Solution enthalpies of 1,4-dioxane: Study of solvent effects through quantitative structure-property relationships

Solution enthalpies of 1,4-dioxane have been obtained in 15 protic and aprotic solvents at 298.15 K. Breaking the overall process through the use of Solomonov's methodology the cavity term was calculated and interaction enthalpies (Delta H-int) were determined. Main factors involved in the interaction enthalpy have been identified and quantified using a QSPR approach based on the TAKA model equation. The relevant descriptors were found to be pi* and beta, which showed, respectively, exothermic and endothermic contributions. The magnitude of pi* coefficient points toward non-specific solute-solvent interactions playing a major role in the solution process. The positive value of the beta coefficient reflects the endothermic character of the solvents' hydrogen bond acceptor (HBA) basicity contribution, indicating that solvent molecules engaged in hydrogen bonding preferentially interact with each other rather than with 1,4-dioxane. (C) 2013 Elsevier B.V. All rights reserved.

Structure et propriétés électroniques de nanotubes de carbone en solution polyélectrolyte

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

A semi-phenomenological approach to the structure and transport properties of macromolecules in solution

Motiviert durch die Lebenswissenschaften (Life sciences) haben sich Untersuchungen zur Dynamik von Makromolekülen in Lösungen in den vergangenen Jahren zu einem zukunftsweisenden Forschungsgebiet etabliert, dessen Anwendungen von der Biophysik über die physikalische Chemie bis hin zu den Materialwissenschaften reichen. Neben zahlreichen experimentellen Forschungsprogrammen zur räumlichen Struktur und den Transporteigenschaften grosser MolekÄule, wie sie heute praktisch an allen (Synchrotron-) Strahlungsquellen und den Laboren der Biophysik anzutreffen sind, werden gegenwärtig daher auch umfangreiche theoretische Anstrengungen unternommen, um das Diffusionsverhalten von Makromolekülen besser zu erklären. Um neue Wege für eine quantitative Vorhersagen des Translations- und Rotationsverhaltens grosser Moleküle zu erkunden, wurde in dieser Arbeit ein semiphänomenologischer Ansatz verfolgt. Dieser Ansatz erlaubte es, ausgehend von der Hamiltonschen Mechanik des Gesamtsystems 'Molekül + Lösung', eine Mastergleichung für die Phasenraumdichte der Makromoleküle herzuleiten, die den Einfluss der Lösung mittels effektiver Reibungstensoren erfasst. Im Rahmen dieses Ansatzes gelingt es z.B. (i) sowohl den Einfluss der Wechselwirkung zwischen den makromolekularen Gruppen (den sogenannten molekularen beads) und den Lösungsteilchen zu analysieren als auch (ii) die Diffusionseigen schaften für veschiedene thermodynamische Umgebungen zu untersuchen. Ferner gelang es auf der Basis dieser Näherung, die Rotationsbewegung von grossen Molekülen zu beschreiben, die einseitig auf einer Oberfläche festgeheftet sind. Im Vergleich zu den aufwendigen molekulardynamischen (MD) Simulationen grosser Moleküle zeichnet sich die hier dargestellte Methode vor allem durch ihren hohen `Effizienzgewinn' aus, der für komplexe Systeme leicht mehr als fünf Grössenordnungen betragen kann. Dieser Gewinn an Rechenzeit erlaubt bspw. Anwendungen, wie sie mit MD Simulationen wohl auch zukünftig nicht oder nur sehr zögerlich aufgegriffen werden können. Denkbare Anwendungsgebiete dieser Näherung betreffen dabei nicht nur dichte Lösungen, in denen auch die Wechselwirkungen der molekularen beads zu benachbarten Makromolekülen eine Rolle spielt, sondern auch Untersuchungen zu ionischen Flüssigkeiten oder zur Topologie grosser Moleküle.

GDASH: a grid-enabled program for structure solution from powder diffraction data

The simulated annealing approach to structure solution from powder diffraction data, as implemented in the DASH program, is easily amenable to parallelization at the individual run level. Very large scale increases in speed of execution can therefore be achieved by distributing individual DASH runs over a network of computers. The GDASH program achieves this by packaging DASH in a form that enables it to run under the Univa UD Grid MP system, which harnesses networks of existing computing resources to perform calculations.

MDASH: a multi-core-enabled program for structure solution from powder diffraction data

The simulated annealing approach to structure solution from powder diffraction data, as implemented in the DASH program, is easily amenable to parallelization at the individual run level. Modest increases in speed of execution can therefore be achieved by executing individual DASH runs on the individual cores of CPUs.

