Background gradient suppression in stimulated echo NMR diffusion studies using magic pulsed field gradient ratios

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.     

Determination of pore space shape and size in porous systems using NMR diffusometry. Beyond the short gradient pulse approximation

The influence of finite length gradient pulses on NMR diffusion experiments on liquids confined to diffuse between two parallel planes is investigated. It is experimentally verified that the pore size decreases when determined using finite gradient pulses if the results are analyzed within the short gradient pulse approximation. The results are analyzed using the matrix formulation. The observed minima in the echo decay profiles are considerably less sharp than theoretical analysis would indicate and we suggest that this is due to the presence of a distribution of pore sizes in the sample. In addition, effects due to the presence of background gradients are discussed. It is argued that effects due to the finite length gradient pulses are relatively minor and in realistic applications the effects due to inhomogeneities in pore sizes and effects due to background gradients will constitute more serious problems in pore size determinations by means of NMR diffusometry.     

Probing four orders of magnitude of the diffusion time in porous silica glass with unconventional NMR techniques

The combined use of two unconventional NMR diffusometry techniques permits measurements of the self-diffusion coefficient of fluids confined in porous media in the time range from 100 microseconds to seconds. The fringe field stimulated echo technique (FFStE) exploits the strong steady gradient in the fringe field of a superconducting magnet. Using a standard 9.4 T (400 MHz) wide-bore magnet, for example, the gradient is 22 T/m at 375 MHz proton resonance and reaches 60 T/m at 200 MHz. Extremely short diffusion times can be probed on this basis. The magnetization grid rotating frame imaging technique (MAGROFI) is based on gradients of the radio frequency (RF) field. The RF gradients not necessarily need be constant since the data are acquired with spatial resolution along the RF gradient direction. MAGROFI is also well suited for unilateral NMR applications where all fields are intrinsically inhomogeneous. The RF gradients reached depend largely on the RF coil diameter and geometry. Using a conic shape, a value of at least 0.3 T/m can be reached which is suitable for long-time diffusion measurements. Both techniques do not require any special hardware and can be implemented on standard high RF power NMR spectrometers. As an application, the influence of the tortuosity increasing with the diffusion time is examined in a saturated porous silica glass.     

Analysis of the magic asymmetric gradient stimulated echo sequence with shaped gradients

Recently a 13-interval magic asymmetrical gradient stimulated echo (MAGSTE) sequence has been proposed for accurate displacement measurements in the presence of spatially varying background gradients. In this paper, the commonly used trapezoidal and sine shaped gradients are studied for the MAGSTE sequence, and the magic asymmetrical gradient ratio and b-factor are provided. The derivation enables the MAGSTE sequence to be implemented on systems with non-negligible gradient rise times.     

Predictions of pulsed field gradient NMR echo-decays for molecules diffusing in various restrictive geometries. Simulations of diffusion propagators based on a finite element method

Pulsed field gradient NMR diffusometry is a promising tool for investigating structures of porous material through determinations of dynamic displacements of molecules in porous systems. A problem with this approach is the lack of closed analytical expressions for echo-decays in anything but idealized pore geometries. We present here an approach based on calculating the appropriate diffusion propagator by means of finite element calculations. The suggested method is quite general, and can be applied to arbitrary porous systems. The protocol for the calculations is outlined and we show results from some different cases: diffusion in confined geometries and in systems that are spatially inhomogeneous with respect to concentration.     

Clustering of magnetic nanoparticles using a double hydrophilic block copolymer, poly(ethylene oxide)-b-poly(acrylic acid)

The use of a double hydrophilic block copolymer (DHBC), poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) to prepare magnetic nanoparticle (MNP) clusters was investigated. In this one-pot synthesis method, the DHBC controlled the particle growth and served as both stabilizer and clustering agent. Depending on the iron-to-polymer ratio, the synthesized particles can be in the form of colonies of small iron oxide particles or clusters of these particles with size larger than 100 nm. Compared to the previous reported result using random copolymers, the clusters prepared with DHBC were more compact and homogeneous. The yield of clusters increased when the amount of polymer added was limiting. Insufficient amounts of polymer resulted in the formation of bare patches on the magnetite surface, and the strong van der Waals attraction induced cluster formation.     

Spectral characterization of diffusion in porous media by the modulated gradient spin echo with CPMG sequence

Carr-Purcell-Meiboom-Gill train of radiofrequency pulses applied to spins in the constant magnetic field gradient is an efficient variant of the modulated magnetic field gradient spin echo method, which provides information about molecular diffusion in the frequency-domain instead in the time-domain as with the two-pulse gradient spin echo. The frequency range of novel technique is broad enough to sample the power spectrum of displacement fluctuation in water-saturated pulverized silica (SiO(2)) and provides comprehensive information about the molecular restricted motion as well as about the structure of medium.     

