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PubMed1997

Magnetic resonance microscopy studies of cation diffusion in cartilage.

The diffusion of copper ions in bovine nasal cartilage (BNC), a dense connective tissue, was investigated to further the understanding of ion transport in charged biopolymer systems. Using an inversion-recovery null-point imaging technique, it was found that the diffusion rate of divalent copper ions into cartilage was significantly lower in normal BNC than in BNC in which the matrix fixed charges had been reduced by enzymatic digestion or acid neutralization. In normal cartilage, counterion diffusion was not well described by a simple Fickian process, likely owing to the high charge density of the constituent molecules. In contrast, in both digested and acid neutralized BNC, counterion diffusion appeared Fickian. Features of the ion transport process were modeled using a diffusion equation which included a linear sorption term to account for cation binding. The diffusion coefficient of copper in cartilage increased with decreasing matrix fixed charge and was constant for reservoir concentrations up to 30 mM. The activation energy for the diffusion of copper into BNC was determined to be 34.5 kJ/mol.

Animals↗

PubMed1998

Extravascular diffusion of tirapazamine: effect of metabolic consumption assessed using the multicellular layer model.

PURPOSE: Hypoxia-selective cytotoxic agents, like tirapazamine (TPZ), must diffuse considerable distances in tumors to reach their target cell population. This study uses a new three-dimensional tissue culture model, in which cells are grown as multicellular layers (MCL), to investigate whether metabolic consumption of TPZ is sufficiently rapid to compromise its extravascular diffusion in tumors. METHODS AND MATERIALS: V79-171b and MGH-U1 cells were grown as MCL to thicknesses of approximately 120 and 360 microm respectively. The extent of hypoxia in MCL, as assessed by EF5 binding, was modulated by altering gas-phase O2 content, and flux of TPZ through MCL was investigated by high-performance liquid chromatography (HPLC). Data were fitted to a diffusion-reaction mathematical model to determine the diffusion coefficient of TPZ in the MCL (DM) and the rate of its metabolic consumption under anoxia. These parameters were used to simulate TPZ transport in tumors. RESULTS: The flux of TPZ through well-oxygenated MCL (equilibrated with 95% O2) was well fitted as Fickian diffusion without reaction, with a D(M) of 7.4 x 10(-7) cm2s(-1) (12-fold lower than in culture medium) for V79 and 1.3 x 10(-6) cm2s(-1) for MGH-U1 MCL. Flux of TPZ was suppressed under anoxia, and fitting the data required inclusion of a reaction term with a rate constant for metabolic consumption of TPZ of 0.52 min(-1) for V79 and 0.31 min(-1) for MGH-U1 MCL. These transport parameters would translate into a 43% or 30% decrease respectively in TPZ exposure, as a result of drug metabolism, in the center of a slab of anoxic tissue 100 microm in thickness. CONCLUSIONS: MCL cultures provide an in vitro model for investigating the interaction between metabolic consumption and diffusion of bioreductive drugs. If rates of diffusion and metabolism similar to those measured in V79 and MGH-U1 MCL apply in tumors, then cells in large confluent regions of hypoxia would be partially protected by failure of TPZ penetration. Simulation of extravascular transport of TPZ-like bioreductive drugs demonstrates that the optimum metabolic rate constant is determined by two competing requirements: it should be high enough to ensure potent cytotoxicity under hypoxia, yet low enough that penetration is not severely compromised.

Animals↗

PubMed2003

Characterization of normal brain and brain tumor pathology by chisquares parameter maps of diffusion-weighted image data.

OBJECTIVE: To characterize normal and pathologic brain tissue by quantifying the deviation of diffusion-related signal from a simple monoexponential decay, when measured over a wider than usual range of b-factors. METHODS AND MATERIALS: Line scan diffusion imaging (LSDI), with diffusion weighting at multiple b-factors between 100 and 5000 s/mm(2), was performed on 1.5 T clinical scanners. Diffusion data of single slice sections were acquired in five healthy subjects and 19 brain tumor patients. In-patients, conventional T2-weighted and contrast-enhanced T1-weighted images were obtained for reference purposes. The chisquare (chi(2)) error parameter associated with the monoexponential fits of the measured tissue water signals was then used to quantify the departure from a simple monoexponential signal decay on a pixel-by-pixel basis. RESULTS: Diffusion-weighted images over a wider b-factor range than typically used were successfully obtained in all healthy subjects and patients. Normal and pathologic tissues demonstrated signal decays, which clearly deviate from a simple monoexponential behavior. The chi(2) of cortical and deep grey matter was considerably lower than in white matter. In peritumoral edema, however, chi(2) was 68% higher than in normal white matter. In highly malignant brain tumors, such as glioblastoma multiforme (GBM) or anaplastic astrocytoma, chi(2) values were on average almost 400% higher than in normal white matter, while for one low grade astrocytoma and two cases of metastasis, chi(2) was not profoundly different from the chi(2) value of white matter. Maps of the chi(2) values provide good visualization of spatial details. However, the tumor tissue contrast generated appeared in many cases to be different from the enhancement produced by paramagnetic contrast agents. For example, in cases where the contrast agent only highlighted the rim of the tumor, chi(2) enhancement was present within the solid part of the tumor. CONCLUSION: The deviation from a purely monoexponential diffusion signal decay becomes evident as diffusion encoding is extended well beyond the normal range. The chi(2) error parameter as a measure of this deviation seems to provide sufficient lesion contrast to permit differentiation of malignant brain tumors from normal brain tissue.

Adult↗

PubMedDate not supplied

Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media.

We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects.

