Relaxation properties differences

For explaining the apparent contradictory results concerning the restricted dynamics in intercalated and exfoliated PLSNs, Lu and Nutt [2003] proposed a model with three different relaxation domains and three different relaxation rates. The relaxation properties differ depending on the extent to which the iayered silicates are exfoliated, the strength of interactions between silicate layers and polymer matrices, the grafting density, and the ceramic content. The authors concluded that a system with fully exfoliated silicate dispersion and strong interactions is expected to exhibit slow relaxation behavior (high Tg), whereas a system with intercalated silicates and weak interaction should display fast relaxation dynamics (low Tg). 

Data of Figs 8-10 give a simple pattern of yield stress being independent of the viscosity of monodisperse polymers, indicating that yield stress is determined only by the structure of a filler. However, it turned out that if we go over from mono- to poly-disperse polymers of one row, yield stress estimated by a flow curve, changes by tens of times [7]. This result is quite unexpected and can be explained only presumably by some qualitative considerations. Since in case of both mono- and polydisperse polymers yield stress is independent of viscosity, probably, the decisive role is played by more fine effects. Here, possibly, the same qualitative differences of relaxation properties of mono- and polydisperse polymers, which are known as regards their viscosity properties [1]. 

In this section, the characteristics of the spectra displayed by the different types of iron—sulfur centers are presented, with special emphasis on how they depend on the geometrical and electronic structure of the centers. The electronic structure is only briefly recalled here, however, and interested readers are referred to the excellent standard texts published on this topic (3, 4). Likewise, the relaxation properties of the centers are described, but the nature of the underlying spin-lattice relaxation processes is not analyzed in detail. However, a short outline of these processes is given in the Appendix. The aim of this introductory section is therefore mainly to describe the tools used in the practical applications presented in Sections III and IV. It ends in a discussion about some of the issues that may arise when EPR spectroscopy is used to identify iron-sulfur centers. 

With trinuclear clusters, we are now dealing with systems whose electronic structure depends on multiple intersite interactions that may differ from one iron pair to another. As a result, the separation between adjacent energy levels depends, not on the magnitude of these interactions, but on their difference. This may give rise to low-lying excited levels, which may have far-reaching effects on both the EPR spectrum and the relaxation properties. 

In many products, the spin-relaxation properties of the components can be different due to molecular sizes, local viscosity and interaction with other molecules. Macromolecules often exhibit rapid FID decay and short T2 relaxation time due to its large molecular weight and reduced rotational dynamics [18]. Mobile water protons, on the other hand, are often found to have long relaxation times due to their small molecular weight and rapid diffusion. As a result, relaxation properties, such as T2, have been used extensively to quantify water/moisture content, fat contents, etc. [20]. For example, oil content in seeds is determined via the spin-echo technique as described according to international standards [64]. 

NMR signals are highly sensitive, via a number of different mechanisms, to the physical and chemical properties of porous materials. Using the set of NMR-based measurement methods that we have developed, it is possible to non-invasively and non-destructively characterize both the microstructural properties of the materials and relaxation properties of fluids imbibed into these materials. 

Aime et al. took advantage of the different redox states of manganese and of the difference in the related relaxation properties to design a p02 responsive contrast agent. The adducts formed between Mn /Mnn tpps complexes and poly-P-cyclodex-trin have considerably different relaxivities depending on the redox state of the metal, itself determined by the partial oxygen pressure of the solution (tpps — 5,10,15,20-tetrakis-(p-sulfonato-phenyl porphinate) (243). 

The anisotropy of the overall tumbling will result in the dependence of spin-relaxation properties of a given 15N nucleus on the orientation of the NH-bond in the molecule. This orientational dependence is caused by differences in the apparent tumbling rates sensed by various internuclear vectors in an anisotropically tumbling molecule. Assume we have a molecule with the principal components of the overall rotational diffusion tensor Dx, Dy, and l)z (x, y, and z denote the principal axes of the diffusion tensor), and let Dx< Dy< Dz. 

