Diffusion Spectrum of Polymer Melt Measured by Varying Magnetic Field Gradient Pulse Width in PGSE NMR.

The translational motion of polymers is a complex process and has a big impact on polymer structure and chemical reactivity. The process can be described by the segment velocity autocorrelation function or its diffusion spectrum, which exhibit several characteristic features depending on the observational time scale-from the Brownian delta function on a large time scale, to complex details in a very short range. Several stepwise, more-complex models of translational dynamics thus exist-from the Rouse regime over reptation motion to a combination of reptation and tube-Rouse motion. Accordingly, different methods of measurement are applicable, from neutron scattering for very short times to optical methods for very long times. In the intermediate regime, nuclear magnetic resonance (NMR) is applicable-for microseconds, relaxometry, and for milliseconds, diffusometry. We used a variation of the established diffusometric method of pulsed gradient spin-echo NMR to measure the diffusion spectrum of a linear polyethylene melt by varying the gradient pulse width. We were able to determine the characteristic relaxation time of the first mode of the tube-Rouse motion. This result is a deviation from a Rouse model of polymer chain displacement at the crossover from a square-root to linear time dependence, indicating a new long-term diffusion regime in which the dynamics of the tube are also described by the Rouse model.

Study of translational dynamics in molten polymer by variation of gradient pulse-width of PGSE.

Pulsed gradient spin echo is a method of measuring molecular translation. Changing Δ makes it sensitive to diffusion spectrum. Spin translation effects the buildup of phase structure during the application of gradient pulses as well. The time scale of the self-diffusion measurement shortens if this is taken into account. The method of diffusion spectrometry with variable δ is also less sensitive to artifacts caused by spin relaxation and internal gradient fields. Here the method is demonstrated in the case of diffusion spectrometry of molten polyethylene. The results confirm a model of constraint release in a system of entangled polymer chains as a sort of tube Rouse motion.

The Muon F-µ+-F Hydrogen Bond-like Complex.

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.

Influence of sodium nitroprusside on human erythrocyte membrane water permeability: an NMR study.

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.

Proton magnetic relaxation and the aggregation of n-octylammonium n-octadecanoate surfactant in deuterochloroform solution.

(1)H NMR spin-lattice and spin-spin relaxation times of isotropic solutions of n-octylammonium n-octadecanoate in deuterochloroform containing ca. 0.1-0.2% tetramethylsilane (v/v) at ca. 292 K are observed to vary with position of the functional group in the amphiphile ion-pair, and with solute concentration. The latter dependence can be satisfactorily described using either single or multiple equilibria models of association complex formation of the reverse micelle type above a critical concentration (ca. 0.13 mol kg(-1)). Transverse relaxation is accounted for predominantly via reorientation/rotational diffusion of monomers and micellar aggregates, and is analyzed in terms of two component times, while longitudinal relaxation principally involves motions of different size segments around covalent bonds. Picosecond correlation times are attributed to intramolecular and monomer rotations, whereas multimer reorientation/tumbling processes are an order of magnitude longer. Results are analyzed for size of the reorienting species in terms of theoretical calculations for rotational diffusion of model cylindrical and ellipsoidal volumes of revolution, which above the critical micelle concentration correspond to association complexes of 2-4 monomers. Dilution shifts of the proton NMR peak positions also comply with the model of reverse micelle formation. The use of nonspinning liquid samples for the characterization of micellization phenomena via a nuclear magnetic resonance imaging spectrometer is investigated.

Influence of confinement in controlled-pore glass on the layer spacing of smectic- a liquid crystals.

A detailed x-ray scattering study has been performed in the temperature range of the smectic- A phase for the liquid crystal compounds dodecylcyanobiphenyl (12CB) and octylcyanobiphenyl (8CB) confined in different controlled-pore glasses (CPGs) characterized by their average void radius R . On decreasing the temperature in bulk samples the layer thickness is increasing for 12CB and decreasing for 8CB, respectively. In nontreated CPG samples the layers dilate significantly with respect to the bulk liquid crystal. In order to explain the layer thickness behavior on varying temperature and R , one has to take into account molecular details of the liquid crystalline samples as well as memory effects.

Presmectic wetting and supercritical-like phase behavior of octylcyanobiphenyl liquid crystal confined to controlled-pore glass matrices.

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 eta(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 eta(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 approximately<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 approximately 15.1 and approximately 7.5 nm, respectively.

Na-nitroprusside and HgCl2 modify the water permeability and volume of human erythrocytes.

