Examinando por Materia "Hydrogen bonds"

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    Correlations between thermal and tensile behavior with friction coefficient in copolyamides 6/12
    (Elsevier Ltd, 2017-02-15) Álvarez-Láinez, M.L.; Palacio R., J.A.; Universidad EAFIT. Departamento de Ingeniería de Diseño; Ingeniería de Diseño (GRID)
    Although polyamide 6 (PA6) obtained from e-caprolactame (CL) is an engineering polymer with outstanding properties used in sliding applications, it exhibits low impact strength and high water absorption. Those are some of the reasons why copolymerization between CL and laurolactame (LL) is desired. In this work, copolymers from 0–100 wt% LL are prepared to evaluate crystallinity, melting behavior, tensile properties and those properties are correlated with coefficient of friction. Experimental results show that PA6 (0 wt%) crystallinity and elasticity modulus are higher than those obtained from 100 wt%LL (PA12), but friction coefficient in PA6 is lower than that of PA12. While with 60 wt% LL crystallinity and elastic modulus reach a minimum value, with 350% elongation and coefficient of friction they register a maximum value. Our results suggest that crystallinity and elastic modulus are opposed to coefficient of friction. The absence of hydrogen bonds produces irregularities in the chain, reducing the crystal formation; such behavior is a consequence of copolymerization. Our findings will help to customize copolyamide, modulate the response between mechanical properties and friction behavior, as well as evaluate when it is necessary to add lubricants in the copolymer formulations. © 2016 Elsevier B.V.
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    Hydrogen bonding in the binary water/ammonia complex
    (IOS Press, 2014-01-01) Guerra, D.; David, J.; Restrepo, A.; Universidad EAFIT. Departamento de Ciencias Básicas; Electromagnetismo Aplicado (Gema)
    A detailed study of the interactions leading to stabilization of the NH3(H2O){n =1,2} clusters is presented in this work. The Potential Energy Surface for the trimers was explored using an adapted version of the simulated annealing optimization procedure that produced cluster candidate structures that were further optimized, refined, and characterized at the MP2/6-311++G(d, p) level. Our results indicate that hydrogen bonding of the N-H type is stronger and more covalent than of the O-H type. We provide evidence that suggests that the topological complexity of the electron distributions is directly correlated with cluster stability and that most of the stabilization energy originates in electrostatic and exchange contributions. Our calculated trimerization enthalpy, H° 298-41.75 kJ/mol, is in excellent agreement with the experimental enthalpy of adsorption of NH3 into surface water, reported to be-(41 ± 5) kJ/mol. © 2014-IOS Press.
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    Interfibril hydrogen bonding improves the strain-rate response of natural armour
    (Royal Society Publishing, 2019-01-01) Arola D.; Ghods S.; Son C.; Murcia S.; Ossa E.A.; Arola D.; Ghods S.; Son C.; Murcia S.; Ossa E.A.; Universidad EAFIT. Departamento de Ingeniería de Producción; Materiales de Ingeniería
    Fish scales are laminated composites that consist of plies of unidirectional collagen fibrils with twisted-plywood stacking arrangement. Owing to their composition, the toughness of scales is dependent on the intermolecular bonding within and between the collagen fibrils. Adjusting the extent of this bonding with an appropriate stimulus has implications for the design of next-generation bioinspired flexible armours. In this investigation, scales were exposed to environments of water or a polar solvent (i.e. ethanol) to influence the extent of intermolecular bonding, and their mechanical behaviour was evaluated in uniaxial tension and transverse puncture. Results showed that the resistance to failure of the scales increased with loading rate in both tension and puncture and that the polar solvent treatment increased both the strength and toughness through interpeptide bonding; the largest increase occurred in the puncture resistance of scales from the tail region (a factor of nearly 7). The increase in strength and damage tolerance with stronger intermolecular bonding is uncommon for structural materials and is a unique characteristic of the low mineral content. Scales from regions of the body with higher mineral content underwent less strengthening, which is most likely the result of interference posed by the mineral crystals to intermolecular bonding. Overall, the results showed that flexible bioinspired composite materials for puncture resistance should enrol constituents and complementary processing that capitalize on interfibril bonds. © 2019 The Author(s) Published by the Royal Society. All rights reserved.
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    Structural characterization of the (methanol)4 potential energy surface
    (AMER CHEMICAL SOC, 2009-09-24) David, Jorge; Guerra, Doris; Restrepo, Albeiro; Universidad EAFIT. Departamento de Ciencias Básicas; Electromagnetismo Aplicado (Gema)
    In this paper, we report the geometries and properties of the structural isomers obtained from a random walk of the potential energy surface (PES) of the methanol tetramer. Thirty-three structures were obtained after B3LYP/6-31+g* optimization of 94 candidate structures generated from a stochastic search of the PM3 conformational space. The random search was carried out using a recently proposed modified Metropolis acceptance test in the simulated annealing (SA) procedure. Corrections for the basis set superposition error (BSSE) show improvements on the binding energies of the clusters in an average of approximately 2.0 kcal/mol, while geometries are predicted to be less sensitive to BSSE corrections. MP2/aug-cc-pvdz calculations on representative structures did not change the geometries but predicted better binding energies. Highly correlated CCSD(T) energies were calculated on the B3LYP and MP2 stationary points and used to establish relative stabilities. We report several new conformations and group the structures into six distinct geometrical motifs. Only the cyclic tetramers with four primary hydrogen bonds in the same plane are predicted to have significant populations. Secondary hydrogen bonds, those for which the donated proton comes from an alkyl group, lead to a rich conformational space.
