共查询到20条相似文献,搜索用时 15 毫秒
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Moreau P van Effenterre D Navailles L Nallet F Roux D 《The European physical journal. E, Soft matter》2008,26(3):225-234
The dynamic behaviour of three hydrophilic probes (two dyes and one fluorescently-labelled protein) inserted in the water layers of lyotropic lamellar phases has been studied by confocal fluorescence recovery experiments. Two different, ionic (AOT/NaCl/ H(2)O and non-ionic ( C(12)E(5) /hexanol/ H(2)O host systems were studied. The confinement effect has been carefully monitored using the swelling properties of the lamellar phases. In all cases, we measure the evolution of the probe diffusion coefficient in the layer plane D ( perpendicular) versus the separation between the membranes d(w). Depending on the composition of the lamellar phase, this distance can be continuously adjusted from 500A to about 20A. For all systems, we observe a first regime, called dilute regime, where the diffusion coefficient decreases almost linearly with 1/d (w) . In this regime, the Faxén theory for the friction coefficient of a spherical particle symmetrically dragged between two rigid walls can largely explain our results. More unexpectedly, when the membranes are non-ionic, and also quite flexible ( C(12)E(5) /hexanol in water), we observe the existence of a second, concentrated (or confined) regime, where the diffusion coefficient is nearly constant and different from zero for membrane separations smaller than the particle size. This new regime can be heuristically explained by simple arguments taking into account the membrane fluidity. 相似文献
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In this study the zero length column (ZLC) technique is extended to the case where the decay of the adsorbed phase concentration is observed directly by nuclear magnetic resonance (NMR). An adsorption-desorption apparatus compatible with a 400-MHz NMR spectrometer was developed. It operates with nitrogen or helium as the inert purge gas. The column of the adsorbent material is placed in the sensitive region of the superconducting magnet and the rf coil of the NMR spectrometer. The time scales of the adsorption and desorption processes depend on concentration, temperature and crystal shape and are found to be in the range of 1-10 min. From the desorption branch, the non-equilibrium ZLC-NMR measurements yield intracrystalline diffusion coefficients in the range of 10(-13) to 10(-11) m2/s for different alkanes in silicalite-1. These values are always found to be smaller than the values measured by pulsed field gradient NMR under equilibrium condition indicating that there must be additional transport resistance at the external surface of these silicalite-1 zeolite crystals. 相似文献
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Robert C. Bowman Dieter M. Gruen Marshall H. Mendelsohn 《Solid State Communications》1979,32(7):501-506
Proton relaxation times have been measured in β-phase LaNi5?yAlyHx, where 0<y<1.2, to determine the role of Al on hydrogen diffusion. Al substitution significantly increases the observed activation energy with a corresponding 100-fold decrease in the room temperature (300K) diffusion constant between y=0 and y=1.2. Comparisons are also made with previous studies of β-LaNi5Hx and possible diffusion mechanisms are suggested. 相似文献
6.
Nuclear magnetic resonance spectroscopy has had extensive applications for the characterization of numerous metal-hydrogen
systems. Although the greatest emphasis of proton NMR has been to evaluate diffusion behavior, increasing attention has been
addressed upon the correlation of proton Knight shifts and the conduction electron contributions to proton spin-lattice relaxation
times to the electronic structure properties of the hydride. The general principles of NMR, that pertain to the usual situations
for most transition metal hydrides, will be briefly reviewed. Several specific examples from some recent research will be
discussed in greater detail. In particular, the roles of host crystal structure and hydrogen site occupancy to hydrogen diffusion
behavior are examined for the Ti1-y
Cu
y
H
x
and Zr1-y
Pd
y
H
x
systems. The proton hyperfine parameters in TiH
x
and ZrH
x
, as well as several related ternary hydrides, are used to qualitatively assess the character of the Fermi level electronic
states. The relationship between the tetragonal distortions of the Ti and Zr dihydrides and a solid-state Jahn-Teller mechanism
will also be examined.
Mound is operated by the Monsanto Research Corporation for the U.S. Department of Energy under Contract No. DE-AC04-76-DP00053. 相似文献
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《Solid State Ionics》1988,26(3):209-215
1H NMR spin-lattice relaxation times, T1 (Zeeman) and T1ϱ (rotating frame) and spin-spin relaxation times, T2, and 31P NMR solid-echoes are reported for phase I and II of hydrogen uranyl phosphate tetrahydrate (HUP) at temperatures in the range 200–323 K. The spectral density functions extracted from the measured relaxation times for phases I and II are consistent with a 2D diffusion mechanism for hydrogen motion. 31P second moments determined from the solid-echoes show that all the hydrogens diffuse rapidly in phase I, and that the hydrogen-bond site nearest to the phosphate oxygen is not occupied in phase II. The mechanism for diffusion in phase II is discussed. 相似文献
9.
