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PROTONATION EQUILIBRIA OF L-DOPA AND 1,10 PHENONTHROLINE IN PROPYLENE GLYCOL-WATER MIXTURES

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      Abstract

      Protonation equilibria of L-Dopa and 1,10 phenonthroline have been studied in varying concentrations (0-60% v/v) of propylene glycol-water mixtures maintaining an ionic strength of 0.16 mol dm-3 at 303 K using pH metric method. The protonation constants have been calculated with the computer program MINIQUAD75 and the best fit models are arrived at based on statistical grounds employing crystallographic R factor, χ2 , skewness and kurtosis. Dopa has three dissociable protons and one amino group which associate with proton. It exists as LH4+ at low pH and gets deprotonated with the formation of LH3, LH2- and LH2- successively with increase in pH. Phen forms LH2(2+) at low pH and gets deprotonated with the formation of LH+ and L with increase in pH. Secondary formation functions confirm the existence of 3 and 2 protonation equilibria for dopa and phen, respectively. The linear increase of log values of protonation constants of Dopa with decreasing dielectric constant of PG-water mixtures indicates the dominance of electrostatic forces in the protonation-deprotonation equilibria. Phen exhibits non-linear trend indicating the dominance of non-electrostatic forces.

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      A subfraction of the yeast endoplasmic reticulum associates with the plasma membrane and has a high capacity to synthesize lipids.

      Large parts of the endoplasmic reticulum of the yeast, Saccharomyces cerevisiae, are located close to intracellular organelles, i.e. mitochondria and the plasma membrane, as shown by fluorescence and electron microscopy. Here we report the isolation and characterization of the subfraction of the endoplasmic reticulum that is closely associated with the plasma membrane. This plasma membrane associated membrane (PAM) is characterized by its high capacity to synthesize phosphatidylserine and phosphatidylinositol. As such, PAM is reminiscent of MAM, a mitochondria associated membrane fraction of the yeast [Gaigg, B., Simbeni, R., Hrastnik, C., Paltauf, F. & Daum, G. (1995) Biochim. Biophys. Acta 1234, 214-220], although the specific activity of phosphatidylserine synthase and phosphatidylinositol synthase in PAM exceeds several-fold the activity in MAM and also in the bulk endoplasmic reticulum. In addition, several enzymes involved in ergosterol biosynthesis, namely squalene synthase (Erg9p), squalene epoxidase (Erg1p) and steroldelta24-methyltransferase (Erg6p), are highly enriched in PAM. A possible role of PAM in the supply of lipids to the plasma membrane is discussed.
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        Photo-induced spin-state conversion in solvated transition metal complexes probed via time-resolved soft X-ray spectroscopy.

        Solution-phase photoinduced low-spin to high-spin conversion in the Fe(II) polypyridyl complex [Fe(tren(py)(3))](2+) (where tren(py)(3) is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following (1)A(1) --> (1)MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L(2)- and L(3)-edges were observed concomitant with formation of the transient high-spin (5)T(2) state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of approximately 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 A increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.
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          Analyst

           G Gran,  Wenli Liu (1952)
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            Author and article information

            Affiliations
            [1 ] Andhra University India
            Contributors
            Role: ND
            Role: ND
            Role: ND
            Role: ND
            Journal
            jcchems
            Journal of the Chilean Chemical Society
            J. Chil. Chem. Soc.
            Sociedad Chilena de Química (Concepción )
            0717-9707
            December 2011
            : 56
            : 4
            : 842-847
            S0717-97072011000400004 10.4067/S0717-97072011000400004

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

            Product
            Product Information: SciELO Chile
            Categories
            CHEMISTRY, MULTIDISCIPLINARY

            General chemistry

            1,10-Phenanthroline, L-Dopa, propylene glycol, Protonation equilibria

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