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We demonstrate that ferroelectric layered perovskite Bi3.8Nd0.2Ti3O12 micro-platelets can be reoriented in the nematic liquid crystal by the linear coupling to an external electric field. The electric dipole moment of platelets is perpendicular to the plane of platelets and provides torque that rotates the platelets. The experiments were made in dispersions of ferroelectric platelets in a zero dielectric anisotropy nematic liquid crystal (LC), which excludes the reorientation of the dispersion via the dielectric coupling of a LC. Typical reorientation times for micrometre-size ferroelectric platelets are of the order of 100 ms for 0.5 V/μm applied electric field. The electric dipole moment in the absence of external field is very small and does not contribute to the force between the platelets. This could be either due to very narrow hysteresis loop of the ferroelectric material, or screening of dipolar electric field by ions in the LC. A stable and homogenous dispersion of ferroelectric nano-platelets could not be observed in any range of platelets' concentration. To create a ferroelectric LC the shape and thickness of the nano-platelets has to be controlled, and the electrostatic screening of dipolar field should be minimised. [ABSTRACT FROM AUTHOR]

The influence of controlled-pore glass (CPG) confinement on the phase behavior of octylcyanobiphenyl liquid crystal (LC) is studied by means of x-ray scattering and high precision calorimetry. For CPG samples with pore diameter 2R>24 nm, the smectic order parameter temperature dependence η(T) reveals apparent presmectic ordering far above the bulk smectic A–nematic (SmA-N) phase transition for both nontreated and silane-treated CPG matrices. The behavior of η(T) is qualitatively similar in all samples, well obeying the mean field approach (MFA) in which the surface wetting tendency plays the dominant role. In contrast, the critical fluctuations remain important in the specific heat data, which cannot be described within the MFA. We show experimentally that randomness and surface wetting become dominant over finite-size effects for 2R≤=10 nm, in agreement with theoretical analysis. In nontreated samples, the noncritical character of the static disorder and the interfacial LC-CPG coupling almost completely suppress the quasi-SmA-N and nematic-isotropic phase transitions at 2R∼15.1 and ∼7.5 nm, respectively. [ABSTRACT FROM AUTHOR]

1H NMR spin-lattice (T1) and spin-spin (T2) relaxation times have been measured for the residual CHCl3 component of deuterochloroform (99.8 atom% D) in neat solvent samples and in a series of isotropic solutions of the ionic surfactant n-octylammonium-n-octadecanoate and also in degassed/dried and aerated solvent systems at 298 K. Analysis of the proton relaxation times as composite values from various relaxation mechanisms suggests that the spin-lattice process is predominantly via spin-rotation while spin-spin relaxation principally involves 1H-Cl scalar coupling. Rotational correlation times from relaxation rates via the dipolar and spin-rotation mechanisms reveal similar fast picosecond molecular rotation of chloroform in the different samples. The presence of surfactant in the solution appreciably affects the 1H NMR spin-lattice relaxation time of CHCl3 and the chemical shift, which is concentration dependent owing to weak intermolecular interactions. Effects of sample condition and solvent degassing, drying, and aeration treatments on the NMR relaxation times and line shape properties of the residual CHCl3 isotopomers are also examined. [ABSTRACT FROM AUTHOR]

H NMR chemical shift, line width, indirect nuclear splitting value, peak area integration value, and spin-lattice and spin-spin relaxation times at 298 K are compared for low-concentration isotropic solutions of n-octylammonium n-octadecanoate prepared via different techniques and conditions using dried, distilled, and degassed deuterochloroform and the nontreated solvent containing tetramethylsilane. The nature of the variation of observed spectral parameters and relaxation/rotational behavior with chemical composition (presence of oxygen and other paramagnetic species, stabilizer, impurities, and degradation products) of the solvent, history of the solution, and sample containment are analyzed. Relaxation times are interpreted in terms of monomer structure and reorientation and internal rotation modes as a function of atomic position along the n-alkyl chains. Collectively, the relaxation behavior of the surfactant complies with the two-step model of fast picosecond internal rotations of different size segments containing methylene groups separated in timescale from slower large segment and overall molecular tumbling modes of the monomer. Fast motional phenomena do not appear to be appreciably influenced by the chemistry of the solvent in contrast to spectral parameters such as chemical shift and line width of the labile ammonium protons. A model is also presented to explain anomalous variation of the peak area integration value with chemical shift of the ammonium resonance peak. [ABSTRACT FROM AUTHOR]

Abstract: The passage of water through the aquaporin-1 (AQP1) transmembrane channel protein of the human erythrocyte is known to be inhibited by organic mercurials such as p-chloromercuribenzoate (pCMB), which react with the free SH-group of the critical cysteine (Cys189) located near the constriction of the AQP1 water-specific channel. Sodium nitroprusside (SNP), which is known as a nitric oxide (NO) donor in interactions with SH-containing molecules, is shown here to suppress the diffusional water permeability (P d) of the erythrocyte membrane, presumably as a result of reaction with the Cys189 of the human erythrocyte AQP1 water channels. Further, treatment of erythrocytes with HgCl2 is found to result in a cell volume decrease that can be related to activation of membrane K+-selective Gárdos channels and subsequent loss of intracellular K+ and cell shrinkage. The variations in P d and volume of the erythrocyte were deduced from induced variations in the measured proton (1H) nuclear magnetic resonance (NMR) transverse (T 2) relaxation functions of water exchanging between diamagnetic intracellular and paramagnetic extracellular compartments of the 20–25% hematocrit samples. The extracellular solvent contained 10 mM membrane-impermeable paramagnetic Mn2+ ions. The 1H-T 2 NMR technique allows determination of the time constant τ exch (for exchange of the erythrocyte intracellular water) that is inversely proportional to the permeability coefficient P d when the intracellular water volume is left unmodified, as in the case of SNP-treated erythrocytes. However, for HgCl2-treated erythrocytes, this technique showed simultaneous variation of both τ exch and the volume ratio V in/V out of intracellular and extracellular water in proportions suggesting that P d was left unmodified. The HgCl2 effect has been found to be partly reversible by the reducing activity of added mercaptoethanol. [Copyright &y& Elsevier]

