Spin probe structure

Dendrimers have precise compositional and constitutional aspects, but they can exhibit many possible conformations. Thus, they lack long-range order in the condensed phase, which makes it inappropriate to characterize the molecular-level structure of dendrimers by X-ray diffraction analysis. However, there have been many studies performed using indirect spectroscopic methods to characterize dendrimer structures, such as studies using photophysical and photochemical probes by UV-Vis and fluorescence spectroscopy, as well as studies using spin probes by EPR spectroscopy. 

The exact value of g depends on the magnitude of local magnetic fields induced in the atom by the applied external field, H. Nitroxide spin probes possess an unpaired electron which is largely localized on the 2px orbital of the N atom (16), as is shown in the molecular structure of TEMPAMINE" " below ... 

Less frequently used at present is electron spin resonance spectroscopy, which is based on the use of spin probes as model componnds or covalent spin labeling of drugs. Microviscosity and micropolarity of the molecnlar environment of the probe can be derived from electron spin resonance spectra. Moreover, the spectra allow us to differentiate isotropic and anisotropic movements, which result from the incorporation of the probe into liposomal structures. Quantitative distribution of the spin probes between the internal lipid layer, the snrfactant, and the external water phase is to be determined noninvasively. On the basis of the chemical degradation of drugs released from the lipid compartment, agents with reductive features (e.g., ascorbic acid) allow us to measure the exchange rate of the drugs between lipophilic compartments and the water phase [27,28]. 

Carper, W. R., Pflug, J. L., and Wilkes, J. S., Dual spin probe NMR relaxation studies of ionic structure in l-ethyl-3-methylimidazolium chloride-AlClg molten-salts, Inorg. Chim. Acta, 202,89,1992. 

The 2,2,6,6-tetramethylpiperidinoxyl radical (TEMPO) was first prepared in 1960 by Lebedev and Kazarnovskii by oxidation of its piperidine precursor.18 The steric hindrance of the NO bond in TEMPO makes it a highly stable radical species, resistant to air and moisture. Paramagnetic TEMPO radicals can be employed as powerful spin probes for elucidating the structure and dynamics of both synthetic and biopolymers (e.g., proteins and DNA) by ESR spectroscopy.19 Unlike solid-phase 1H-NMR where magic angle spinning is required in order to reduce the anisotropic effects in the solid-phase environment, solid-phase ESR spectroscopy can be conducted without specialized equipment. Thus, we conducted comparative ESR studies of various polymers with persistent radical labels, and we also determined rotational correlation times as a function of... 

Besides using the EPR to evaluate the binding capacity of NOM for metal ions, it is also possible to use the latter as spin probe (Senesi, 1990a). Analyses of spectroscopic data comprise studying the adsorptive properties, surface interactions, and structural chemistry of soil, synthetic metal oxides, hydrous oxides, and clay minerals (McBride et al., 1984 Coyne and Banin, 1986 Senesi et al., 1991a Spagnuolo et al., 2004). 

Recent advances in the development of non-invasive, in situ spectroscopic scanned-probe and microscopy techniques have been applied successfully to study mineral particles in aqueous suspension (Hawthorne, 1988 Hochella and White, 1990). In situ spectroscopic methods often utilise molecular probes that have diagnostic properties sensitive to changes in short-range molecular environments. At the particle-solution interface, the molecular environment around a probe species is perturbed, and the diagnostic properties of the probe, which can be either optical or magnetic, then report back on surface molecular structure. Examples of in situ probe approaches that have been used fruitfully include electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spin-probe studies perturbed vibrational probe (Raman and Fourier-transform IR) studies and X-ray absorption (Hawthorne, 1988 Hochella and White, 1990 Charletand Manceau, 1993 Johnston et al., 1993). 

Okamoto, A., et ah (2004). Nitroxide-labeled guanine as an ESR spin probe for structural study ofDNA. Bioorg. Med. Chem. 14, 3415—3418. 

Electron spin resonance (ESR) studies of radical probe species also suggest complexity. Evans et al. [250] study the temperature dependence of IL viscosity and the diffusion of probe molecules in a series of dissimilar IL solvents. The results indicate that, at least over the temperature range studied, the activation energy for viscous flow of the liquid correlates well with the activation energies for both translational and rotational diffusion, indicative of Stoke-Einstein and Debye-Stokes-Einstein diffusion, respectively. Where exceptions to these trends are noted, they appear to be associated with structural inhomogeneity in the solvent. However, Strehmel and co-workers [251] take a different approach, and use ESR to study the behavior of spin probes in a homologous series of ILs. In these studies, comparisons of viscosity and probe dynamics across different (but structurally similar) ILs do not lead to a Stokes-Einstein correlation between viscosity and solute diffusion. Since the capacities for specific interactions are... 

According to the experimental data on rate constants of spin exchange at encounters between heme groups and nitroxides presented in Table 4.2., the accessibility of the heme group of cytochrome c to the encounters with neutral spin-probes IV is -31-33 times lower than that observed for free hemin. At present, it is difficult to separate the effect of heme group immersion into the protein globular structure from that of association in the relatively concentrated solutions (2-10mM) utilized in these studies. 

Fig. 7. Molecular structure of the spin probe 4-(A, A -dimethyl-A -hexadecyl)-ammonium-2,2,6,6-tetramethyl piperidinyloxy iodide (CAT16) and the surfactant cetyltrimethylammonium chloride (CTAC).

The two algorithms already developed and used to reproduce ESR line-shapes of paramagnetic species in free diffusion are applied in this subsection to the case of spin probes dissolved in liquid crystalline mesophases. The main point of diffoence with the previously examined cases is due to the introduction of an orienting potential v ose nature is directly reflected in the structure of the Fokker-Planck opoator, whidi in the difiusional assumption is given by Eq. (2.6). The explicit form of the potential we use in this... 

Metal- and proton-exchanged zeolites have been recently attracted much attention because of their selective catalytic activity to efficiently reduce nitrogen monoxide (NO) by hydrocarbon in an 02-rich atmosphere [1]. The formation of nitrogen dioxide (NO2) from NO and O2 has been suggested as an important step in the selective reduction [2, 3] NO2 is one of rare stable paramagnetic gaseous molecules and has been subjected to electron spin resonance (ESR) studies [4-7]. The ESR parameters and their relation/to the electronic structure have been well established [4] and NO2 can be used as a "spin probe" for the study of molecular dynamics at the gas-solid interface by ESR. 

Spin Probes and Spin Traps with a Spiroindolinic Structure... 

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