes and Sodium Azide in Water as a "Green" Solvent

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009
Hashem Sharghi
Abstract A one-pot procedure for synthesis of 1,2,3-triazole derivatives via the three-component coupling (TCC) reaction between terminal alkynes, benzyl or alkyl halides, and sodium azide in the presences of 1,mol% nanoparticles copper/carbon (Cu/C) catalyst has been developed. The catalyst showed high catalytic activity and 1,4-regioselectivity for the [3+2],Huisgen cycloaddition in water as a "green" solvent and good to excellent yields were obtained in all cases. This procedure eliminates the need to handle organic azides, and they are generated in situ. The reaction has a broad scope and is especially practical for the synthesis of new azacrown ether and anthraquinone derivatives of triazole. The heterogeneous catalysts were fully characterized by scanning electron microscopy (SEM), atomic forced microscopy (AFM), X-ray diffraction (XRD), inductively coupled plasma (ICP) analysis and FT-IR experimental techniques. The catalyst was recycled ten times without significant loss of activity. [source]

About the efficiency of the early FOMs in ab initio protein phasing

JOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 5 2004
Maria C. Burla
All ab initio techniques for solving protein crystal structures use multisolution approaches. Several figures of merit that are found in the literature are efficient in the last steps of the phasing process, when some trials converge to the correct solution with a relatively small average phase error. Early figures of merit are much more critical; they should be able to recognize useful trials when the phase error is still large, and their efficiency determines the efficiency of the program. In the present work, a wide variety of known figures of merit at atomic and quasi-atomic (,1.4,Å) resolution have been tested; new figures have also been devised and tested. Their application to a large set of test structures allows the study of their properties at different data resolutions and the selection of the most efficient figures within the SIR2003-N framework. [source]

Hildebrand and Hansen solubility parameters from Molecular Dynamics with applications to electronic nose polymer sensors

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2004
M. Belmares
Abstract We introduce the Cohesive Energy Density (CED) method, a multiple sampling Molecular Dynamics computer simulation procedure that may offer higher consistency in the estimation of Hildebrand and Hansen solubility parameters. The use of a multiple sampling technique, combined with a simple but consistent molecular force field and quantum mechanically determined atomic charges, allows for the precise determination of solubility parameters in a systematic way (, = 0.4 hildebrands). The CED method yields first-principles Hildebrand parameter predictions in good agreement with experiment [root-mean-square (rms) = 1.1 hildebrands]. We apply the CED method to model the Caltech electronic nose, an array of 20 polymer sensors. Sensors are built with conducting leads connected through thin-film polymers loaded with carbon black. Odorant detection relies on a change in electric resistivity of the polymer film as function of the amount of swelling caused by the odorant compound. The amount of swelling depends upon the chemical composition of the polymer and the odorant molecule. The pattern is unique, and unambiguously identifies the compound. Experimentally determined changes in relative resistivity of seven polymer sensors upon exposure to 24 solvent vapors were modeled with the CED estimated Hansen solubility components. Predictions of polymer sensor responses result in Pearson R2 coefficients between 0.82 and 0.99. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1814,1826, 2004 [source]

Novel computer program for fast exact calculation of accessible and molecular surface areas and average surface curvature

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2002
Oleg V. Tsodikov
Abstract New computer programs, SurfRace and FastSurf, perform fast calculations of the solvent accessible and molecular (solvent excluded) surface areas of macromolecules. Program SurfRace also calculates the areas of cavities inaccessible from the outside. We introduce the definition of average curvature of molecular surface and calculate average molecular surface curvatures for each atom in a structure. All surface area and curvature calculations are analytic and therefore yield exact values of these quantities. High calculation speed of this software is achieved primarily by avoiding computationally expensive mathematical procedures wherever possible and by efficient handling of surface data structures. The programs are written initially in the language C for PCs running Windows 2000/98/NT, but their code is portable to other platforms with only minor changes in input-output procedures. The algorithm is robust and does not ignore either multiplicity or degeneracy of atomic overlaps. Fast, memory-efficient and robust execution make this software attractive for applications both in computationally expensive energy minimization algorithms, such as docking or molecular dynamics simulations, and in stand-alone surface area and curvature calculations. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 600,609, 2002 [source]

Improved intermolecular force field for molecules containing H, C, N, and O atoms, with application to nucleoside and peptide crystals