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    Structural studies of the water hexamer
    (AMER CHEMICAL SOC, 2010-07-29) Hincapie, Gina; Acelas, Nancy; Castano, Marcela; David, Jorge; Restrepo, Albeiro; Universidad EAFIT. Departamento de Ciencias Básicas; Electromagnetismo Aplicado (Gema)
    In this paper we report the geometries and properties of 24 structural isomers located on the MP2/6-311++g**potential energy surface of the water hexamer. At least 15 structural patterns are located within 3 kcal/mol of the most stable conformation, leading to a very complex potential energy surface, several isomers having significant contributions. A quadratic correlation between the distance from the proton to the center of the hydrogen bond with the distance between oxygen atoms for all clusters is reported. MP2/6-311++g**and CCSD(T)/aug-cc-pvdz//MP2/6-311++g**predict different stabilization orderings but are in good agreement for binding energies. Compact structures are energetically favored by electronic energies with zero point energy corrections, while noncompact cyclic structures are preferred when temperature and entropy are accounted for. © 2010 American Chemical Society.
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    Structural studies of the water pentamer
    (ELSEVIER SCIENCE BV, 2011-05-09) Ramirez, Frank; Hadad, C. Z.; Guerra, Doris; David, Jorge; Restrepo, Albeiro; Universidad EAFIT. Departamento de Ciencias Básicas; Electromagnetismo Aplicado (Gema)
    A computational study of the water pentamer gas phase conformational space is reported in this Letter. Forty-four stationary points distributed among 12 structural patterns were located at the MP2/6-311++G(d,p) level. At least 5 geometrical motifs (25 structures) are predicted within 3 kcal/mol of the most stable conformation at the CCSD(T)/aug-cc-pVTZ//MP2/6-311++G(d,p) level. We show evidence that dipole-dipole interactions are at play in stabilizing the clusters. Electron densities and their Laplacians at the hydrogen bond critical points were found to be linearly correlated with relative energies for all clusters. Logarithmic relationships were found for the [req, ?(rc)] and [req,?2?( rc)] pairs in all hydrogen bonds. © 2011 Elsevier B.V. All rights reserved.
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    Structures, energies, and bonding in the water heptamer
    (AMER INST PHYSICS, 2013-07-28) Acelas, Nancy; Hincapie, Gina; Guerra, Doris; David, Jorge; Restrepo, Albeiro; Universidad EAFIT. Departamento de Ciencias Básicas; Electromagnetismo Aplicado (Gema)
    In this paper we report the geometries and properties of 38 distinct geometrical motifs located on the B3LYP/6-31+G(d), MP2/6-311++G(d, p) potential energy surfaces of the water heptamer. Binding energies of up to 45 kcal/mol are calculated. All motifs fall within 10 kcal/mol of the most stable conformation, with at least 13 structural patterns located no more than 3 kcal/mol above, leading to a very complex potential energy surface, populated by a multitude of motifs each one allowing large numbers of conformations. Cluster stability does not seem to be correlated with the number of hydrogen bonds. Compact structures are energetically favored by electronic energies with zero-point energy corrections, while more open structures are preferred when temperature and entropy are accounted for. The molecular interactions holding the clusters as discrete units lead to large binding energies but are not strong enough to cause significant changes in the geometries of the interacting monomers. Our results indicate that bonding in the water heptamers can be considered as largely non-shared interactions with contributions from intermediate character of increasing covalency. © 2013 AIP Publishing LLC.
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    Substantial improvement of electrocatalytic predictions by systematic assessment of solvent effects on adsorption energies
    (Elsevier B.V., 2020-01-01) Rendón-Calle A.; Builes S.; Calle-Vallejo F.; Universidad EAFIT. Departamento de Ingeniería de Procesos; Desarrollo y Diseño de Procesos
    Electrocatalytic activities are largely determined by the interplay of adsorbates with substrates and solvents. Although capturing the interactions of those three components is usually arduous, here we provide a simple micro-solvation method to evaluate them in aqueous media. The method helps determine: (a) the number of water molecules making hydrogen bonds with the adsorbates, and (b) the energetic stabilization of the adsorbates by those hydrogen bonds. To evaluate the usefulness of the method, we consider CO2 reduction to CO, CH4, and CH3OH on Cu, Ag, Au, and Zn. Applying the calculated solvation corrections, we find good agreement with experiments in the predicted pathways and onset potentials, with an average error of only 0.07 V. Conversely, models with ad hoc or implicit solvation corrections predict unlikely pathways and onset potentials with considerably larger errors. These results indicate that accurate methods to assess solvent-adsorbate interactions contribute to improve computational electrocatalysis models. © 2020 Elsevier B.V.