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PubMedDate not supplied

Diffusion-weighted MR in experimental sustained seizures elicited with kainic acid.

PURPOSE: To investigate the early changes in diffusion-weighted MR images in the sustained limbic seizures. METHOD: Intraperitoneal injection of kainic acid was used to induce sustained limbic seizures in seven rats. The animals were investigated with serial 2.0-T MR imaging beginning immediately after kainic acid-induced seizures, and at 24 hours, 3 days, and 7 days after the kainic acid injection. Diffusion-weighted spin-echo and T2-weighted images and apparent diffusion coefficients were sequentially assessed and compared with histologic changes. The results were compared with eight control animals given buffered saline intraperitoneally. RESULTS: Diffusion-weighted MR images revealed an increase in signal intensity bilaterally in the amygdala and the piriform cortices immediately after the sustained seizures, whereas T2-weighted images did not show changes in signal intensity at this time. Both diffusion-weighted and T2-weighted images showed marked increase in signal intensities in these same areas 24 hours after kainic acid injection. The apparent diffusion coefficient values were significantly lower in the area of the amygdala and the piriform cortex immediately after and lower again 24 hours after the sustained seizures. The area of hyperintensity in diffusion-weighted images was concordant with the histologic distribution of neuronal pyknosis and neuropile vacuolation. CONCLUSION: Diffusion-weighted MR revealed focal abnormalities in the limbic system after 1 hour of sustained seizures induced with kainic acid, before changes on T2-weighted imaging. Diffusion-weighted MR is a potential method for studying the mechanisms of brain damage caused by sustained seizures.

Amygdala↗

PubMed1994

Localization and diffusion of glucagon receptor in rat hepatocytes.

The lateral diffusion rate of glucagon receptor in rat hepatocyte plasma membrane in the absence and presence of glucagon was measured to be approximately 7.0 x 10(-10) cm2/s. The percentage of glucagon receptor molecules remaining on the cell surface after the activation of signal transduction process by 100 nM glucagon was approximately 74% of its original number. Although the number of glucagon receptors on the plasma membrane capable of interacting with its signal transduction partners decreases on addition of glucagon, the lateral diffusion rate and the percentage of mobile receptors remain essentially unchanged. A hypothesis has been developed that for signal transduction to occur, the random diffusion-dependent collision of one, two, or all three components is an essential part, and it may be the rate-limiting step. An approximate calculation has been made of random diffusion-dependent theoretical and experimental collision frequencies using experimentally measured concentrations and reasonable value for diffusion rate of G protein to investigate the role of diffusion in signal transduction. These calculations indicate that the diffusion of individual components is important and may be the rate-limiting step in the signal transduction process. The diffusion rate and percent mobile fraction of glucagon receptor data presented in this article are the first step toward elucidating the validity of the diffusion-dependent signal transduction hypothesis.

Adenylyl Cyclases↗

PubMed1998

Diffusion-weighted MR imaging in hypertensive encephalopathy: clues to pathogenesis.

PURPOSE: Hypertensive encephalopathy, a complex of cerebral disorders, including headache, seizures, visual disturbances, and other neurologic manifestations, is associated with a variety of conditions in which blood pressure rises acutely. It has been ascribed to either exuberant vasospasm with ischemia/infarction or breakthrough of autoregulation with interstitial edema. Diffusion-weighted MR imaging may be used to determine whether the edema in hypertensive encephalopathy is cytotoxic or vasogenic in origin. METHODS: Diffusion-weighted imaging was performed using the double line scan diffusion imaging technique on a 1.5-T MR system. Seven patients with hypertensive encephalopathy were imaged within 1 day of the onset of their symptoms. Apparent diffusion coefficient maps as well as low and high b-factor images were acquired. The two-tailed paired Student's t-test was used to compare the apparent diffusion coefficients in edematous brain regions with those of normal white matter. RESULTS: In all cases the apparent diffusion coefficient maps of the patients with hypertensive encephalopathy showed increased signal in regions corresponding to increased T2 signal on standard T2-weighted (low b-factor) images. Quantitative apparent diffusion coefficients in regions of abnormal T2 signal were 1.36 +/- 0.14 microm2/ms, compared with 0.80 +/- 0.05 microm2/ms in normal white matter. Diffusion-weighted (high b-factor) T2-weighted images did not show abnormal signal. CONCLUSION: Diffusion-weighted MR imaging shows that the edema in hypertensive encephalopathy is of vasogenic origin and does not represent ischemia or infarction. This finding may have therapeutic implications.

