1. Atmospheric lifetimes of long-lived halogenated species
A R Ravishankara, S Solomon, A A Turnipseed, R F Warren Science. 1993 Jan 8;259(5092):194-9. doi: 10.1126/science.259.5092.194.
The atmospheric lifetimes of the fluorinated gases CF(4), C(2)F(6), c-C(4)F(8), (CF(3))(2)c-C(4)F(6), C(5)F(12), C(6)F(14), C(2)F(5)Cl, C(2)F(4)C(12), CF(3)Cl, and SF(6) are of concern because of the effects that these long-lived compounds acting as greenhouse gases can have on global climate. The possible atmospheric loss processes of these gases were assessed by determining the rate coefficients for the reactions of these gases with O((1)D), H, and OH and the absorption cross sections at 121.6 nanometers in the laboratory and using these data as input to a two-dimensional atmospheric model. The lifetimes of all the studied perfluoro compounds are >2000 years, and those of CF(3)Cl, CF(3)CF(2)Cl, and CF(2)ClCF(2)Cl are >300 years. If released into the atmosphere, these molecules will accumulate and their effects will persist for centuries or millennia.
2. Influence of the geometry around the manganese ion on the peroxidase and catalase activities of Mn(III)-Schiff base complexes
M Ángeles Vázquez-Fernández, Manuel R Bermejo, M Isabel Fernández-García, Gustavo González-Riopedre, M Jesús Rodríguez-Doutón, Marcelino Maneiro J Inorg Biochem. 2011 Dec;105(12):1538-47. doi: 10.1016/j.jinorgbio.2011.09.002. Epub 2011 Sep 10.
The peroxidase and catalase activities of eighteen manganese-Schiff base complexes have been studied. A correlation between the structure of the complexes and their catalytic activity is discussed on the basis of the variety of systems studied. Complexes 1-18 have the general formulae [MnL(n)(D)(2)](X)(H(2)O/CH(3)OH)(m), where L(n)=L(1)-L(13); D=H(2)O, CH(3)OH or Cl; m=0-2.5 and X=NO(3)(-), Cl(-), ClO(4)(-), CH(3)COO(-), C(2)H(5)COO(-) or C(5)H(11)COO(-). The dianionic tetradentate Schiff base ligands H(2)L(n) are the result of the condensation of different substituted (OMe-, OEt-, Br-, Cl-) hydroxybenzaldehyde with diverse diamines (1,2-diaminoethane for H(2)L(1)-H(2)L(2); 1,2-diamino-2-methylethane for H(2)L(3)-H(2)L(4); 1,2-diamino-2,2-dimethylethane for H(2)L(5); 1,2-diphenylenediamine for H(2)L(6)-H(2)L(7); 1,3-diaminopropane for H(2)L(8)-H(2)L(11); 1,3-diamino-2,2-dimethylpropane for H(2)L(12)-H(2)L(13)). The new Mn(III) complexes [MnL(1)(H(2)O)Cl](H(2)O)(2.5) (2), [MnL(2)(H(2)O)(2)](NO(3))(H(2)O) (4), [MnL(6)(H(2)O)(2)][MnL(6)(CH(3)OH)(H(2)O)](NO(3))(2)(CH(3)OH) (8), [MnL(6)(H(2)O)(OAc)](H(2)O) (9) and [MnL(7)(H(2)O)(2)](NO(3))(CH(3)OH)(2) (12) were isolated and characterised by elemental analysis, magnetic susceptibility and conductivity measurements, redox studies, ESI spectrometry and UV, IR, paramagnetic (1)H NMR, and EPR spectroscopies. X-ray crystallographic studies of these complexes and of the ligand H(2)L(6) are also reported. The crystal structures of the rest of the complexes have been previously published and herein we have only revised their study by those techniques still not reported (EPR and (1)H NMR for some of these compounds) and which help to establish their structures in solution. Complexes 1-12 behave as more efficient mimics of peroxidase or catalase in contrast with 13-18. The analysis between the catalytic activity and the structure of the compounds emphasises the significance of the existence of a vacant or a labile position in the coordination sphere of the catalyst.