Electrochemical characteristics of the dimercaptan-poly(ethylene oxide) grafted polyaniline electrodes

The electrochemical and transport properties of the 2,5-dimercapto-1,3,4-thiadiazole (DMcT)/poly(ethylene oxide) (PEO) grafted polyaniline electrodes and the DMcT/polyaniline electrode interfaced with the poly(acrylonitrile) (PAN) based solid-polymer-electrolyte (SPE) containing lithium perchlorate and ethylene carbonate were studied. Compared with the electrochemical and transport properties of the DMcT/polyaniline electrode, the capacitance and voltammetric current density, obtained by cyclic voltammetry, were increased for the electrode with low grafted polyaniline (less than 3 mol. %), while decreased when the applied copolymers were highly grafted ones. The charge transfer resistance obtained from impedance measurements was much smaller in the DMcT/PEO grafted polyaniline electrode than that in the DMcT/polyaniline electrode, and more pronounced reduction of charge transfer resistance was observed for the electrode with low grafted polyaniline. The diffusion coefficient of lithium cation in the electrode was increased when the PEO grafted polyaniline was used as an electrode material, however, the increase of the diffusion coefficient was less significant at higher graft degrees. All these changes in electrochemical and transport characteristics by the employment of PEO chains upon polyaniline backbones were attributed to the enhancement of lithium ion solvation and enlarged free volume in the electrode.     

Improving the sensitivity of a humidity sensor based on fiber bend coated with a hygroscopic coating

A highly sensitive all-fiber humidity sensor is demonstrated. The sensor behaves as a humidity dependent optical switch between 85% and 90% RH. This sensor also offers the advantages of simple structure and low cost and its response is fast and reversible in nature. The typical humidity response of the sensor is suitable for using it as a human breath rate monitor.     

59Co, 23Na NMR and electric field gradient calculations in the layered cobalt oxides NaCoO2 and HCoO2

⁵⁹Co and ²³Na NMR has been applied to the layered cobalt oxides NaCoO₂ and HCoO₂ at three different magnetic field strengths (4.7, 7.1 and 11.7 T). The ⁵⁹Co and ²³Na quadrupole and anisotropic shift tensors have been determined by iterative fitting of the NMR line shapes at the three magnetic field strengths. Due to the large ⁵⁹Co quadrupole interaction in NaCoO₂, a frequency-swept irradiation procedure was used to alleviate the limited bandwidth of the excitation. While the ⁵⁹Co and ²³Na shift and quadrupole coupling tensors in NaCoO₂ are found to be coincident and axially symmetric in agreement with the crystal symmetry requirements, the fits of the ⁵⁹Co NMR spectra clearly show the presence of structural disorder in HCoO₂. The ²³Na chemical shift anisotropy can be reproduced by shift tensor calculations using a point dipole model and considering that the magnetic susceptibility in NaCoO₂ is due to Van Vleck paramagnetism for Co³⁺. Electric field gradient calculations using either the empirical point charge model or the ab initio full potential-linearized augmented plane wave method are compared with the experimental NMR data.     

脂肪醇聚氧乙烯醚在空气-水界面上铺展单分子膜的脱附性质

采用Wilhelmy法测定脂肪醇聚氧乙烯醚在空气-水界面上铺展单分子膜的动态表面压,并由此计算动态脱附动力学参数.实验结果表明,样品铺展膜的脱附初期扩散系数约10-3～10- 4cm2/sec,远远大于溶液表面吸附的扩散系数,铺展膜的初始表面浓度越大,其初期脱附扩散系数也越大.但是从脱附整个过程看,铺展膜的初始表面浓度越大,其平均脱附速率常数越小,脱附过程是属于扩散控制和表面能垒控制共同作用的混合模式.     

Adsorption and electrically stimulated desorption of the triblock copolymer poly(propylene sulfide-bl-ethylene glycol) (PPS-PEG) from indium tin oxide (ITO) surfaces

Protein-resistant triblock copolymers, poly(propylene sulfide-bl-ethylene glycol) (PPS-PEG) have been previously demonstrated to chemisorb onto gold surfaces forming monolayers that resist non-specific protein adsorption and are stable against oxidation. In this paper, we report on the adsorption of PPS-PEG onto a transparent and electrically conductive substrate, indium tin oxide (ITO). In addition, we demonstrate the controlled desorption of PPS-PEG by applying an electrical stimulus. We have used three complementary surface characterization techniques: variable angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to analyze the adsorption and electro-desorption of PPS-PEG from an ITO surface. All three methods confirmed the formation of PPS-PEG adlayers on the ITO surfaces. Based on our experimental XPS and ToF-SIMS results as well as former publications, we postulate that the chemisorption of the PPS-PEG on ITO involves direct sulfide-indium (or tin) interactions. When an ascending anodic electrical stimulus was applied to the surface of the modified samples, a gradual and steady polymer removal was observed, with complete loss of the polymeric monolayer at a potential of 2000 mV (referenced to Ag electrode). Anodic polarization did not result in oxidation of the thioether function of the PPS-PEG adlayers, indicating excellent oxidation resistance of PPS-PEG on ITO surfaces. This work is focused on exploiting electrical stimuli for the in situ surface modification under dynamic control.     