Adult↗

PubMed2004

Water diffusion in a rat glioma during ganciclovir-thymidine kinase gene therapy-induced programmed cell death in vivo: correlation with cell density.

PURPOSE: To study the characteristics of diffusion magnetic resonance imaging (MRI) contrast in a rat brain BT4C glioma during progression of ganciclovir (GCV)-thymidine kinase gene therapy-induced programmed cell death (PCD) in vivo. MATERIALS AND METHODS: The trace of the diffusion tensor (Dav = 1/3TraceD), T2, and spin density were determined by MRI and the apparent diffusion coefficient (ADC) of water by diffusion nuclear MR (NMR) spectroscopy using largely varying b values and diffusion times (tD) at 4.7 T. Cell count and apoptotic cells were quantified by histological means. RESULTS: Decline in cell count was strongly associated with increase in both Dav and T2. Spin density ratio between tumor and contralateral parietal cortex increased with a very similar time course as Dav and T2, indicating net water gain into the eradicating tumor. Diffusion spectroscopy showed a nonmonoexponential signal decay at all tD values ranging from 14-192 msec. During PCD, the ADC of the component yielding fast diffusion coefficient (D1), as acquired with tD > or = 47 msec, increased with kinetics similar to those of Dav (tD = 4.8 msec). The fractional size of D1 increased by 10% to 15% throughout the entire tD range. Apparent water residence time of the slow diffusion component, D2, shortened from a value of 38.3 +/- 1.7 msec on day 0 to 33.4 +/- 0.5 msec by day 8. CONCLUSION: The present results show that reduced cell density and increased water content, leading to altered water microenvironment, are associated with increased water diffusion coefficient in eradicating gliomas as a result of PCD.

Animals↗

PubMed2005

Autofluorescence and diffuse reflectance spectroscopy for oral oncology.

BACKGROUND AND OBJECTIVES: Autofluorescence and diffuse reflectance spectroscopy have been used separately and combined for tissue diagnostics. Previously, we assessed the value of autofluorescence spectroscopy for the classification of oral (pre-)malignancies. In the present study, we want to determine the contributions of diffuse reflectance and autofluorescence spectroscopy to diagnostic performance. STUDY DESIGN/MATERIALS AND METHODS: Autofluorescence and diffuse reflectance spectra were recorded from 172 oral lesions and 70 healthy volunteers. Autofluorescence spectra were corrected in first order for blood absorption effects using diffuse reflectance spectra. Principal Components Analysis (PCA) with various classifiers was applied to distinguish (1) cancer and (2) all lesions from healthy oral mucosa, and (3) dysplastic and malignant lesions from benign lesions. Autofluorescence and diffuse reflectance spectra were evaluated separately and combined. RESULTS: The classification of cancer versus healthy mucosa gave excellent results for diffuse reflectance as well as corrected autofluorescence (Receiver Operator Characteristic (ROC) areas up to 0.98). For both autofluorescence and diffuse reflectance spectra, the classification of lesions versus healthy mucosa was successful (ROC areas up to 0.90). However, the classification of benign and (pre-)malignant lesions was not successful for raw or corrected autofluorescence spectra (ROC areas <0.70). For diffuse reflectance spectra, the results were slightly better (ROC areas up to 0.77). CONCLUSIONS: The results for plain and corrected autofluorescence as well as diffuse reflectance spectra were similar. The relevant information for distinguishing lesions from healthy oral mucosa is probably sufficiently contained in blood absorption and scattering information, as well as in corrected autofluorescence. However, neither type of information is capable of distinguishing benign from dysplastic and malignant lesions. Combining autofluorescence and reflectance only slightly improved the results.

Adolescent↗

PubMed2003

Analysis and generalized correction of the effect of spatial gradient field distortions in diffusion-weighted imaging.