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 11 2001
Donald E. Williams
Abstract A new intermolecular force field for nitrogen atoms in organic molecules was derived from a training dataset of 76 observed azahydrocarbon crystal structures and 11 observed heats of sublimation. The previously published W99 force field for hydrogen, carbon, and oxygen was thus extended to include nitrogen atoms. Nitrogen atoms were divided into four classes: N(1) for triply bonded nitrogen, N(2) for nitrogen with no bonded hydrogen (except the triple bonded case), N(3) for nitrogen with one bonded hydrogen, and N(4) for nitrogen with two or more bonded hydrogens. H(4) designated hydrogen bonded to nitrogen. Wavefunctions of 6-31g** quality were calculated for each molecule and the molecular electric potential (MEP) was modeled with net atomic and supplementary site charges. Lone pair electron charge sites were included for nitrogen atoms where appropriate, and methylene bisector charges were used for CH2 and CH3 groups when fitting the MEP. XH bond distances were set to standard values for the wave function calculation and then foreshortened by 0.1 Å for the MEP and force field fitting. Using the force field optimized to the training dataset, each azahydrocarbon crystal structure was relaxed by intermolecular energy minimization. Predicted maximum changes in unit cell edge lengths for each crystal were 3% or less. The complete force field for H, C, N, and O atoms was tested by intermolecular energy relaxation of nucleoside and peptide molecular crystals. Even though these molecules were not included in any of the training datasets for the force field, agreement with their observed crystal structures was very good, with predicted unit cell edge shifts usually less than 2%. These tests included crystal structures of representatives of all eight common nucleosides found in DNA and RNA, 15 dipeptides, four tripeptides, two tetrapeptides, and a pentapeptide with two molecules in the asymmetric unit. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1154,1166, 2001 [source]

Simultaneous determination of mono-, di- and tributyltin in environmental samples using isotope dilution gas chromatography mass spectrometry

JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 5 2004
Giuseppe Centineo
Abstract The development of a rapid, precise and accurate speciation method for the simultaneous determination of mono-, di- and tributyltin in environmental samples is described. The method is based on using isotope dilution gas chromatography/mass spectrometry (GC/MS) with electron ionization, a widely used technique in routine testing laboratories. A mixed spike containing 119Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) was used for the isotope dilution of the samples. Five molecular ions were monitored for each analyte, corresponding to the 116Sn, 117Sn, 118Sn, 119Sn and 120Sn isotopes. The detection at masses corresponding to 116Sn and 117Sn were used to correct for m + 1 and m + 2 contributions of 13C from the organic groups attached to the tin atom on the 118Sn, 119Sn and 120Sn masses with simple mathematical equations and the concentrations of the butyltin compounds were calculated based on the corrected 118Sn/119Sn and 120Sn/119Sn isotope ratios. The 119Sn-enriched multispecies spike was applied with satisfactory results to the simultaneous determination of MBT, DBT and TBT in three certified reference materials: two sediments, PACS-2 and BCR 646, and the mussel tissue CRM 477. The method was compared with a previously published GC/inductively coupled plasma MS isotope dilution procedure, developed in our laboratory, by injecting the same samples into both instruments. Comparable analytical results in terms of precision and accuracy are demonstrated for both atomic and molecular mass spectrometric detectors. Thus, reliable quantitative organotin speciation analysis can be achieved using the more widespread and inexpensive GC/MS instrument. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Performance of the atomic and molecular physics beamline at the National Synchrotron Radiation Laboratory

JOURNAL OF SYNCHROTRON RADIATION, Issue 6 2006
Sisheng Wang
At the National Synchrotron Radiation Laboratory, The University of Science and Technology of China, an atomic and molecular physics beamline with an energy range of 7.5,124,eV has been constructed for studying the spectroscopy and dynamics of atoms, molecules and clusters. The undulator-based beamline, with a high-resolution spherical-grating monochromator (SGM), is connected to the atomic and molecular physics end-station. This end-station includes a main experimental chamber for photoionization studies and an additional multi-stage photoionization chamber for photoabsorption spectroscopy. A mid-photon flux of 5 × 1012,photons,s,1 and a high resolving power is provided by this SGM beamline in the energy range 7.5,124,eV. The size of the synchrotron radiation beam spot at the sample is about 0.5,mm in the vertical direction and 1.0,mm in the horizontal direction. Some experimental results of photoionization efficiency spectroscopy and photoabsorption spectroscopy of atoms and molecules are also reported. [source]

Anisotropic features in XMCD spectra

JOURNAL OF SYNCHROTRON RADIATION, Issue 2 2001
Shin-ichi Nagamatsu
The angular dependent K -edge X-ray magnetic circular dichroism (XMCD) spectra based on the semi-relativistic full multiple scattering theory are discussed, where 2-spinor formalism is used to describe spin-orbit coupling. So far most of theoretical approaches have been limited to the simplest case where the circularly polarized X-ray propagation coincides with the direction of the magnetic field. Here we discuss more general cases, using the above theoretical approaches. We separately discuss atomic, single and full multiple scattering XMCD spectra; in particular anisotropic features of them are studied in detail. [source]