Restricted diffusion and exchange of water in porous media: average structure determination and size distribution resolved from the effect of local field gradients on the proton NMR spectrum

NMR Pulsed field gradient measurements of the restrained diffusion of confined fluids constitute an efficient method to probe the local geometry in porous media. In most practical cases, the diffusion decay, when limited to its principal part, can be considered as Gaussian leading to an apparent diffusion coefficient. The evolution of the latter as a function of the diffusion interval yields average information on the surface/volume ratio of porosities and on the tortuosity of the network. In this paper, we investigate porous model systems of packed spheres (polystyrene and glass) with known mean diameter and polydispersity, and, in addition, a real porous polystyrene material. Applying an Inverse Laplace Transformation in the second dimension reveals an evolution of the apparent diffusion coefficient as a function of the resonance frequency. This evolution is related to a similar evolution of the transverse relaxation time T2. These results clearly show that each resonance frequency in the water proton spectrum corresponds to a particular magnetic environment produced by a given pore geometry in the porous media. This is due to the presence of local field gradients induced by magnetic susceptibility differences at the liquid/solid interface and to slow exchange rates between different pores as compared to the frequency differences in the spectrum. This interpretation is nicely confirmed by a series of two-dimensional exchange experiments.     

Vanadium-51 solid-state NMR electric field gradient tensors: a DFT-embedded ion and isolated cluster study of crystalline vanadium oxides

Density functional theory (DFT) calculations (6–311+G(2d,p)/B3LYP level of theory) of ⁵¹V electric field gradient (EFG) tensor elements are performed for embedded and isolated cluster models of orthovanadates. The structural models used to calculate the EFGs of ⁵¹V are (I) an isolated H₄VO₄⁺ cluster, (II) an isolated H_nVO₄ⁿ⁻³ cluster (n=number of next-neighbor cations) (III) an isolated orthovanadate anion, VO₄^−x, and (IV) a VO₄^−x ion embedded in a finite point-charge array whose electrostatic potential, at the embedded ion, is equivalent to that of the infinite lattice. For models III and IV, a charge x is assigned estimating the covalence of the system. Models III and IV provide results in good agreement with the experiment. Calculations, employing the embedded and isolated VO₄^−x models, are used to discuss site assignments for AlVO₄. Correlations between quadrupole coupling parameters and deviations of the orthovanadate structure from ideal tetrahedral symmetry are shown.     

Solid-state 13C and 1H spin diffusion NMR analyses of the microfibril structure for bacterial cellulose

To obtain further information about the cause for the rather large splitting of the C4 resonance line into the downfield (C4D) and upfield (C4U) lines in CP/MAS ¹³C NMR spectra for native cellulose, ¹³C and ¹H spin diffusion measurements have been conducted by using different types of bacterial cellulose samples. In ¹³C spin diffusion measurements, the C4D resonance line is selectively inverted by the Dante π pulse sequence and the ¹³C spin diffusion is allowed to proceed from the C4D carbons to other carbons including the C4U carbons with use of the ¹³C4-enriched bacterial cellulose sample. The analysis based on the simple spin diffusion theory for the process experimentally observed reveals that the C4U carbons may be located at distances less than about 1 nm from the C4D carbons. In ¹H spin diffusion measurements, poly(vinyl alcohol) (PVA) films in which ribbon assemblies of bacterial cellulose are dispersed are employed and the ¹H spin diffusion process is examined from the water-swollen PVA continuous phase to the dispersed ribbon assemblies by the ¹³C detection through the ¹H–¹³C CP technique. As a result, it is found that the C4D and C4U carbons are almost equally subjected to the ¹H spin diffusion from the PVA phase, indicating that the C4U carbons are not localized in some limited area, e.g. in the surfacial region, but are distributed in the whole area in the microfibrils. These experimental results suggest that the C4U carbons may exist as structural defects probably due to conformational irregularity associated with disordered hydrogen bonding of the CH₂OH groups in the microfibrils.     

Observation of restricted diffusion in the presence of a free diffusion compartment: Single- and double-PFG experiments

Theoretical and experimental studies of restricted diffusion have been conducted for decades using single pulsed field gradient (s-PFG) diffusion experiments. In homogenous samples, the diffusion–diffraction phenomenon arising from a single population of diffusing species has been observed experimentally and predicted theoretically. In this study, we introduce a composite bi-compartmental model which superposes restricted diffusion in microcapillaries with free diffusion in an unconfined compartment, leading to fast and slow diffusing components in the NMR signal decay. Although simplified (no exchange), the superposed diffusion modes in this model may exhibit features seen in more complex porous materials and biological tissues. We find that at low q-values the freely diffusing component masks the restricted diffusion component, and that prolongation of the diffusion time shifts the transition from free to restricted profiles to lower q-values. The effect of increasing the volume fraction of freely diffusing water was also studied; we find that the transition in the signal decay from the free mode to the restricted mode occurs at higher q-values when the volume fraction of the freely diffusing water is increased. These findings were then applied to a phantom consisting of crossing fibers, which demonstrated the same qualitative trends in the signal decay. The angular d-PGSE experiment, which has been recently shown to be able to measure small compartmental dimensions even at low q-values, revealed that microscopic anisotropy is lost at low q-values where the fast diffusing component is prominent. Our findings may be of importance in studying realistic systems which exhibit compartmentation.