RESUMO
The immobilization and properties of the nitric oxide donor trans-[Ru(NO)Cl(cyclam)](PF(6))(2), RuNO, entrapped in a silica matrix by the sol-gel process is reported herein. The entrapped nitrosyl complex was characterized by spectroscopic (UV-vis, infrared (IR), X-ray photoelectron, and (13)C and (29)Si MAS NMR) and electrochemical techniques. The entrapped species exhibit one characteristic absorption band in the UV-vis region of the electronic spectrum at 354 nm and one IR nu(NO) stretching band at 1865 cm(-1), as does the RuNO species in aqueous solution. Our results show that trans-[Ru(NO)Cl(cyclam)](PF(6))(2) can be entrapped in a SiO(2) matrix with preservation of the molecular structure. However, in a SiO(2)/SiNH(2) matrix, the complex undergoes a nucleophilic attack by the amine group at the nitrosonium. Irradiation of the complex, entrapped in the SiO(2) matrix, with light of 334 nm, resulted in NO release. The material was regenerated to its initial nitrosyl form by reaction with nitric oxide.
Assuntos
Géis/química , Espectroscopia de Ressonância Magnética/métodos , Doadores de Óxido Nítrico/farmacologia , Óxido Nítrico/química , Compostos Organometálicos/química , Dióxido de Silício/química , Espectrofotometria Infravermelho/métodos , Aminas/química , Tetracloreto de Carbono/química , Desenho de Fármacos , Eletroquímica/métodos , Luz , Microscopia Eletrônica de Varredura , Doadores de Óxido Nítrico/química , Nitrogênio/química , Rutênio/química , Raios XRESUMO
Myo-inositol-1,2,3,4,5,6-hexakisphosphate, also known as phytate, is a natural metal chelate present in cereals, an important feedstock worldwide. This article reports the characterization of three metal storage model complexes: the homometallic Mn(II) myo-inositol-1,2,3,4,5,6-hexakisphosphate (IP6), the heterometallic Zn(II), Mn(II) analogue Na4MnZn4(C6H6O24P6) x (NO3)2 x 8H2O (MnZn4IP6) and the homometallic Zn(II) metal complex Na3Zn5(C6H6O24P6)OH x 9H2O (Zn5IP6). The techniques of high-resolution 23Na, 13C and 31P NMR, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) were applied in this study. The complexation of Zn(II) and Mn(II) by phosphate groups of IP6 is demonstrated by NMR and XPS results. 13C NMR results show a conformation for IP6 consisting of five equatorial phosphate groups to one axial group showing only one chemical environment for Zn and two for Mn, when characterized by XPS and EPR, in both Mn complexes. These results support, for the first time, a probable supramacromolecular structure for phytate complexes of transition metals. Based on the similarity between the EPR spectra of wheat seeds and that of the MnZn4IP6 compound, the manganese storage centers in wheat grains can be assigned to similar heterometallic phytate complexes.