A vector field q (the order parameter of the molecular packing) describing the packing (specifically, the orientation) of membrane-forming
amphiphilic molecules is introduced to describe the structures of lyotropic phases constructed from membranes. In the general
case q·n≠0 (where n is the unit normal vector) and therefore the singularities of the vector field q are not determined uniquely by the topology of the surface. The condition q·n=0 signifies disruption of the packing of the molecules. This corresponds to holes, which can form in membranes when lyotropic
systems are diluted. As an illustration, the simplest type of such singularities, in which the distribution of the field q around a hole is described by a part of an instanton with unit topological charge, is studied. It is shown that such a distribution
guarantees the existence of a local minimum under the condition that the tension per unit length λ of the hole boundary is small compared with the deformation energy of the field q:
λh/K≪l (K is the modulus of the orientational elasticity of the field q and h is the thickness of the membrane). The radius of the hole which is formed equals L≈2.52(K/λh)1/3 and the energy E≈59.79K(λh/K)1/3.
Pis’ma Zh. éksp. Teor. Fiz. 64, No. 8, 575–580 (25 October 1996) 相似文献
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N Nestle P Galvosas O Geier M Dakkouri C Zimmermann J K?rger 《Magnetic resonance imaging》2001,19(3-4):547-548
The NMR relaxation properties of hydrating blast-furnace slag cements have recently been shown to be dominated by the effect of water self-diffusion in internal magnetic field gradients in the pastes. While this was suggested on the basis of NMR relaxometry and magnetic susceptibility data, we report here the results from first direct studies of the water self-diffusion in the hydrating paste using a specialized PFG sequence and very intensive magnetic field gradient pulses. 相似文献
11.
An NMR technique is described which allows the observation of ionic charge carriers moving in the electric field within a porous system saturated with electrolyte solution. This method, which was recently developed in our laboratory, gives experimental access to the study of electric transport in disordered media on a microscopic level and offers new potential for morphology studies. We performed 1H NMR PFG self-diffusion measurements on ions combined with ionic drift velocity measurements by electrophoretic NMR (ENMR), each as a function of observation time Delta. In this way we obtained time-dependent self-diffusion coefficients D(+/-) (Delta) and time-dependent electric mobilities mu(+/-) (Delta) of polyatomic cations and anions in porous media. The porous media used were gels and glass bead packs. From the behaviour of D(+/-) (Delta) and mu(+/-) (Delta) at long observation times the tortuosities T(p) (D(+/-)) and T(p) (mu(+/-)) are derived, allowing a direct experimental check of the validity of the Einstein relation (D(+/-) is proportional to mu(+/-)) in a disordered medium. The tortuosities obtained via the diffusivity of ions are compared with those obtained via the diffusivity of water molecules. We also make a first attempt to derive the specific surface S/V(p) from the time-dependence of the ionic mobility at short observation times and discuss possible advantages of those measurements in morphology studies of porous media. 相似文献
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A novel microimaging method is described for measuring the effective diffusion coefficient (D∞) of water in saturated, microporous materials. A simple multicompartment computer simulation was used to show how the value of D∞, when combined with measurements of water proton relaxation times and pulsed field gradient spin-echo amplitudes, allows the pore size distribution and pore connectivity to be characterized. 相似文献
13.
Ultrasonic absorption and velocity measurements have been made on cetyl trimethyl ammonium bromide (CTAB) solution in heavy water. Velocity measurements have been made of CTAB concentration at 25°C and a frequency of 2.0?MHz. Absorption measurements have been made in the frequency range of 5.0–55.0?MHz for various CTAB concentration. The results of these measurements indicate micelle formation. Absorption measurements show the existence of a single relaxation frequency. A detailed analysis of the data has been presented. Theoretical and experimental relaxation frequencies are approximately the same. 相似文献
14.
Hebbar S Suryaprakash N 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,210(1):123-125
Multiple quantum-single quantum correlation experiments are employed for spectral simplification and determination of the relative signs of the couplings. In this study, we have demonstrated the excitation of three nuclei, triple quantum coherences and discussed the information obtainable from such experiments. The experiments have been carried out on doubly labeled acetonitrile and fluoroacetonitrile aligned in liquid crystalline media. The experiment is advantageous in providing many spectral parameters from a single experiment. The coherence pathways involved in the pulse sequence are described using product operators. 相似文献
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A large asymmetry parameter in the deuterium spectral pattern is idetified for the first time near the gel position of the of the potassium palmitate-water system. This asymmetry, measured at the deuterated terminal methyl position of the hydrocarbon chain, implies biaxial order suggesting cooperative tilt of the chains in the bilayer. 相似文献
16.