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 HgCl(2) 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 ((1)H) 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 Mn(2+) ions. The (1)H-T(2) NMR technique allows determination of the time constant tau(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 HgCl(2)-treated erythrocytes, this technique showed simultaneous variation of both tau(exch) and the volume ratio V(in)/V(out) of intracellular and extracellular water in proportions suggesting that P(d) was left unmodified. The HgCl(2) effect has been found to be partly reversible by the reducing activity of added mercaptoethanol.

Electrical conduction in macroscopically oriented deoxyribonucleic and hyaluronic acid samples.

Measurements of the quasistatic and frequency dependent electrical conductivity below 1 MHz were carried out on wet-spun, macroscopically oriented, calf thymus deoxyribonucleic (DNA) and umbilical cord hyaluronic acid (HA) bulk samples. The frequency dependence of the electrical conductivity in the frequency range of approximately 10(-3) - 10(6) Hz of both materials is surprisingly rather similar. Temperature dependence of the quasistatic electrical conductivity above the low temperature saturation plateau can be well described by the activated Arrhenius law with the activation energy of approximately 0.8 eV for both DNA and HA. We discuss the meaning of these findings for the possible conduction mechanism in these particular charged polyelectrolytes.

Quantitative evaluation of polymer concentration profile during swelling of hydrophilic matrix tablets using 1H NMR and MRI methods.

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.

Influence of finite size and wetting on nematic and smectic phase behavior of liquid crystal confined to controlled-pore matrices.

The high-resolution calorimetric study was carried out on octylcyanobiphenyl liquid crystal (LC) confined to various controlled-pore glass (CPG) matrices with silane-treated surface. The diameter of the voids cross section ranged between 23.7 and 395 nm. The results are compared to those obtained previously on CPG voids nontreated with silane. We found a striking similarity between the shifts in the isotropic to nematic and nematic to smectic-A phase transition temperatures as a function of the void radius in which order parameter variations at the LC-void interface play the dominant role. Weaker temperature shifts are observed in silane-treated samples, where surface ordering tendency is larger. In nontreated samples, a finite-size scaling law in the maximum value of the heat capacity at the nematic to smectic-A transition was observed for void diameters larger than 20 nm. In silane-treated samples, this behavior is considerably changed by surface wetting interactions.

Calorimetric study of octylcyanobiphenyl liquid crystal confined to a controlled-pore glass.

We present a calorimetric study of the phase behavior of octylcyanobiphenyl (8CB) liquid crystal confined to a controlled-pore glass (CPG). We used CPG matrices with characteristic void diameters ranging from 400 to 20 nm. In bulk we obtain weakly first-order isotropic to nematic (I-N) phase transition and nearly continuous character of the nematic to smectic-A (N-SmA) phase transition. In all CPG matrices the I-N transition remains weakly first order, while the N-SmA one becomes progressively suppressed with decreasing CPG pore radius. With decreased pore diameters both phase transition temperatures monotonously decrease following similar trends, but increasing the stability range of the N phase. The heat-capacity response at the weakly first order I-N and continuous N-SmA phase transitions gradually approaches the tricritical-like and three-dimensional XY behavior, respectively. The main observed features were explained using a bicomponent single pore type phenomenological model.

Quantification of the MR images of hydrogels by NMR relaxation measurements.

Layers of hydrogel represent a diffusional barrier that retards the process of drug release. For better prediction of drug release, a method for evaluating the polymer concentration profile was developed.

Alternating electric fields stimulate ATP synthesis in Escherichia coli.

External alternating electric fields of low intensity stimulated membrane bound ATP synthesis in starving Escherichia coli cells with electric field amplitudes of 2.5-50 V/cm and a frequency optimum at 100 Hz. The model of electrocon-formational coupling was used to analyze the frequency and amplitude responses of ATP synthesis. Two relaxation frequencies of the system were obtained at 44 Hz and 220 Hz, and an estimate of roughly 12 was obtained as the effective charge displacement for the catalytic cycle of ATP synthesis.

Investigation of the state and dynamics of water in hydrogels of cellulose ethers by 1H NMR spectroscopy.

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 spin-lattice (T1) and spin-spin (T2) relaxation times were measured in these systems at room temperature. The observed proton NMR T1 and T2 of water in hydrogels at different cellulose ether concentrations at room temperature were shown to decrease with increasing polymer concentration. The relaxation rate 1/T1 is sensitive to the type of polymer substituent but insensitive to the polymer molecular mass. The rate 1/T2 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 T1 and T2 data, shows that this amount is the largest for HPC followed by HEC, HPMC 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.