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1.
J Am Chem Soc ; 132(6): 2064-8, 2010 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-20102192

RESUMO

We report here on the preparation and characterization of a fullerenium salt in the solid state, where the fullerene is in the 2+ oxidized state. To succeed in this long-standing challenge, we exploit the oxidizing power of one of the strongest Lewis acids, AsF(5). The weak nucleophilic character of its conjugate base is essential in stabilizing the fullerene dication in a crystal lattice. High-resolution structural analysis of this compound, with the formula C(60)(AsF(6))(2), indicates that the highly reactive C(60)(2+) units are arranged according to a novel 1D "zigzag" polymer structure. The molecules are connected by an alternating sequence of four-membered carbon rings ([2 + 2] cycloaddition) and single C-C bonds. The long awaited high-T(c) superconductivity and magnetism, expected in a hole-doped C(60) compound, are replaced instead by a semiconducting behavior, quite probably originating from the reduced crystal and molecular symmetry upon polymerization. The small value of the energy gap (approximately 70 meV) suggests, nevertheless, the proximity of a metallic phase.

2.
Plant Physiol Biochem ; 43(1): 45-54, 2005 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-15763665

RESUMO

In this work, we first investigated if the bread wheat (Triticum aestivum L.) cv. Albimonte can be defined as "shoot cadmium excluder"--by comparing the cadmium (Cd) content in leaves and roots and by calculating the shoot-to-root Cd concentration ratio. Furthermore, we evaluated if the exposure to Cd excess could generate oxidative stress in leaves and roots of this cv., in terms of hydrogen peroxide (H(2)O(2)) accumulation, NAD(P)H oxidation rate, and variations in reduced glutathione (GSH) content and peroxidase (POD, EC 1.11.1.7) activity. Finally, we surveyed possible quali- quantitative differences in thiol-peptide compound pattern between roots and leaves, in order to verify whether phytochelatins (PCs) and related thiol-peptides could contribute in limiting the Cd-induced oxidative stress. Unambiguous characterisation of PCs and related forms present in the root samples was obtained by electrospray ionisation mass spectrometry (ESI-MS) and ESI-tandem MS (ESI-MS/MS). Our results indicate that in leaves the stress generated by the low accumulation of Cd (due to a moderate translocation in planta) seems to be counteracted by the antioxidant response and by the PC biosynthesis. On the contrary, in roots, in spite of the elevated presence of PCs and related thiol-peptide-compounds, the excess of Cd causes a decline in the antioxidant protection of the organ, with the consequent generation of considerable amounts of H(2)O(2), a direct agent of oxidative stress.


Assuntos
Cádmio/toxicidade , Estresse Oxidativo/fisiologia , Folhas de Planta/metabolismo , Raízes de Plantas/metabolismo , Triticum/metabolismo , Ativação Enzimática/efeitos dos fármacos , Ativação Enzimática/fisiologia , Glutationa/metabolismo , Peróxido de Hidrogênio/metabolismo , Espectrometria de Massas , Metaloproteínas/metabolismo , NADP/metabolismo , Peroxidase/metabolismo , Fitoquelatinas , Folhas de Planta/efeitos dos fármacos , Raízes de Plantas/efeitos dos fármacos , Triticum/efeitos dos fármacos
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