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      DOSY Experiments to Monitor Block Copolymer Polymerization

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          Abstract

          Block copolymers are a class of polymeric materials made by the covalent bonding of at least two macromolecular chains each with a different chemical nature. The performance of these materials is highly dependent on the physical and chemical properties of the constituting blocks, especially with regard to their chemical composition and molecular weight distribution. Usually, the block copolymer molecular weight is determined using Size-Exclusion Chromatography (SEC). In addition to traditional techniques, Diffusion Order SpectroscopY (DOSY) was introduced in the early 90s to obtain polymer composition and molecular weight information. In the present work, we have successfully used DOSY as a method to monitor block co-polymer polymerization as well as to account for the SEC results of a typical analysis.

          Translated abstract

          Los copolímeros en bloque son un grupo de polímeros constituidos por al menos dos cadenas poliméricas de diferente naturaleza química unidas por un enlace covalente. El desempeño de estos materiales está ligado a las propiedades físicas y químicas de cada uno de sus bloques, especialmente a su composición química y distribución de peso molecular. Usualmente, el peso molecular de estos materiales es determinado por Cromatografía de exclusión (CE). Adicionalmente a las técnicas tradicionales, la espectroscopia de difusión ordenada (DOSY) se introdujo a principios de los 90s en el análisis de polímeros para obtener información de la composición y peso molecular. En el presente trabajo se ha utilizado con éxito el método DOSY para monitorear la polimerización de un copolímero en bloques y explicar los resultados de CE en un análisis de rutina.

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          Density functional self-consistent quantum mechanics/molecular mechanics theory for linear and nonlinear molecular properties: Applications to solvated water and formaldehyde.

          A combined quantum mechanics/molecular mechanics (QM/MM) method is described, where the polarization between the solvent and solute is accounted for using a self-consistent scheme linear in the solvent polarization. The QM/MM method is implemented for calculation of energies and molecular response properties including the calculation of linear and quadratic response functions using the density-functional theory (DFT) and the Hartree-Fock (HF) theory. Sample calculations presented for ground-state energies, first-order ground-state properties, excitation energies, first-order excited state properties, polarizabilities, first-hyperpolarizabilities, and two-photon absorptions strengths of formaldehyde suggests that DFT may in some cases be a sufficiently reliable alternative to high-level theory, such as coupled-cluster (CC) theory, in modeling solvent shifts, whereas results obtained with the HF wave function deviate significantly from the CC results. Calculations carried out on water gives results that also are comparable with CC calculations in accuracy for ground-state and first-order properties. However, to obtain such accuracy an exchange-correlation functional capable of describing the diffuse Rydberg states must be chosen.
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            Generating long-lasting 1H and 13C hyperpolarization in small molecules with parahydrogen-induced polarization.

            Recently, Levitt and co-workers demonstrated that conserving the population of long-lasting nuclear singlet states in weak magnetic fields can lead to a preservation of nuclear spin information over times substantially longer than governed by the (high-field) spin-lattice relaxation time T1. Potential benefits of the prolonged spin information for magnetic resonance imaging and spectroscopy were pointed out, particularly when combined with the parahydrogen induced polarization (PHIP) methodology. In this contribution, we demonstrate that an increase of the effective relaxation time by a factor up to three is achieved experimentally, when molecules hyperpolarized by PHIP are kept in a weak magnetic field instead of the strong field of a typical NMR magnet. This increased lifetime of spin information makes the known PHIP phenomena more compatible with the time scales of biological processes and, thus, more attractive for future investigations.
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              Resonating valence bond wave function with molecular orbitals: Application to first-row molecules

              We introduce a method for accurate quantum chemical calculations based on a simple variational wave function, defined by a single geminal that couples all the electrons into singlet pairs, combined with a real space correlation factor. The method uses a constrained variational optimization, based on an expansion of the geminal in terms of molecular orbitals. It is shown that the most relevant non-dynamical correlations are correctly reproduced once an appropriate number \(n\) of molecular orbitals is considered. The value of \(n\) is determined by requiring that, in the atomization limit, the atoms are described by Hartree-Fock Slater determinants with Jastrow correlations. The energetics, as well as other physical and chemical properties, are then given by an efficient variational approach based on standard quantum Monte Carlo techniques. We test this method on a set of homonuclear (Be2, B2, C2, N2, O2, and F2) and heteronuclear (LiF, and CN) dimers for which strong non-dynamical correlations and/or weak van der Waals interactions are present.
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                Author and article information

                Journal
                jmcs
                Journal of the Mexican Chemical Society
                J. Mex. Chem. Soc
                Sociedad Química de México A.C. (México, DF, Mexico )
                1870-249X
                June 2011
                : 55
                : 2
                : 101-104
                Affiliations
                [01] Acolman de Nezahualcoyotl Estado de México orgnameGrupo Comex orgdiv1Centro de Investigación en Polímeros México
                [02] México D.F. orgnameUniversidad Nacional Autónoma de México orgdiv1Facultad de Química orgdiv2Unidad de Servicios y Apoyo a la Investigación México esturau_nuria@ 123456comunidad.unam.mx
                Article
                S1870-249X2011000200007 S1870-249X(11)05500200007
                61137f41-e601-4a53-a9bd-92f7fe5d38ea

                This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.

                History
                : 07 October 2010
                : 11 February 2011
                Page count
                Figures: 0, Tables: 0, Equations: 0, References: 25, Pages: 4
                Product

                SciELO Mexico

                Categories
                Articles

                Gradientes de campo magnético pulsados RMN,Copolímero en bloques,Peso molecular,Diffusion Ordered NMR Spectroscopy,Pulsed-field-gradient NMR,Block copolymer,Molecular weight,Espectroscopia de Difusión Ordenada por RMN

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