Nonuniformities of magnetic field gradients can cause serious artifacts in diffusion imaging. While it is well known that nonlinearities of the imaging gradients lead to image warping, those imperfections can also cause spatially dependent errors in the direction and magnitude of the diffusion encoding. This study shows that the potential errors in diffusion imaging are considerable. Further, we show that retrospective corrections can be applied to reduce these errors. A general mathematical framework was formulated to characterize the contribution of gradient nonuniformities to diffusion experiments. The gradient field was approximated using spherical harmonic expansion, and this approximation was employed (after geometric distortions were eliminated) to predict and correct the errors in diffusion encoding. Before the corrections were made, the experiments clearly revealed marked deviations of the calculated diffusivity for fields of view (FOVs) generally used in diffusion experiments. These deviations were most significant farther away from the magnet's isocenter. For an FOV of 25 cm, the resultant errors in absolute diffusivity ranged from approximately -10% to +20%. Within the same FOV, the diffusion-encoding direction and the orientation of the calculated eigenvectors can be significantly altered if the perturbations by the gradient nonuniformities are not considered. With the proposed correction scheme, most of the errors introduced by gradient nonuniformities can be removed.

Anisotropy↗

PubMed1992

MR imaging of anisotropic and restricted diffusion by simultaneous use of spin and stimulated echoes.

A new magnetic resonance imaging technique for evaluating anisotropic and restricted diffusion effects in a single experiment is described. The method is based on a pulse sequence that simultaneously excites a spin echo (SE) and a stimulated echo (STE) and contains two pairs of diffusion-sensitive gradient pulses. The diffusion attenuation of the SE and STE can be controlled independently by separate adjustment of the parameters associated with each pair of the diffusion-sensitive gradient pulses. This method can be more time efficient than acquiring separate SE and STE images for the same study. Furthermore, the pulse sequence minimizes the effect of motion and instrumental and physiological variations that occur between separate image acquisitions which can give rise to artifactual results when difference imaging is employed. In addition to applications to anisotropic and restricted diffusion, this technique can be used for: (1) simultaneous acquisition of T2-weighted and diffusion-weighted images during cerebral ischemia studies; (2) calculation of diffusion coefficients from a pair of diffusion-weighted images; (3) separating fast and slow diffusion components in a single imaging experiment; and (4) two-dimensional velocity-encoded imaging.

Animals↗

PubMed1996

Detection of different water populations in brain tissue using 2H single- and double-quantum-filtered diffusion NMR spectroscopy.

This paper presents the first simultaneous 2H single- and double-quantum (SQ and DQ, respectively) diffusion study of excised brain tissue. The apparent diffusion coefficients (ADCs) of the 2H SQ and DQ signals were measured at a fixed diffusion time (Delta - delta/3 = 21.3 ms) and as a function of the diffusion time to assess restricted diffusion [(Delta - delta/3) was changed from 21.3 to 271. 3 ms]. As expected, the ADC of the SQ signal was higher than that of the DQ signal [0.53 +/- 0.03 x 10(-5) (n = 3) and 0.30 +/- 0.03 x 10(-5) cm2 s-1 (n = 4), respectively]. When the ADCs of the SQ and DQ signals were measured as a function of the diffusion time, two components, a fast and a slow component, were observed in each case. The ADCs for the SQ signal were 1.16 +/- 0.2 x 10(-5) and 0.35 +/- 0.06 x 10(-5) cm2 s-1 (n = 3) for the fast and the slow components, respectively. The ADCs for the DQ signal were 0.31 +/- 0.05 x 10(-5) and approximately 0.03 +/- 0.03 x 10(-5) cm2 s-1 (n = 2) with the slow component being relatively small. Interestingly, the slow-diffusion component of the SQ signal was found to have an ADC similar to that of the fast component of the DQ signal. These results suggest that brain water can be divided into at least three water populations and that the DQ signal originates from water molecules which interact with slow-diffusing structural components of the brain. The new insights that one can obtain using simultaneous SQ and DQ diffusion measurement and the ability to distinguish among water populations in biological tissues using the above approach are discussed.