Effects of restricted diffusion on MR signal formation 总被引:2,自引:0,他引:2
Sukstanskii AL Yablonskiy DA 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,157(1):92-105
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Recent progress in the application of solid-state NMR (SS NMR) spectroscopy in structural studies of active pharmaceutical ingredients (APIs) embedded in different drug carriers is detailed. This article is divided into sections. The first part reports short characterization of the nanoparticles and microparticles that can be used as drug delivery systems (DDSs). The second part shows the applicability of SS NMR to study non-steroidal anti-inflammatory drugs (NSAIDs). In this section, problems related to API–DDS interactions, morphology, local molecular dynamics, nature of inter- or intramolecular connections, and pore filling are reviewed for different drug carriers (e.g. mesoporous silica nanoparticles (MSNs), cyclodextrins, polymeric matrices and others). The third and fourth sections detail the recent applications of SS NMR for searching for antibiotics and anticancer drugs confined in zeolites, MSNs, amorphous calcium phosphate and other carriers. 相似文献
18.
Galvosas P Stallmach F Kärger J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,166(2):610-173
By evaluating the spin echo attenuation for a generalized 13-interval PFG NMR sequence consisting of pulsed field gradients with four different effective intensities (F(p/r) and G(p/r)), magic pulsed field gradient (MPFG) ratios for the prepare (G(p)/F(p)) and the read (G(r)/F(r)) interval are derived, which suppress the cross term between background field gradients and the pulsed field gradients even in the cases where the background field gradients may change during the z-store interval of the pulse sequence. These MPFG ratios depend only on the timing of the pulsed gradients in the pulse sequence and allow a convenient experimental approach to background gradient suppression in NMR diffusion studies with heterogeneous systems, where the local properties of the (internal) background gradients are often unknown. If the pulsed field gradients are centered in the tau-intervals between the pi and pi/2 rf pulses, these two MPFG ratios coincide to eta=G(p/r)/F(p/r)=1-8/[1+(1/3)(delta/tau)(2)]. Since the width of the pulsed field gradients (delta) is bounded by 0< or =delta< or =tau, eta can only be in the range of 5< or =-eta< or =7. The predicted suppression of the unwanted cross terms is demonstrated experimentally using time-dependent external gradients which are controlled in the NMR experiment as well as spatially dependent internal background gradients generated by the magnetic properties of the sample itself. The theoretical and experimental results confirm and extend the approach of Sun et al. (J. Magn. Reson. 161 (2003) 168), who recently introduced a 13-interval type PFG NMR sequence with two asymmetric pulsed magnetic field gradients suitable to suppress unwanted cross terms with spatially dependent background field gradients. 相似文献
19.
A stochastic computer simulation is used to investigate the effects of restricted diffusion in NMR microscopy. It is shown that diffusion contributes to a loss of interfacial resolution through two main mechanisms. The first applies to spatial regions bound by impermeable interfaces and involves diffusive averaging of the frequency differences set up by the applied field gradients. This effect can be made arbitrarily small by increasing the magnitude of the field gradient. The second mechanism involves diffusion through permeable membranes or interfaces defining the sample morphology. This effect can, in principle, be reduced by multiple echo imaging with short pulse spacings. The possibility of imaging diffusive flow through a permeable interface is discussed. 相似文献
20.
R. Kimmich F. Klammler V. D. Skirda I. A. Serebrennikova A. I. Maklakov N. Fatkullin 《Applied magnetic resonance》1993,4(4):425-440
Geometrical restrictions of water diffusion in different aqueous protein systems were studied using two versions of the NMR field gradient technique. The samples were aqueous systems of bovine serum albumin, gelatin and horse myoglobin at concentrations ranging from diluted solutions to almost dry powders being only partly hydrated. Hydrated protein aerogels were produced by the aid of a special preparation procedure and studied in addition. The experiments referred to the, temperature and concentration dependences of the water diffusion coefficient above and below the free-water freezing temperature. The diffusion coefficient within clusters of overlapping hydration shells is reduced by one order of magnitude compared with that of bulk water. Geometrical restrictions manifest themselves (a) by the obstruction effect observed at low protein concentrations, (b) by the topologically two-dimensional diffusion in the network of overlapping hydration shells, (c) by the percolation threshold appearing at about 15%b.w. water and (d) by the anomalous diffusion behaviour concluded from the protein aerogel study. 相似文献