Sodium nitroprusside (SNP) is among the most widely studied nitric oxide donors, and its capability of producing NO seems to depend on its interaction with sulfhydryl-containing molecules present in vivo. The aim of this research has been the study of the mechanism of interaction between SNP and sulfhydryl-containing compounds, such as cysteine and glutathione, through detection by EPR, UV-vis, and IR spectroscopy of both the radical and nonradical species involved. An electron-transfer process can be invoked as the key step, which leads to the formation of the reduced SNP radical, the main detectable radical intermediate, and the corresponding S-nitrosothiol, the ending product of NO that can be considered the real storage and transporters of NO. When cysteine was used, a second radical species (A) is detectable: it can be accounted for by the interaction of a byproduct with unreacted cysteine.

The formation of the S-nitrosocysteine (CySNO) in aqueous solution starting from cysteine (CySH) and sodium nitrite is shown to strongly depend on the pH. Experiments conducted within the pH range 0.5-7.0 show that at pH below 3.5 the NO+ (or H2NO 2 +) is the main nitrosating species, while at higher pH (>3.5) the nitrosating species is most likely the N2O3. A kinetic study provided a general kinetic equation, V(CySNO) = k1[HNO2][CySH]eq [H+] + k2[HNO2]2. The first term of this equation is predominant at pH lower than 3.5, in agreement with the literature for the direct nitrosation of thiols with nitrous acid; the value for the third-order rate constant, k(1) = 7.9 x 10(2) L(2) mol(-2) min(-1), was calculated. For experiments at pH higher than 3.5, the second term becomes prevalent and the second-order rate constant k(2) = (3.3 +/- 0.1) x 10(3) L mol(-1) min(-1) was calculated. A competitive oxidation process leading to the direct formation of cystine (CySSCy) has been also found. Most likely also for this process two different mechanisms are involved, depending on the pH, and a general kinetic equation, V(CySSCy) = k3[CySH](eq)[HNO2][H+] + k3'[CySH]eq[HNO2], is proposed.

No abstract

We have studied a system composed of a hydrophobic aerosil (R812) dispersed in the liquid crystal 4-noctyl-4′-cyanobiphenyl (8CB) using the spin probe electron spin resonance (ESR) technique, and in particular, we have determined, for different aerosil concentrations, the temperature dependence of the orientational order parameter, 〈P 2 〉, and the rotational diffusion coefficient, D ⊥ , of the probe 5-doxyl stearic acid in the ordered and isotropic phases of the system. We have found that increasing the silica concentration up to 10 wt % does not significantly change the transition temperatures of the system. The probe order parameter is instead depressed, and we found that the β exponent of an empirical Haller-type equation, used to fit its temperature dependence, changes roughly linearly with the aerosil concentration. The concentration effect on the probe dynamics is relatively small in the isotropic phase, where the D ⊥ temperature dependence is well fitted for all of the systems with an Arrhenius-type equation. In the nematic phase, the dynamical behavior is more complex: we found that, while local probe motion is still rather fast even when the macroscopic behavior is gellike, the temperature dependence of D ⊥ is still of Arrhenius-type up to 3 wt % aerosil concentration but it becomes of Vogel-Fulcher-Tammann-type for the 10 wt % R812 system.

No abstract