Animals↗

PubMed1998

Spin Echo Attenuation of Restricted Diffusion as a Discord of Spin Phase Structure

By using the particle probability density we analyze the spin echo attenuation of particles, diffusing in a bounded region. It provides a means to expand a nonuniform spin phase distribution into a series of waves that characterize the geometry and boundary conditions of confinement. Random motion disrupts the initial phase structure created by applied gradients and consequently discords its structure waves. By assuming the spin phase fluctuation and/or the randomness of spin phase distribution in the subensemble as a Gaussian stochastic process, we derive a new analytical expression for the echo attenuation related to the particle velocity correlation. For a diffusion in porous structure we get the expression featuring the same "diffusive diffraction" patterns as those being found and explained by P. T. Callaghan and A. Coy ("Principles of Nuclear Magnetic Resonance Microscopy," Oxford Univ. Press, Oxford (1991); J. Chem. Phys. 101, 4599-4609 (1994)) with the use of propagator theory. With the new approach we cast a new light on the phenomena and derive analitically how the diffusive diffractions appear when the sequence of finite or even modulated gradients are applied. The method takes into account the non-Markovian character of restricted diffusion, and therefore the echo dependence on the diffusion lengths and on the strength of applied gradient differs from the results of authors assuming the Markovian diffusion either by dealing with the diffusion propagators or by the computer simulation of Fick's diffusion. Copyright 1998 Academic Press.

Journal Article↗

PubMed2006

Antibiotic susceptibility of Helicobacter pylori clinical isolates: comparative evaluation of disk-diffusion and E-test methods.

Antimicrobial susceptibility of 25 Helicobacter pylori strains isolated from patients with acid peptic diseases were tested for in vitro sensitivity to commonly used antibiotics using disk-diffusion and E-test, methods. All strains tested were susceptible to tetracycline by E-test, with the minimum inhibitory concentration (MIC) values being <0.125 microg/ml for all strains except for 6 (<0.023 microg/ml). However 1 strain was resistant by disk-diffusion method. One strain was resistant to clarithromycin both by disk diffusion and E-test (MIC <48 microg/ml), and 1 strain was resistant only by disk diffusion. Only one strain was resistant to amoxicillin by disk diffusion and E-test (MIC >256 microg/ml). For ciprofloxacin, three strains were resistant by disk diffusion and two by E-test (MIC <32 microg/ml). Sixteen strains were resistant to metronidazole by disk diffusion and E-test (MIC >or= 8 microg/ml), and 1 was resistant only by E-test (MIC <48 microg/ml). Overall, 64% of the strains were resistant to metronidazole. The MIC for metronidazole was also tested by agar-dilution method, and metronidazole resistant strains had an, MIC >8 microg/ml. The disk-diffusion method showed excellent correlation with E-test results; there was 100% agreement for amoxicillin a other antibiotics showed 90% to 95% accuracy. Disk diffusion is cheaper than E-test (approximately 2.6 cents vs. 2.60 US dollars), is easy to perform, and is a reliable method for testing H. pylori susceptibility to antimicrobial agents in the clinical microbiology laboratory.

Anti-Bacterial Agents↗

PubMed2000

Does diffusion-weighted magnetic resonance imaging enable detection of early ischemic change following transient cerebral ischemia?

To examine the usefulness of diffusion-weighted imaging for detecting neuronal damage following ischemia, dynamic changes in diffusion-, T1- and T2-weighted images of rats subjected to 10 min of 4-vessel occlusion and of humans who had suffered 10-20 min of cardiac arrest were observed. In rats, no remarkable alteration was observed on day 1. On day 3, however, diffusion-weighted images showed high signal intensity in the hippocampal area, in which the apparent diffusion coefficient was significantly lower than that of the control (760+/-28x10(-6) mm(2)/s in control vs. 480+/-29x10(-6) mm(2)/s on day 3, P<0.0001). Histological observation revealed microvacuolation in 92+/-4% of pyramidal neurons in the CA1 region. On day 7, the hyperintensity in diffusion-weighted images had disappeared and microvacuolation had also disappeared in the CA1 region, but severely disrupted pyramidal neurons containing pyknotic nuclei had appeared in the CA1 region instead. In humans, diffusion-weighted images did not show any apparent abnormality in the cerebral cortex on the day of resuscitation. On day 3, however, diffusion-weighted images consistently showed hyperintensities in the temporal or occipital cortex, and these hyperintensities had disappeared in images obtained on days 7 and 14. From day 14, T1-weighted images showed laminar hyperintensity, suggesting laminar necrosis, along the cortex, where diffusion-weighted images showed high signal intensity on day 3. These results suggested that diffusion-weighted imaging has a potential for detection of the occurrence of microvacuolation and is useful for detecting the progression of ischemic changes in humans following global ischemia.

