Characterisation of crosslinked elastomeric materials by 1H NMR relaxation time distributions.

One of the most critical structural parameters in elastomeric materials is the density of cross-linking between the polymeric chains. This chemical feature greatly affects chain motions and is determinant in controlling mechanical properties of the final product. NMR techniques are widely and efficiently applied to investigation of such materials. In this study we have measured both transverse and longitudinal 1H relaxation times of a series of polybutadiene rubber samples with increasing crosslink density induced by chemical treatment. This approach allowed the observation of T(1) and T(2) decrease with the increase of crosslink density in the samples examined. The data obtained have been analyzed and compared to theoretical models.     

1H-NMR relaxation times and water compartmentalization in experimental tumor models

The present studies were conducted with RIF-1, M5076 and Panc02 subcutaneous tumor models to assess the relationship between tissue-free water compartmentalization and observed tissue T1 and T2 changes at 10 MHz. Observed T1 was shown to correlate directly with total extracellular water and interstitial water volumes. T1 and T2 were also inversely related to intracellular water volumes. T1 and T2 decreases after dexamethasone treatment were, however, most closely correlated with changes in tumor extracellular water and not changes in cell or total water volumes. Studies to assess Gd-DTPA-dimeg dose dependent T1 and T2 modification in model serum protein solutions indicated that although the Gd concentration that reduced T2 by 50% was about 2.5 fold greater than that required to reduce T1 equally, the of the concentration dependent T1 and T2 modifications were similar. In studies with tumor models, the injected dose of Gd-DTPA-dimeg that reduced T1 by 50% was inversely correlated with tumor extracellular water volumes. The slopes for dose dependent T1 modification in all tumors were similar and similar to that observed for model protein solutions. Gd-DTPA-dimeg had a different effect on observed T2 values for the 3 tumor models. Exponential slopes were about twice that observed for T2 modification of serum protein solutions, and Gd-DTPA-dimeg doses that reduced observed tumor T2 ranged from 9 to 50 times that necessary to similarly reduce T1. The results from these studies indicate that the observed T1, for these tumors, was dominated by relaxation of water protons in interstitial water but that the observed T2 was most strongly influenced by proton relaxation in water compartments that were unavailable to the Gd labeled probe.     

From porous media to trabecular bone relaxation analysis: spatial variation of marrow 1H relaxation time distributions detected in vitro by quasi-continuous distribution analysis.

Quasi-continuous distributions of T(1) and T(2) of 1H nuclei were analyzed in vitro at 20MHz on some twenty fresh bone samples of pig femur. Large numbers of data points allowed a detailed investigation. Relaxation data were inverted by UPEN (Uniform PENalty inversion). In all samples the widths of the distributions, covering more than two decades, are not even close to being compatible with single exponential components. Moreover, the T(1) and T(2) distributions show enough character to distinguish the samples. We observe a spatial variation of these characteristics and in particular a second peak centered at 500-600 ms appearing in some proximal femur samples. The quasi-continuous distribution allows one to correlate the water content of the sample with parts of the distributions in specific time ranges. The signal fraction with T(1) values longer than a cutoff time of about 170 ms is in very good agreement with the water content of the samples and is significantly larger in the group of samples cored from proximal femur. Also T(2) distributions differentiate the samples, and the signal fraction with T(2) shorter than about 30 ms is significantly larger in the group of distal femur samples.     

The dependence on magnetic field strength of correlated internal gradient relaxation time distributions in heterogeneous materials

Magnetic susceptibility differences in porous media produce local gradients within the pore space. At high magnetic fields, these inhomogeneities have the potential to greatly affect nuclear magnetic resonance measurements. We undertake a study using a new NMR technique to measure the internal gradients present in highly heterogeneous samples over a wide range of magnetic field strengths. Our results show that even at ultra-high fields there can exist signal at internal gradient strengths sufficiently small that techniques for suppressing unwanted side effects have the possibility to be used. Our findings encourage the use of these high and ultra-high field strengths for a broader range of samples. Our results also give experimental evidence to support the theory of internal gradient scaling as a function of field strength within pores.     