Chemists pay much less attention to the NMR relaxation rates than to the coupling constants and chemical shifts. From the point of view of the NMR spectroscopist, however, the relaxation characteristics are far more basic, and may mean the difference between the observation or not of a signal. For the quadrupolar nucleides such as 14N the relaxation characteristics are dominated by the quadrupole relaxation. This is shown by the absence of any nuclear Overhauser effect for the 14N ammonium ion despite its high symmetry, which ensures that the quadrupole relaxation is minimized. Relaxation properties are governed by motional characteristics normally represented by a correlation time, or several translational, overall rotational and internal rotational, and thus are very different for solids, liquids and solutions. 

The analysis of these phenomena requires the use of more complicated models which take into account the fact that at the moment of excitation individual aromatic molecules in the ensemble under study may interact differently with their environment." 7l The existence of a distribution of fluorophores differing in such interactions leads to inhomogeneous broadening of the spectra. Upon excitation by light whose energy is insufficient to excite all the fluorophores in the ensemble, there occurs a selection of those species whose spectral properties differ from the average ones. These properties and their changes with time may characterize the relaxation process/1,24,33,98)... 

The stress relaxation properties of SA-modified wood in media of different pH have also been studied (Nakano etal., 1990a,b, 1991 Nakano, 1993a,b). It was found that an increase in pH led to an increase in stress relaxation properties due to side chain ionization, with maximum swelling of the wood occurring between pH 5-8. In addition, cross-linking within the wood was achieved by treatment with bivalent or trivalent metal ions. The rheological properties of maleic acid esterified wood also show that thermoplasticity is imparted to the wood by such modification (Norimoto etal, 1992). 

The aggregation of the nanomagnets has two different consequences on the proton relaxation properties on one hand, those related to the global structure of the cluster and to the magnetic field distribution around them and, on the other hand, those limited to the inner part of the aggregate (75). While the global effect dominantly affects i 2> the inner one influences R. ... 

Unlike the lanthanides, the actinides U, Np, Pu, and Am have a tendency to form linear actinyl dioxo cations with formula MeO and/or Me02. All these ions are paramagnetic except UO and they all have a non-spherical distribution of their unpaired electronic spins. Hence their electronic relaxation rates are expected to be very fast and their relaxivities, quite low. However, two ions, namely NpO and PuOl", stand out because of their unusual relaxation properties. This chapter will be essentially devoted to these ions that are both 5/. Some comments will be included later about UOi (5/°) and NpOi (5/ ). One should note here that there is some confusion in the literature about the nomenclature of the actinyl cations. The yl ending of plutonyl is often used indiscriminately for PuO and PuOl and the name neptunyl is applied to both NpO and NpOi. For instance, SciFinder Scholar" makes no difference between yl compounds in different oxidation states. Here, the names neptunyl and plutonyl designate two ions of the same 5f electronic structure but of different electric charge and... 

Buspirone has selective anxiolytic effects, and its pharmacologic characteristics are different from those of other drugs described in this chapter. Buspirone relieves anxiety without causing marked sedative, hypnotic, or euphoric effects. Unlike benzodiazepines, the drug has no anticonvulsant or muscle relaxant properties. Buspirone does not interact directly with GABAergic systems. It may exert its anxiolytic effects by acting as a partial agonist at brain 5-HTia receptors, but it also has affinity for brain dopamine D2 receptors. Buspirone-treated patients show no... 

The excellent resolution of the 0-tensor components at W band has been used to measure the relaxation properties of QA in the Zn-substituted bRC of R. sphaeroides.m The experiment showed, in contrast to the respective ubiquinone radical in organic solution, an anisotropic relaxation behavior in the pulse high field ESE experiments. From the analysis of the T2 experiments a motional anisotropy of Q% in the protein pocket was deduced with a preferred libration about the C-O symmetry axis. Recently, similar experiments were also performed on Qb- in ZnbRCs. Compared to QA different echo decay time constants were found. A model was proposed in which the relaxation is related to reorientational fluctuations around the quinones specific H-bonds to the protein.142... 

---