Synthesis, structure and solution chemistry of mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands

In the title family, the ONO donor ligands are the acetylhydrazones of salicylaidehyde (H2L1) and 2-hydroxyacetophenone (H2L2) (general abbreviation, H2L). The reaction of bis(acetylacetonato)oxovanadium(IV) with a mixture of tridentate H2L and a bidentate NN donor [e.g., 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen), hereafter B] ligands in equimolar ratio afforded the tetravalent complexes of the type [(VO)-O-IV(L)(B)]; complexes (1)-(4) whereas, if B is replaced by 8-hydroxyquinoline(Hhq) (which is a bidentate ON donor ligand), the above reaction mixture yielded the pentavalent complexes of the type [(VO)-O-V(L)(hq)]; complexes (5) and (6). Aerial oxygen is most likely the oxidant (for the oxidation of V-IV -> V-V) in the synthesis of pentavalent complexes (5) and (6). [(VO)-O-IV(L)(B)] complexes are one electron paramagnetic and display axial EPR spectra, while the [(VO)-O-V(L)(hq)] complexes are diamagnetic. The X-ray structure of [(VO)-O-V(L-2)(hq)] (6) indicates that H2L2 ligand is bonded with the vanadium meridionally in a tridentate dinegative fashion through its phenolic-O, enolic-O and imine-N atoms. The general bond length order is: oxo < phenolato < enolato. The V-O (enolato) bond is longer than V-O (phenolato) bond by similar to 0.07 angstrom and is identical with V-O (carboxylate) bond. H-1 NMR spectrum of (6) in CDCl3 solution indicates that the binding nature in the solid state is also retained in solution. Complexes (1)(4) display two ligand-field transitions in the visible region near 820 and 480 nm in DMF solution and exhibit irreversible oxidation peak near +0.60 V versus SCE in DMSO solution, while complexes (5) and (6) exhibit only LMCT band near 535 nm and display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. The VO3+-VO2+ E-1/2 values shift considerably to more negative values when neutral NN donor is replaced by anionic ON donor species and it also provides better VO3+ binding via phenolato oxygen. For a given bidentate ligand, E-1/2 increases in the order: (L-2)(2-) < (L-1)(2-). (c) 2004 Elsevier B.V. All rights reserved.

Synthesis, structure, solution chemistry and the electronic effect of para substituents on the vanadium center in a family of mixed-ligand [(VO)-O-V(ONO)(ON)] compexes

Four tridentate dibasic ONO donor hydrazone ligands derived from the condensation of benzoylhydrazine with either 2-hydroxyacetophenone or its para substituted derivatives (H2L1-4, general abbreviation H2L) have been used as primary ligands and 8-hydroxyquinoline (Hhq, a bidentate monobasic ON donor species) has been used as auxiliary ligand. The reaction of [(VO)-O-IV(acac)21 with H2L in methanol followed by the addition of Hhq in equimolar ratio under aerobic condition afforded the mixed-ligand oxovanadium(V) complexes of the type [(VO)-O-V(L)(hq)] (1-4) in excellent yield. The X-ray structure of the compound [(VO)-O-V(L-4)(hq)] (4) indicates that the H2L4 ligand is bonded with vanadium meridionally in a tridentate dinegative fashion through its deprotonated phenolic-O, deprotonated enolic-O and imine-N atoms. The V-O bond length order is: oxo < phenolato < enolato. H-1 NMR spectra of 4 in CDCl3 solution indicates that it's solid-state structure is retained in solution. Complexes are diamagnetic and exhibit only ligand to metal charge transfer (LMCT) transition band near 530 nm in CH2Cl2 solution in addition to intra-ligand pi-pi* transition band near 335 rim and they display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. lambda(max) (for LMCT transition) and the reduction peak potential (E-p(c)) values of the complexes are found to be linearly related with the Hammett (sigma) constants of the substituents in the aryloxy ring of the hydrazone ligands. lambda(max) and E-p(c) values show large dependence d lambda(max)/d sigma = 32.54 nm and dE(p)(c)/d sigma = 0.19 V, respectively, on the Hammett constant. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis, structure and solution chemistry of quaternary oxovanadium(V) complexes incorporating hydrazone ligands