Aged↗

PubMed1997

Repeatable diffuse visual field loss in open-angle glaucoma.

PURPOSE: The authors determined the frequency of repeatable diffuse loss as the only form of visual field damage in patients with early to moderate open-angle glaucoma in a prospective follow-up study. METHODS: The study contained 113 patients (median age, 64 years; range, 17-89 years) who were tested at 6-month intervals with program 30-2 of the Humphrey Field Analyzer (Humphrey Instruments Inc., San Leandro, CA). Although the inclusion criterion for visual acuity was > or = 20/40, on entry, 94 (83.2%) patients had an acuity of > or = 20/25. Cumulative defect curves were generated for all visual fields (median per patient, 7; range, 4-9). After randomizing the order and removing all patient information, two observers independently rated each visual field as being "normal" or showing "diffuse," "localized," or "diffuse and localized" loss. We defined repeatable diffuse loss as occurring when at least two thirds of the number of fields in the follow-up were classified as "diffuse." RESULTS: Fourteen patients (12.4%) had repeatable diffuse loss according to the cumulative defect curves. After reviewing their clinical charts, we excluded six of these patients because of early lens changes despite good visual acuity and three because of a suggestion of localized loss (on pattern deviation probability plots) in addition to the predominantly diffuse loss. The remaining five (4.4%) patients had repeatable diffuse loss that was due solely to open-angle glaucoma. CONCLUSION: Although diffuse visual field loss is exaggerated by factors other than glaucoma in the majority of patients, it can occur repeatedly in a small number of patients as the only sign of visual field damage.

Adolescent↗

PubMed1998

Direct injection of 90Y MoAbs into glioma tumor resection cavities leads to limited diffusion of the radioimmunoconjugates into normal brain parenchyma: a model to estimate absorbed radiation dose.

PURPOSE: Previously we have demonstrated that radioimmunoconjugates can be injected into glioma resection cavities to deliver a boost of radiation to the cavity edge with little toxicity to the normal brain. In the mathematical models we have previously published to assist in the development of this strategy we assumed that antibody remains associated with the cavity edge and no diffusion occurs. However, moderate diffusion might be beneficial while, if this were excessive, it would decrease the therapeutic index markedly. METHODS AND MATERIALS: Selected individuals with relapsed malignant glioma underwent further surgical debulking; 90Y MoAb radioimmunotherapy; and open biopsy to determine the extent to which the conjugate diffuses from the cavity edge. Samples from these patients were taken in radial tracts and the corrected activity in each sample was plotted against distance from the cavity wall to determine appropriate diffusion constants. RESULTS: Our data indicates that diffusion of radioimmunoconjugate from the edge of a glioma resection cavity appears to be an exponential process. The mean Ro for each patients data set ranged from 0.48-0.63 (overall mean 0.6) cm. A dosimetric model was developed that translates these measurements into estimates of radiation dose. Applying the clinical data to this model indicates that, in each patient, the peak dose is delivered 0.16-0.18 cm below the cavity margin, and the mean dose at 2 cm deep is 5.3% (4.4-5.8%) of the peak. CONCLUSION: The model described can be used to translate diffusion constants measured by any method into estimates of absorbed radiation dose. Assuming similar diffusion kinetics, it can also be used to predict the dose deposited if alternative radionuclides are linked to MoAb, although the effect of dose rate should also be considered. In the future, it may be possible to manipulate diffusion by using either different antibodies or antibody fragments for intracavity radioimmunotherapy. Before this can be done, however, further data are needed and a noninvasive approach to measuring diffusion would clearly be optimal.

Antibodies, Monoclonal↗

PubMed2002

Diffusion-weighted images in neonatal cerebral hypoxic-ischemic injury.