The measurement of extracellular water volumes in tissues by gadolinium modification of 1H-NMR spin lattice (T1) relaxation

The present studies were conducted in RIF-1, M5076 and Panc02 murine tumor models to compare extracellular water measurements made by 51Cr-EDTA dilution techniques and a new method which exploits the concentration dependent modification of 1H-NMR proton relaxation by Gadolinium-DTPA-dimethyl glucamine (Gd-DTPA-dimeg) in plasma and tissues. The time dependent changes in T1 modification in tissue and plasma were determined at various intervals after i.v. injection of 0.1 ml of 100 mM Gd-DTPA-dimeg and Gd concentrations determined from standard curves of Gd concentration dependent T1 modification of mouse plasma. Comparison of tissue and plasma Gd concentrations permitted the calculation of Gd-DTPA-dimeg distribution volumes. In unperturbed RIF-1, M5076 and Panc02 tumors, Gd-DTPA-dimeg distribution volumes determined by the T1 modification technique were similar to extracellular water spaces determined by 51Cr-EDTA dilution assays. In mouse liver, the 51Cr-EDTA assay resulted in artifactually high extracellular water space estimates due to internalization of the probe; Gd-DTPA-dimeg distribution volumes determined in liver with both the 153Gd-DTPA-dimeg and by the T1 modification method were approximately 150 ul/gram. The Gd-DTPA-dimeg T1 modification method also provided good approximations of changes in extracellular water volumes in RIF-1 tumors after dexamethasone and cyclophosphamide treatments. These results indicate that Gd-DTPA-dimeg modification of proton relaxation may be extremely useful for monitoring changes in tumor water dynamics during cancer therapy.     

1H-NMR relaxation times and water content of red blood cells from chronic alcoholic patients during withdrawal

Red blood cell proton nmr, T1 and T2 times, and water content were measured for normal control subjects and thirteen patients with chronic alcoholism during the withdrawal phase. T1 and T2 were significantly increased without significant alteration in cell water content. The relaxation times were more markedly affected in those with symptoms of delirium tremens. These findings suggest that the intracellular free:bound water states rather than water content is the more likely explanation for these changes. The results are discussed in relation to similar findings obtained from in vivo studies in man and in vitro studies in animals.     

On the probability distributions of relaxation times in glasses

The scale of relaxation times in glasses has led to generalizations of the Drude model of the dielectric function in terms of an integral, containing a Drude kernel and a probability distribution. This integral equation is solved by a Mellin or a Stieltjes transform. Beyond known results, we obtain the probability distribution of the Havriliak-Negami dielectric function. Even more general classes of dielectric models can be dealt with, using Mellin's transform. They may serve as checks for numerical procedures applied to the underlying ill-posed problem, if experimental data for the dielectric function are used. Received: 2 February 1998 / Accepted: 17 March 1998     

Kinetic of the relaxation process of carrier distributions in semiconductors

The process of relaxation of a carrier population created by a light pulse in the conduction band of a direct gap polar semiconductor is studied theoretically using a phenomenological model recently proposed to account for several characteristics in the steady state luminescence spectrum of highly excited GaAs. The model incorporates the three most important carrier collision mechanisms: recombination, electron-optical phonon and electron-electron and it is nonlinear due to the last one. We have obtained numerical results for both low and high density of excitation regimes that compare qualitatively well with experimental and theoretical results reported in the literature.     

Ultrafast relaxation of optically excited nonequilibrium electron-hole distributions in germanium

New measurements of the nonlinear, nonequilibrium optical (1.06μm) properties of the germanium solid-state plasma are presented. Single pulse transmission has been measured as a function of incident pulse energy at sample temperatures of 105 K and 297 K. In addition the relative transmission of a probe pulse as a function of time delay after an excitation pulse has been measured for three different excitation pulse energies and two temperatures. A model which explains the observed behavior of germanium under intense radiation is briefly, qualitatively described, and theorectical curves are plotted with the experimental data.     

Perturbed angular distributions in the presence of isotropic paramagnetic relaxation

The effect of paramagnetic relaxation on perturbed angular distributions is treated for nuclei interacting with their electronic shells via isotropic hyperfine interaction. The conditions are given under which Blume's analytical stochastic-model result for the nuclear perturbation factorsG _k (t) can be derived quantum mechanically. Systems with arbitrary nuclear spin, but electronic spinS=1/2 may be calculated without resorting to the assumption necessary forS>1/2. Explicit closed expressions forG _k (t) can be found for this particular case.     

