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      Determinação da constante de velocidade absoluta para a reação de abstração de hidrogênio fenólico pelo estado excitado triplete de xantona em acetonitrila e no líquido iônico hexafluorfosfato de 1-butil-3-metil-imidazólio [bmim.PF6] Translated title: Determination of absolute rate constant for the phenolic hydrogen abstraction reaction by the triplet excited state of xanthone in acetonitrile and in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim.PF6]

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          Translated abstract

          The triplet excited state of xanthone was generated and characterized by laser flash photolysis in acetonitrile (λmax=620 nm; t=1.8 ms) and in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim.PF6] (λmax=620 nm; t=3.0 ms). It reacts with phenols yielding the corresponding xanthone ketyl radical. Stern-Volmer plots for the reaction of triplet xanthone with phenols led to the determination of absolute rate constants for phenolic hydrogen abstraction in the order of ~10(9) Lmol-1s-1 in acetonitrile and ~10(8) Lmol-1s-1 in [bmim.PF6]. The lower diffusioncontrolled rate constant for [bmim.PF6] is responsible for the difference in the phenolic hydrogen abstraction rate constants in this solvent.

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          Ion Density Deviations in Semipermeable Ionic Microcapsules

          By implementing the nonlinear Poisson-Boltzmann theory in a cell model, we theoretically investigate the influence of polyelectrolye gel permeability on ion densities and pH deviations inside the cavities of ionic microcapsules. Our calculations show that variations in permeability of a charged capsule shell cause a redistribution of ion densities within the capsule, which ultimately affects the pH deviation and Donnan potential induced by the electric field of the shell. We find that semipermeable capsules can induce larger pH deviations inside their cavities that can permeable capsules. Furthermore, with increasing capsule charge, the influence of permeability on pH deviations progressively increases. Our theory, while providing a self-consistent method for modeling the influence of permeability on fundamental properties of ionic microgels, makes predictions of practical significance for the design of microcapsules loaded with fluorescent dyes, which can serve as biosensors for diagnostic purposes.
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            Ion Density Deviations in Polyelectrolyte Microcapsules: Influence on Biosensors

            Polyelectrolyte microcapsules loaded with fluorescent dyes have been proposed as biosensors to monitor local pH and ionic strength for diagnostic purposes. In the case of charged microcapsules, however, the local electric field can cause deviations of ion densities inside the cavities, potentially resulting in misdiagnosis of some diseases. Using nonlinear Poisson-Boltzmann theory, we systematically investigate these deviations induced by charged microcapsules. Our results show that the microcapsule charge density, as well as the capsule and salt concentrations, contribute to deviations of local ion concentrations and pH. Our findings are relevant for applications of polyelectrolyte microcapsules with encapsulated ion-sensitive dyes as biosensors.
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              Order and disorder in quaternary atomic laminates from first-principles calculations.

              We report on the phase stability of chemically ordered and disordered quaternary MAX phases - TiMAlC, TiM2AlC2, MTi2AlC2, and Ti2M2AlC3 where M = Zr, Hf (group IV), M = V, Nb, Ta (group V), and M = Cr, Mo, W (group VI). At 0 K, layered chemically ordered structures are predicted to be stable for M from groups V and VI. By taking into account the configurational entropy, an order-disorder temperature Tdisorder can be estimated. TiM2AlC2 (M = Cr, Mo, W) and Ti2M2AlC3 (M = Mo, W) are found with Tdisorder > 1773 K and are hence predicted to be ordered at the typical bulk synthesis temperature of 1773 K. Other ordered phases, even though metastable at elevated temperatures, may be synthesized by non-equilibrium methods such as thin film growth. Furthermore, phases predicted not to be stable in any form at 0 K can be stabilized at higher temperatures in a disordered form, being the case for group IV, for MTi2AlC2 (M = V, Cr, Mo), and for Ti2M2AlC3 (M = V, Ta). The stability of the layered ordered structures with M from group VI can primarily be explained by Ti breaking the energetically unfavorable stacking of M and C where M is surrounded by C in a face-centered cubic configuration, and by M having a larger electronegativity than Al resulting in a fewer electrons available for populating antibonding Al-Al orbitals. The results show that these chemically ordered quaternary MAX phases allow for new elemental combinations in MAX phases, which can be used to add new properties to this family of atomic laminates and in turn prospects for tuning these properties.
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                Author and article information

                Contributors
                Role: ND
                Role: ND
                Journal
                qn
                Química Nova
                Quím. Nova
                Sociedade Brasileira de Química (São Paulo )
                1678-7064
                2013
                : 36
                : 4
                : 528-532
                Affiliations
                [1 ] Universidade Federal da Bahia Brazil
                [2 ] Universidade Federal Rural do Rio de Janeiro Brazil
                Article
                S0100-40422013000400008
                10.1590/S0100-40422013000400008
                7e1f7522-dce0-4890-a178-6dfd5312c08c

                http://creativecommons.org/licenses/by/4.0/

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                SciELO Brazil

                Self URI (journal page): http://www.scielo.br/scielo.php?script=sci_serial&pid=0100-4042&lng=en
                Categories
                CHEMISTRY, MULTIDISCIPLINARY

                General chemistry
                xanthone,ionic liquid,triplet excited state
                General chemistry
                xanthone, ionic liquid, triplet excited state

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