Atomic Structures and Electrical Properties of ZnO Grain Boundaries

JOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2007
Yukio Sato
Various properties of ceramics can be significantly influenced by the presence of grain boundaries. The influence on the properties is closely related to the grain-boundary atomic structures. As different grain boundaries have different atomic structure, different grain boundaries have different influence on the properties. It is difficult to examine the atomic structure and properties of individual grain boundaries in ceramics. In order to understand the atomic,structure,property relationships, well-defined single grain boundaries should be characterized. In the present paper, we review our recent results on the investigations of atomic structures and electrical properties of ZnO single grain boundaries. The relationships between the atomic structures and the electrical properties were investigated using ZnO bicrystals, whose grain-boundary orientation relationship and grain-boundary planes can be arbitrarily controlled. The discussion focuses on the microscopic origin of nonlinear current,voltage (I,V) characteristics across ZnO grain boundaries. High-resolution transmission electron microscopy (HRTEM) observations and lattice-statics calculations revealed the atomic structures of the undoped ZnO [0001] ,7 and ,49 grain boundaries, enabling a comparison between coincidence site lattice (CSL) boundaries with small and large periodicity. These grain boundaries contained the common structural units (SUs) featuring atoms with coordination numbers that are unusual in ZnO. The ,49 boundary was found to have characteristic arrangement of the SUs, where two kinds of the SUs are alternatively formed. It is considered that the characteristic arrangement was formed to effectively relax the local strain in the vicinity of the boundary. Such a relaxation of local strain is considered to be one of dominant factors to determine the SU arrangements along grain boundaries. I,V measurements of the undoped ZnO bicrystals showed linear I,V characteristics. Although the coordination and bond lengths of atoms in the grain boundaries differ from those in the bulk crystal, this does apparently not generate deep unoccupied states in the band gap. This indicates that atomic structures of undoped ZnO grain boundaries are not responsible for the nonlinear I,V characteristics of ZnO ceramics. On the other hand, the nonlinear I,V characteristic appeared when doping the boundaries with Pr. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of Pr-doped boundaries revealed that Pr segregates to specific atomic columns, substituting Zn at the boundary. However, the Pr itself was not the direct origin of the nonlinear I,V characteristics, as the Pr existed in the three-plus state and would not produce acceptor states in the boundary. First-principles calculations revealed that Pr doping instead promotes the formations of acceptor-like native defects, such as Zn vacancies. We believe that such acceptor-like native defects are microscopic origin of the nonlinear I,V characteristics. Investigations of various types of grain boundaries in the Pr and Co-codoped ZnO bicrystals indicated that the amounts of Pr segregation and the nonlinear I,V characteristics significantly depend on the grain-boundary orientation relationship. Larger amount of Pr segregation and, as a result, higher nonlinearity in I,V characteristics was obtained for incoherent boundaries. This indicates that Pr doping to incoherent boundaries is one of the guidelines to design the single grain boundaries with highly nonlinear I,V characteristics. Finally, a Pr and Co-codoped bicrystal with an incoherent boundary was fabricated to demonstrate a highly nonlinear I,V characteristic. This result indicates that ZnO single-grain-boundary varistors can be designed by controlling grain-boundary atomic structures and fabrication processes. Summarizing, our work firstly enabled us to gain a deeper understanding for the atomic structure of ZnO grain boundaries. Secondly, we obtained important insight into the origin of nonlinear I,V characteristics across the ZnO grain boundaries. And, finally, based on these results, we demonstrated the potential of this knowledge for designing and fabricating ZnO single-grain-boundary varistors. [source]

Energy absorption and emission of harmonics by clusters subject to intense short laser pulses

LASER PHYSICS LETTERS, Issue 9 2008
S.V. Popruzhenko
Abstract Experimental and theoretical achievements in studies of atomic and metal clusters interacting with short intense infrared laser pulses are reviewed. The focus is made on the theoretical concepts describing the energy transfer from the laser field to the cluster nanoplasma and emission of laser harmonics from it. Both effects are considered assuming the collisionless regime, where the interaction of nanoplasma electrons with the self-consistent field dominates the individual collisions. The pivotal role of nonlinear resonances is underlined and described in detail. Possible ways for a further development of the theory and experimental perspectives are briefly discussed. (© 2008 by Astro Ltd., Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA) [source]

Spatio-temporal inhomogeneities of laser induced plasma on surface solutions

LASER PHYSICS LETTERS, Issue 11 2004
J. Ben Ahmed
Abstract A transient plasma created by focusing a nanosecond laser pulse on the surface of ionic solutions of Ca++ and Mg++ is studied spectroscopically. This kind of plasma has a properties which vary significantly with time and over its extended volume. The emissions of ionic and atomic line of calcium and magnesium are analyzed to get information on the electronic temperature, the electronic density and on the kinetics of the population of low atomic and ionic states: 4P1 of CaI, 5S1/2 of CaII, 3P1 of MgII and 3P1/2 of MgII. The temperature is maximal at the plasma center and it drops at the edges. The study of the term as a function of time, where r is the radial position, shows a continue decreasing with time, which implies that the inhomogeneity of the temperature develops with time. On the another side, the electronic density deceases exponentially with time and does not vary significantly with space. These measurements allow us to follow the kinetics of the transformation of calcium (magnesium) from Ca++Mg++ to Ca+(Mg+) to give at the end Ca (Mg) and to understand the behavior of self-absorption phenomena which is observed in the resonance line of CaII at t , 2000 ns to increase with time. The experimental results are simulated by a kinetics model of LTE laser induced plasma in its late relaxation period. (© 2004 by ASTRO, Ltd. Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA) [source]