Anisotropy of the relaxation time in PbTe

The magnetoresistivity of monocrystalline specimens of n- and p-type PbTe is investigated. A small anisotropy of the relaxation time is observed, which diminishes, as does the effective mass anisotropy, with the rise in temperature and concentration.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 24–28, May, 1976.In conclusion, we are grateful to Prof. K. D. Tovstyuk and Dr. P. M. Starik for providing the topic and discussing the results.     

A generalized formula to determine the relaxation time distribution in dielectrics

The distribution of relaxation times is derived for dielectrics with constants featuring general functions in the - plane. A simple algorithm to determine the distribution parameters is also suggested. The algebraic method adopted enables translation of the algorithm into software to facilitate an efficient processing of data. The new distribution developed here could have an effective use in studies of dispersion in dielectrics and interfaces.     

Direct conversion of EPR dipolar time evolution data to distance distributions

Shallow electron spin echo envelope modulations due to dipole-dipole couplings between electron spins provide information on the radial distribution function of the spins in disordered systems while angular correlations between spin pairs are negligible. Under these conditions and in the absence of orientational selection, the dipolar time evolution data can be quantitatively simulated for arbitrary radial distribution functions by shell factorization, i.e., by performing the orientational average separately for thin spherical shells and multiplying the signals of all the shells. For distances below 5 nm, a linear superposition of the signals of the shells is sufficient. The dipolar time evolution data can be separated into this linear contribution and a nonlinear background. The linear contribution can then be converted directly to a radial distribution function. For a series of shape-persistent and flexible biradicals with end-to-end distances between 2 and 5 nm, shell factorization and direct conversion of the data are in good agreement with each other and with force-field computations of the end-to-end distances. The neglect of orientation selection does not cause significant distortions of the determined distance distributions.     

In Vitro Study of Ketoprofen and Indapamide Used in Multidrug Therapy: 1H-NMR Analysis

ABSTRACT

Interaction of ketoprofen (KP, a nonsteroidal anti-inflammatory drug) and indapamide (IDP, a thiazide-related diuretic) with human serum albumin (HSA) in low-affinity binding sites (LAS) and competition between these medicines used in multidrug therapy have been studied by proton nuclear magnetic resonance (¹H-NMR) spectroscopy.

The analysis of chemical shifts, Δσ (ppm), of drug proton resonances and the values of the association constant, K_a [M^?1], were used to estimate the effect of IDP and KP on the KP–HSA and IDP–HSA complexes, respectively. The results showed the changes in the affinity of human serum albumin toward the drug with different mechanisms of action (KP and IDP) and the competition in the binding to HSA.     

Fluctuations of the relaxation time in one-dimensional systems

The direct interaction of electrons with impurity field is represented as interelectronic interaction of a special kind which is called “dissipative”. This type of interaction is responsible for relaxation process and generally leads to fluctuations of the relaxation time. The probability distribution function for the mean free time of electrons is found in the white-noise approximation for a one-dimensional conductor. It is shown that the dielectric response function can be obtained in this case by averaging relevant expression over the fluctuations of the relaxation time.     

In vivo 1H-NMR procedure to determine several rat cerebral metabolite levels simultaneously, undisturbed by water and lipid signals

Methods developed for in vivo 1H-NMR spectroscopy are evaluated and applied using conscious rats. Good quality 1H-spectra of the brain are obtained using a surface coil and a spin echo pulse sequence with the binomial 1-1 and 2-2 water suppression pulses. However, comparing spectra from various rats with each other the water and lipid signals, which cause spectral overlap problems, may differ while the other spectral peaks agree well. Spatially one- and two-dimensional 1H spectroscopic imaging of the rat brain shows that the former signals stem from distinct spatial regions localized close to the rf coil. From a spectroscopic image, a spectrum over a limited spatial region is constructed in which the water signals are strongly reduced, the lipid signals are eliminated and lactic acid can be observed clearly simultaneously with other metabolites.     

On the Strategy of NMR Spectral Analysis. The 1H-NMR Spectrum of Amphetamine

The successive steps of the computer analysis of a NMR spectrum are examined. Better results can be obtained by direct simulation of tentative model spectra. As an example the ¹H-NMR spectrum of amphetamine is analysed.