Diffusion-weighted images of magnetic resonance imaging, obtained by mapping apparent diffusion coefficients, are more sensitive than other magnetic resonance imaging sequences in the earliest detection of acute cytotoxic injury. The usefulness of diffusion-weighted images in focal ischemic brain injury has been documented in children and adults. We report eight full-term neonates with global cerebral hypoxic-ischemic injury and abnormalities on diffusion-weighted images. Distribution of diffusion-weighted imaging abnormalities in the eight neonates was consistent with global hypoxic-ischemic injury in full-term neonates, with diffuse cortical necrosis, border-zone infarcts, or basal ganglia/thalamic injury. Magnetic resonance imaging scans with diffusion-weighted images were obtained within the first 4 days of age in all eight neonates. In each patient, standard magnetic resonance imaging sequences substantially underestimated the extent of injury when compared with diffusion-weighted images in unmyelinated neonatal brains. Extensive injury bilaterally with basal ganglia and thalamic and widespread multifocal cortical injury correlated with a severe neurologic outcome. Lesser degrees of injury, limited to smaller sectors of cortical or border zone involvement, were associated with better neurologic outcome. The high sensitivity of diffusion-weighted images to map the extent of hypoxic-ischemic injury in neonates makes it a potentially useful tool for assessing future neuroprotective strategies for neonatal hypoxic-ischemic injury.

Brain↗

PubMed2002

Characteristics and mechanism of surface diffusion in reversed-phase liquid chromatography using various alkyl ligand bonded silica gels.

Kinetic and thermodynamic parameters concerning surface diffusion were derived in reversed-phase liquid chromatography (RPLC) systems using a series of silica gel packing materials bonded with C1, C4, C8, and C18 alkyl ligands. In this paper, a more detailed study on some characteristics and the mechanism of surface diffusion in the RPLC systems using the different alkyl ligand bonded silica gels was made from a thermodynamic point of view by analyzing the surface diffusion data with consideration of the correlation between the parameters concerning surface diffusion and those relating to the retention equilibrium. The mechanism of surface diffusion seems to be the same irrespective of the length of the alkyl ligands because of the presence of the extrathermodynamic relationships, i.e., the enthalpy-entropy compensation and the linear free energy relationship. It was indicated that the surface diffusion coefficient (Ds) of weakly retained compounds was of the same order of magnitude with corresponding molecular diffusivity and that Ds decreased with increasing retention. The activation energy of surface diffusion (Es) was formulated as a linear function of the isosteric heat of adsorption (Qst). A modified Arrhenius equation, which is derived by taking into account the linear correlation between the two thermodynamic parameters Es and Qst, appropriately explains the intrinsic characteristics and mechanism of surface diffusion.

Journal Article↗

PubMed2005

Diffusion of uncharged probe reveals structural changes in polyacids initiated by their neutralization: poly(acrylic acids).

The diffusion studies of the uncharged probe (1,1'-ferrocenedimethanol) have been successfully applied for the evaluation of the changes in the three-dimensional structure of poly(acrylic acids) of various molecular weights (ranging from 2000 to 4,000,000 g/mol) during their neutralization with a strong base. The qualitative picture of the macromolecule arrangement during the titration of the polyacids has been obtained from the conductometric measurements. The characteristic changes in the poly(acrylic acid) conductivity are practically the same for all polyacids examined and are in a very good agreement with the predictions of our theoretical model of the polyelectrolyte conductance. The transformation of the polyelectrolyte solution into the gel-like or gel phase has been investigated more quantitatively by tracing the changes in the diffusion coefficient of the uncharged probe redox system. The probe diffusivities, D, were determined using steady-state voltammetry at microelectrodes for a wide range of neutralization degree, alpha, of the polyacids tested. The dependencies of D versus alpha are of similar shape for all poly(acrylic acids). The first parts of the dependencies reflect a rapid increase in D (up to neutralization degree of either 45% for the lowest molecular-weight poly(acrylic acid) or 75-80% for other polyacids). They are followed by the parts of a slight drop in the diffusion coefficient. The changes in the probe diffusivity become stronger as the molecular weight of poly(acrylic acid) increases. The maximum probe diffusion coefficients are greater than the initial values in the pure polyacid solutions by 14, 24, 19, 30, and 28% for poly(acrylic acid) of molecular weights of 2000, 450,000, 1,250,000, 3,000,000, and 4,000,000 g/mol, respectively. The variation in the probe diffusion coefficient qualitatively follows the line of the changes in the macroscopic viscosity of the polyelectrolyte system. This is in contrast to the predictions of the Stokes-Einstein relation and, therefore, suggests that the changes in the probe diffusion rate are mainly due to the structural changes in the polyacrylate medium and the macromolecular rearrangements induced by the chemical, acid-base reaction. By adapting the obstruction model for diffusion in homogeneous gels, the transport characteristics of the probe were converted into the structural characteristics of the polyelectrolytic systems. It has been found that the most ordered structure of the polyelectrolyte, or in other words the most permeable structure, is obtained when poly(acrylic acid) is neutralized at 75-80%.