[VIVO(acac)(2)] reacts with an equimolar amount of benzoyl hydrazone of 2-hydroxyacetophenone (H2L1) or 5-chloro-2-hydroxyacetophenone (H2L2) in the presence of excess pyridine (py) in methanol to produce the quaternary [(VO)-O-V(L-1)(OCH3)(py)] (1) and [(VO)-O-V(L-2)(OCH3)(py)] (2) complexes, respectively, while under similar condition, the benzoyl hydrazones of 2-hydroxy-5-methylacetophenone (H2L3) and 2-hydroxy-5-methoxyacetophenone (H2L4) afforded only the methoxy bridged dimeric [(VO)-O-V(L-3/L-4)(OCH3)](2) complexes. The X-ray structural analysis of 1 and 2 indicates that the geometry around the metal is distorted octahedral where the three equatorial positions are occupied by the phenolate-O, enolate-O and the imine-N of the fully deprotonated hydrazone ligand in its enolic form and the fourth one by a methoxide-O atom. An oxo-O and a pyridine-N atom occupy two axial positions. Quaternary complexes exhibit one quasi-reversible one-electron reduction peak near 0.25 V versus SCE in CH2Cl2 and they decompose appreciably to the corresponding methoxy bridged dimeric complex in CDCl3 solution as indicated by their H-1 NMR spectra. These quaternary VO3+ complexes are converted to the corresponding V2O34+-complexes simply on refluxing them in acetone and to the VO2+-complexes on reaction with KOH in methanol. An equimolar amount of 8-hydroxyquinoline (Hhq) converts these quaternary complexes to the ternary [(VO)-O-V(L)(hq)] complexes in CHCl3. (C) 2009 Elsevier B. V. All rights reserved.

Synthesis, structure and solution chemistry of a family of dinuclear hydrazonato-vanadium(V) complexes with [OV(mu-O)VO](4+) core

Dinuclear trioxidic [{VOL}(2)mu-O] (1-4) complexes were synthesized from the reaction of [(VO)-O-IV(acac)(2)] with an equimolar amount of H2L [H2L is the general abbreviation of hydrazone ligands (H2L1-4) derived from the condensation of benzoyl hydrazine with either 2-hydroxyacetophenone or its para substituted derivatives] in acetone or CH2Cl2 or acetonitrile. These V2O3L2 complexes were also obtained from the reaction of VOSO4 with H2L in the presence of two equivalents sodium acetate in aqueous-methanolic (50% V/V) medium and also from the decomposition of [(VO)-O-IV(L)(bipy/phen)] complexes in CH2Cl2 Solution. Black monoclinic crystals of 2 and 4 with C2/c space group were obtained from the reaction of [(VO)-O-IV(acac)(2)], respectively, with H2L2 and H2L4 in acetone in which the respective ligands are bonded meridionally to vanadium in their fully deprotonated enol forms. The V-O bond lengths follow the order: V-O(oxo) < V-O(oxo-bridged) < V-O(phenolate) < V-O(enolate). Complexes (1-4) are diamagnetic exhibiting LMCT transition band near 380 nm in CH2Cl2 solution and they are electroactive displaying a quasi-reversible reduction peak in the 0.14-0.30 V versus SCE region. The and the reduction peak potential (E-p(c)) values show linear relationships with the Hammett constant (sigma) of the substituents in the hydrazone ligands. These dinuclear complexes are converted to the corresponding mononuclear cis dioxo complexes K(H2O)(+)[(VO2)-O-V(L)](-) (5-8) and mixed-ligand [(VO)-O-V(L)(hq)] complexes on reaction, respectively, with two equivalents KOH in methanol and two equivalents 8-hydroxyquinoline (Hhq) in CHCl3. Ascorbic acid reduces the dioxovanadium(V) complexes reversibly under aerobic condition. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, structure and solution chemistry of dioxidovanadium(V) complexes with a family of hydrazone ligands. Evidence of formation of centrosymmetric dimers via H-bonds in the solid state

[(VO)-O-IV(acac) 2] reacts with the methanol solution of tridentate ONO donor hydrazone ligands (H2L1-4, general abbreviation H2L; are derived from the condensation of benzoyl hydrazine with 2-hydroxyacetophenone and its 5-substituted derivatives) in presence of neutral monodentate alkyl amine bases having stronger basicity than pyridine e. g., ethylamine, diethylamine, triethylamine and piperidine (general abbreviation B) to produce BH+[VO2L] (1-16) complexes. Five of these sixteen complexes are structurally characterized revealing that the vanadium is present in the anionic part of the molecule, [VO2L] in a distorted square pyramidal environment. The complexes 5, 6, 15 and 16 containing two H-atoms associated with the amine-N atom in their cationic part (e. g., diethylammonium and piperidinium ion) are involved in H-bonding with a neighboring molecule resulting in the formation of centrosymmetric dimers while the complex 12 (containing only one hydrogen atom in the cationic part) exhibits normal H-bonding. The nature of the H-bonds in each of the four centrosymmetric dimeric complexes is different. These complexes have potential catalytic activity in the aerial oxidation of L-ascorbic acid and are converted into the [VO(L)(hq)] complexes containing VO3+ motif on reaction with equimolar amount of 8-hydroxyquinoline (Hhq) in methanol.