Abstract: Many pharmaceutical tablets are based on hydrophilic polymers, which, after exposure to water, form a gel layer around the tablet that limits the dissolution and diffusion of the drug and provides a mechanism for controlled drug release. Our aim was to determine the thickness of the swollen gel layer of matrix tablets and to develop a method for calculating the polymer concentration profile across the gel layer. MR imaging has been used to investigate the in situ swelling behaviour of cellulose ether matrix tablets and NMR spectroscopy experiments were performed on homogeneous hydrogels with known polymer concentration. The MRI results show that the thickest gel layer was observed for hydroxyethylcellulose tablets, followed by definitely thinner but almost equal gel layer for hydroxypropylcellulose and hydroxypropylmethylcellulose of both molecular weights. The water proton NMR relaxation parameters were combined with the MRI data to obtain a quantitative description of the swelling process on the basis of the concentrations and mobilities of water and polymer as functions of time and distance. The different concentration profiles observed after the same swelling time are the consequence of the different polymer characteristics. The procedure developed here could be used as a general method for calculating polymer concentration profiles on other similar polymeric systems. [Copyright &y& Elsevier]

The aim of this work was to study the effect of the type of substituent of the cellulose ethers and the molecular mass on the state and dynamics of water in the respective hydrogels to specify the quantity of adsorbed water on the polymers or, more explicitly, to calculate the average number of water molecules bound to a polymer repeating unit (PRU).1H NMR relaxation experiments were performed on equilibrated systems of cellulose ether polymers (HEC, HPC, HPMC K4M, and HPMC K100M) with water. In particular, the water proton spinlattice ( T 1) and spin-spin ( T 2) relaxation times were measured in these systems at room temperature. The observed proton NMR T 1 and T 2 of water in hydrogels at different cellulose ether concentrations at room temperature were shown to decrease with increasing polymer concentration. The relaxation rate 1/ T 1 is sensitive to the type of polymer substituent but insensitive to the polymer molecular mass. The rate 1/ T 2 appears much less influenced by the polymer substitution. The procedure developed for calculating the amount of water bound per PRU, based on the analysis of the T 1 and T 2 data, shows that this amount is the largest for HPC followed by HEC, HP MC K4M, and HPMC K100M. The results correlate well with the degree of hydrophilic substitution of the polymer chains. This NMR analysis deals with a single molecular layer of adsorbed water for the investigated cellulose ether polymers at all concentrations, while the rest of the water in the hydrogel is bulk-like. Therefore, the mesh size of polymer network in the view of a single molecular layer is not effectively changed. [ABSTRACT FROM AUTHOR]

Muon spin rotation (μSR) and relaxation has been used to study the local magnetic structure of K3Fe5F15. A collinear F--μ+--F "hydrogen bond-like" symmetric double minimum type complex with a F…F distance of 2.8 Å and a separation between the two minima of 0.8 Å has been found in the paramagnetic phase. The apparent central position of the muon seems to be the result of fast muon tunneling between two equivalent minima in the F--μ+--F bond. [ABSTRACT FROM AUTHOR]

Muon spin rotation (µSR) and relaxation has been used to study the local magnetic structure of K3Fe5F15. A collinear F-µ+-F "hydrogen bond-like" symmetric double minimum type complex with a F...F distance of 2.8 Å and a separation between the two minima of 0.8 Å has been found in the paramagnetic phase. The apparent central position of the muon seems to be the result of fast muon tunneling between two equivalent minima in the F-µ+-F bond.

Sodium nitroprusside (SNP) is a nitric oxide (•NO) donor in vitro and in vivo. In this paper the time variation of the intracellular water proton nuclear magnetic resonance (NMR) effective relaxation time T'(2a) in SNP-treated human erythrocyte suspensions, containing 10 mM membrane impermeable paramagnetic MnCl2, has been measured. The observed T'(2a) time-course was analyzed in terms of the two mechanisms by which released •NO affects T'(2a). These are, respectively, enhancement of the intracellular water proton intrinsic NMR relaxation rate 1/T(2a) by paramagnetism of •NO subsequently bonded to iron atoms of intracellular deoxyhemoglobin, and suppression of diffusional water permeability P(d) as a consequence of nitrosylation of aquaporin-1 (AQP1) channel Cys189, either by direct reaction with •NO or with one of the •NO oxidation products, such as N2O3. The bound •NO on the Cys189 thiol residue appears to impose a less efficient barrier to water permeation through AQP1 than the larger carboxyphenylmercuryl residue from p-chloromercuribenzoate. The effect of •NO on P(d) is discussed in terms of NO-induced vasodilation.