Journal Article↗

PubMed2006

Rubidium impurity diffusion in a poly(ethylene oxide)-sodium iodide polymer electrolyte.

Diffusion of the radioisotope (86)Rb in an amorphous polymer-salt complex consisting of poly(ethylene oxide) and sodium iodide was found to be faster at all temperatures investigated than tracer self-diffusion of the smaller alkali metal cation (22)Na. This is the striking result of the first study on impurity diffusion in a polymer electrolyte system and a comparison with ionic self-diffusion and conductivity data previously obtained from the same system. The experimental findings can be rationalized within an ion transport model based on the occurrence of charged single ions and neutral ion pairs. Simultaneous analysis of all data revealed that the diffusivity of Rb(+) is likely to be lower than that of Na(+). Similarly, the diffusivity of RbI(0) pairs was found to be smaller than that of NaI(0) pairs. Surprisingly, the faster overall transport of Rb as measured by radiotracer diffusion appears to be due to a relatively large fraction of RbI pairs, in conjunction with the finding that the ion pair diffusivities exceed the single cation diffusivities by 2 orders of magnitude.

Journal Article↗

PubMed2006

Structural and diffusion characterizations of steam-stable mesostructured zeolitic UL-ZSM-5 materials.

A series of mesoporous UL-ZSM-5 materials (Si/Al = 50) with different micro- and mesoporosity as well as crystallinity was prepared following the procedure proposed in one of our recent studies (Trong-On, D.; Kaliaguine, S. Angew. Chem. Int. Ed. 2001, 40, 3248-3251. Trong-On, D.; Kaliaguine, S. U.S. Patent 6,669,924, B1, 2003). These materials have zeolitic structure in the form of nanoparticles intergrown in the walls of the amorphous wormhole-like aluminosilicate mesopores of Al-Meso-50, which was used as a precursor in the synthesis. The structure, crystallinity, and textural properties of the synthesized materials, as well as a reference ZSM-5 zeolite sample, were determined by X-ray diffraction (XRD), transmission electron microscopy (TEM)/scanning electron microscoy (SEM) analyses, Fourier transform infrared spectroscopy (FTIR), 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR), and nitrogen adsorption/desorption techniques. The acid properties were examined by FTIR of adsorbed pyridine. UL-ZSM-5 materials were shown to be highly hydrothermally stable. The diffusion of two C7 hydrocarbons, i.e., n-heptane and toluene, in four UL-ZSM-5 materials with different microporosities, related acidities, and crystallinities were investigated using the zero-length column (ZLC) method. Furthermore, the wormhole-like mesostructured aluminosilicate precursor (Al-Meso-50) and a reference MFI zeolite sample were also investigated using the same technique. A theoretical model considering a combination of mesopore diffusion (with surface slip in the main channels) with an activated, mainly surface diffusion mechanism in the intrawall biporous structure, was proposed and employed to interpret the experimental ZLC results. A classical Knudsen type of diffusion was replaced by an activated surface slip type of diffusion mechanism in the mesopores. The transport of n-heptane in UL-ZSM-5 materials was found to be mainly controlled by mesopore diffusion in the main-channel structure, while that of toluene was dominated by the intrawall diffusion process. Diffusion activation energies of n-heptane are about 2 times higher in comparison to toluene, which has a larger kinetic diameter. The main mesopore channel structure seems to appreciably contribute to the overall mass transport. Furthermore, the effect of hydrothermal treatment (20% steam at 800 degrees C for 24 h) on the diffusion of these two sorbates on UL-ZSM-5 materials was also evaluated.

Journal Article↗