CDASH: a cloud-enabled program for structure solution from powder diffraction data

The simulated annealing approach to crystal structure determination from powder diffraction data, as implemented in the DASH program, is readily amenable to parallelization at the individual run level. Very large scale increases in speed of execution can be achieved by distributing individual DASH runs over a network of computers. The CDASH program delivers this by using scalable on-demand computing clusters built on the Amazon Elastic Compute Cloud service. By way of example, a 360 vCPU cluster returned the crystal structure of racemic ornidazole (Z0 = 3, 30 degrees of freedom) ca 40 times faster than a typical modern quad-core desktop CPU. Whilst used here specifically for DASH, this approach is of general applicability to other packages that are amenable to coarse-grained parallelism strategies.

Combining structure and dynamics: non-denaturing high-pressure effect on lysozyme in solution

Small-angle X-ray scattering (SAXS) and elastic and quasi-elastic neutron scattering techniques were used to investigate the high-pressure-induced changes on interactions, the low-resolution structure and the dynamics of lysozyme in solution. SAXS data, analysed using a global-fit procedure based on a new approach for hydrated protein form factor description, indicate that lysozyme completely maintains its globular structure up to 1500 bar, but significant modi. cations in the protein-protein interaction potential occur at approximately 600-1000 bar. Moreover, the mass density of the protein hydration water shows a clear discontinuity within this pressure range. Neutron scattering experiments indicate that the global and the local lysozyme dynamics change at a similar threshold pressure. A clear evolution of the internal protein dynamics from diffusing to more localized motions has also been probed. Protein structure and dynamics results have then been discussed in the context of protein-water interface and hydration water dynamics. According to SAXS results, the new configuration of water in the first hydration layer induced by pressure is suggested to be at the origin of the observed local mobility changes.

gamma-zein secondary structure in solution by circular dichroism

The proline-rich N-terminal domain of gamma-zein has been reported in relevant process, which include its ability to cross the cell membranes. Evidences indicate that synthetic hexapeptide (PPPVHL), naturally found in N-terminal portion of gamma-zein, can adopt the polyproline II (PPII) conformation in aqueous solution. The secondary structure of gamma-zein in maize protein bodies had been analyzed by solid state Fourier transform infrared and nuclear magnetic resonance spectroscopies. However, it was not possible to measure PPII content in physiological environment since the beta-sheet and PPII signals overlap in both solid state techniques. Here, the secondary structure of gamma-zein has been analyzed by circular dichroism in SDS aqueous solution with and without ditiothreitol (DTT), and in 60% of 2-propanol and water with DTT The results show that gamma-zein has high helical content in all solutions. The PPII conformation was present at about 7% only in water/DTT solution. (c) 2007 Wiley Periodicals, Inc.

Crystal structure of the (Mg,Fe)[UO2(P,As)O-4](2) center dot 10H(2)O solid solution - A novel mineral variety of saleeite

The crystal structure of a novel variety {[(Mg0.81Fe0.19)(H2O)(6)](H2O)(4)}{(UO2)[(P0.67As0.33)O-4]}(2) of the mineral saleeite is determined using X-ray diffraction (Bruker Smart diffractometer, lambda MoK alpha, graphite monochromator, 2 theta(max) = 56.62 degrees, R = 0.0321 for 2317 reflections, T = 100 K). The main crystal data are as follows: a = 6.952(6) angstrom, b = 19.865(5) , angstrom, c = 6.969(2) angstrom, beta = 90.806(4)degrees, space group P12(l)/n1, Z = 2, and P-calcd = 3.34 g/cm(3). It is shown that the structure is formed by alternating (along the [010] direction) anionic layers, which are composed of uranium bipyramids and T(P,As) tetrahedra, and cation layers consisting of M(Mg, Fe) octahedra and water molecules, which are joined through a system of asymmetric hydrogen bonds. The hydrogen atoms are located, the scheme of hydrogen bonds is established, and their geometric characteristics are calculated.