Low-frequency proton NMR relaxometry of a polymer dispersed liquid crystal above TNI.

Using proton NMR relaxometry in the kilohertz frequency range, we study dynamics of 5CB liquid crystal molecules dispersed in the form of spherical microdroplets in a PDLC material. The focus of the study is the spin-lattice relaxation in the rotating frame, T1rho(-1), measured above the nematic-isotropic transition TNI. We show that the relaxation rate T1rho(-1)--when induced by uniform molecular translational diffusion in a spherical cavity--depends on the strength of the rotating magnetic field as T1rho(-1) proportional to omega1(-alpha) where alpha varies between 0.7 and 1, depending on the thickness of the ordered surface layer. This relaxation mechanism governs mainly the transverse spin relaxation, whereas the measurements of the frequency and temperature dependence of T1rho(-1) indicate a strong effect of slowing-down of molecular translational diffusion in contact with the polymer surface and yield the average dwell-time of molecules at the surface of the order 10(-5) s.

Suppression of red cell diffusional water permeability by lipophilic solutes.

The inhibitory effect of a series of neutral lipophilic solutes (methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-amylalcohol, n-hexanol, diethylether, nitrobenzene, and pyridine) on the diffusional water permeability (Pd, tot) of bovine erythrocyte membrane at 25 degrees C was studied in comparison to that of p-chloromercuri benzoate (pCMB). Permeability data were obtained by measuring the transmembrane diffusional water exchange time tau(exch) using an 1H-T2 NMR technique. Maximal inhibition by approximately 50% of Pd, tot was produced by 2 mM pCMB which completely blocked the membrane water channels in 20 min, hence suggesting the channel-to-lipid diffusional water permeability ratio of about 1:1. Furthermore, the maximal inhibitory effect of pCMB in combination with the lipophilic solutes was lower than that of pCMB alone. As pCMB does not interfere with the lipid bilayer, and provided that it blocks the water channels in solute presence as well, this confirms that the solutes induce an increase in the lipid-mediated background water permeability contribution (Pd, lipid) by the formation of aqueous leaks in the membrane hydrophobic barrier. However, faster but less efficient in permeability inhibition than pCMB (either alone or combined with solutes) were the lipophilic solutes alone. Taken together, the results indicate that the lipophilic solutes suppress the membrane total permeability Pd, tot by two opposing effects: a reduction of its channel-mediated part (Pd, channel) to the extent exceeding that of a simultaneous Pd, lipid increase. The inhibitory potency of the solutes tested appears to be correlated with their solubility in the membrane medium.

Ethanol- and acetonitrile-induced inhibition of water diffusional permeability across bovine red blood cell membrane.

The effect of 0-3% (v/v) ethanol and acetonitrile on water diffusional permeability of bovine and chicken red blood cells (RBCs) was studied using a pulse 1H-T2 NMR technique. Transmembrane water diffusional exchange times, tau exch, of 9.2 +/- 0.46 ms and 18.3 +/- 1.0 ms were determined for bovine and chicken erythrocytes at 27.5 degrees C, respectively. Arrhenius activation energies Ea of water diffusion were 20.4 and 35.8 kJ mol-1. Ethanol, and acetonitrile being 2-fold more effective, markedly increased both tau exch and Ea in bovine RBC as compared to the well-known mercurial inhibitor of water channels, p-chloromercuribenzene sulfonate. Chicken RBCs that have no protein water channels, were found to be completely insensitive for either agent. It was suggested that ethanol and acetonitrile partitioning into the lipid phase of bovine RBC membrane affects the permeability of CHIP28 water channel but not the lipid confined water diffusion. The results suggest that the inhibition of transmembrane movement of water via CHIP28 channels might be involved in the anti-hemolytic action of anaesthetics such as ethanol.

Magnetic resonance imaging of retracted and nonretracted blood clots during fibrinolysis in vitro.

Magnetic resonance imaging (MRI) of retracted blood clots embedded in nonretracted clots was used to follow their lysis with urokinase in a plasma milieu in vitro. The two types of clots that were imaged in the same plane differed in signal intensity on T2-weighted spin echo MR images throughout the 20-hour observation period. It was thus possible to delineate the contours of both clot types and measure their relative sizes by digital image processing. Lysis of retracted clots proceeded significantly slower than lysis of nonretracted clots. Our in vitro results suggest that MRI might prove useful in detecting thrombus retraction in vivo and in predicting the outcome of thrombolytic therapy.

Water proton NMR relaxation mechanisms in lung tissue.

The NMR relaxation times T'2, T2, and T1 were measured in isolated rat lungs as functions of external magnetic field B0, temperature, and lung inflation. The observed linear dependence on B0 of the tissue-induced free induction decay rate (T'2)-1 provides independent confirmation of the air/water interface model of the lung. Furthermore, measurements of the Larmor frequency dependence of T1 are consistent with a spin-lattice relaxation rate of the form 1/T1 = A omega -1/2 + B as expected for the case in which the relaxation arises from water-biopolymer cross-relaxation, which should be proportional to the surface area of the lung. This prediction was verified by observations of an approximately linear dependence of 1/T1 on transpulmonary pressure and thus on the lung surface area.

Non-Brownian water self-diffusion in lung tissue.

Pulsed field gradient NMR measurements of rat lung tissue have shown that the apparent water self-diffusion coefficient is nearly an order of magnitude smaller than that of free water and moreover is not constant but varies as the inverse square root of the diffusion time. The mean square displacement of water molecules is similarly proportional to the square root of the diffusion time. Possible origins of this non-Brownian behavior are discussed.

Proton magnetic relaxation dispersion in human fluoromethaemoglobin solutions.

The solvent proton spin-lattice relaxation time of high spin Fe3+ (S=5/2) human A fluoromethaemoglobin aqueous solutions was measured at 14 Larmor frequencies in the range from 2.2 to 96 MHz. The observed paramagnetic relaxation rates are analysed in terms of the Solomon-Bloembergen theory, with the g-tensor value of 2 based on the consideration of the protein tertiary structure. From the H2O (pH 6) haemoprotein solution relaxation data, tau(c) =(9.3+/-0.3) X 10(-10) sec. If the total relaxation rates are corrected for the "outer-sphere" paramagnetic contribution, tau(c)=(6.5+/-0.4) X 10(-10) sec. The latter correction is obtained from the p.m.r. of the non-exchangeable aliphatic protons of C2H4(OD)2 added to the D2O-solution of fluoromethaemoglobin. Assuming that single proton transfer is taking place through the protein channel along the axis normal to the haem (g=2), the protein "binding" site is at a distance of 3.93 to 3.98 A from the haem Fe3+ ion.