Diffusion↗

PubMedDate not supplied

Strong gradients for spatially resolved diffusion measurements.

A new multilayer approach to gradient coil design, which allows the production of very strong gradient coils with reasonable resistance and consequent power dissipation, has been developed. Using this approach we have designed and built a strong z-gradient coil that will accommodate vertically mounted samples contained in 5-mm nuclear magnetic resonance tubes. The coil has an efficiency of 1.73 Tm-1A-1, an inductance of 49 microH, and a resistance of 1.8 omega, with a homogeneous volume consisting of a central cylinder of 4.5-mm length and diameter. This coil has been used to monitor the diffusion of water in Nylon 6.6 at room temperature, during desorption. This system is difficult to monitor via nuclear magnetic resonance (NMR), because the diffusion coefficients are typically less than 10(-13) m2s-1, while the T2 relaxation time is less than 1 ms even when the sample is fully saturated. The resulting measurements show a strong concentration dependence of the T2 relaxation time and self-diffusion coefficient of the absorbed water. The measured concentration profiles are consistent with a Fickian diffusion process with a concentration-dependent diffusion coefficient. The measured self-diffusion values are in reasonable agreement with those inferred from the variation of the concentration profiles as a function of time, using the one-dimensional Fickian diffusion equation.

Absorption↗

PubMed1998

Water signal attenuation in diffusion-weighted 1H NMR experiments during cerebral ischemia: influence of intracellular restrictions, extracellular tortuosity, and exchange.

The "concept of restricted intracellular water diffusion at permeable boundaries", which was recently used to model diffusion-weighted 1H NMR experiments on glioma cells, was applied to measurements on the rat brain in vivo. Combined with the "concept of extracellular tortuosity", various physiological states of the brain were simulated. Hereby, a variable intracellular volume fraction, intracellular exchange time, and extracellular tortuosity factor were considered for young, adult, and ischemic rat brains. The model simulated the cytotoxic shift of extracellular water, changes in membrane permeability and tissue morphology, and was able to explain the diffusion time dependence as well as the non-monoexponentiality of the diffusion attenuation curves. Preliminary diffusion time dependent experiments on the healthy rat brain (1H NMR imaging) agreed well with the theoretical concept. Hereby, the intracellular water signal was separated from extracellular signal contributions by large diffusion weighting. It showed the characteristic of restricted diffusion as well as a signal decay due to the exchange of intracellular water across the plasma membrane. A map of the mean intracellular exchange time for water in living animal brain was determined, and the upper limit in rat brain was evaluated to 15 ms. The presented methods can be applied to correlate local differences in a map of exchange times with tissue morphology and to detect pathological deviations of the exchange time, e.g., during ischemia.

Animals↗

PubMed1999

A study of rotationally invariant and symmetric indices of diffusion anisotropy.

This study investigated the properties of a class of rotationally invariant and symmetric (relative to the principal diffusivities) indices of the anisotropy of water self-diffusion, namely fractional anisotropy (FA), relative anisotropy (RA), and volume ratio (VR), with particular emphasis to their measurement in brain tissues. A simplified theoretical analysis predicted significant differences in the sensitivities of the anisotropy indices (AI) over the distribution of the principal diffusivities. Computer simulations were used to investigate the effects on AI image quality of three magnetic resonance (MR) diffusion tensor imaging (DTI) acquisition schemes, one being novel: the schemes were simulated on cerebral model fibres varying in shape and spatial orientation. The theoretical predictions and the results of the simulations were corroborated by experimentally determined spatial maps of the AI in a normal feline brain in vivo. We found that FA mapped diffusion anisotropy with the greatest detail and SNR whereas VR provided the strongest contrast between low- and high-anisotropy areas at the expense of increased noise contamination and decreased resolution in anisotropic regions. RA proved intermediate in quality. By sampling the space of the effective diffusion ellipsoid more densely and uniformly and requiring the same total imaging time as the published schemes, the novel DTI scheme achieved greater rotational invariance than the published schemes, with improved noise characteristics, resulting in improved image quality of the AI examined. Our findings suggest that significant improvements in diffusion anisotropy mapping are possible and provide criteria for the selection of the most appropriate AI for a particular application.

Animals↗

PubMedDate not supplied

Herpes simplex encephalitis: diffusion MR imaging findings.

We studied five patients with herpes simplex encephalitis type 1 with diffusion-weighted MR imaging, as this sequence provides information regarding tissue integrity. Diffusion-weighted imaging was obtained using the echo-planar sequence. True diffusion images (i.e. b=1000s/mm(2) images), and the ADC (apparent diffusion coefficient) values were studied. In addition, diffusion imaging of 12 normal cases, 46 patients with acute ischemia (cytotoxic edema), and 12 patients with vasogenic edema were studied for comparison. In patients with herpes encephalitis, two distinct types of diffusion imaging findings (on b=1000s/mm(2) images, and ADC maps) were noted: lesions similar to cytotoxic edema, and lesions similar to vasogenic edema. The patients with the former type of lesions had fulminating disease, and were in severe clinical condition. Those with the latter represented early cases, and they were in fairly good clinical condition with a good outcome by prompt therapy. Diffusion imaging appears to be a promising sequence to monitor the changes in the brain tissue in herpes encephalitis, and in other infections as well with respect to restriction of movement (cytotoxic edema) or relatively high-motion (vasogenic edema) of water molecules, providing data on the severity of the disease.

Adolescent↗

PubMedDate not supplied

Discrimination of an infected brain tumor from a cerebral abscess by combined MR perfusion and diffusion imaging.

The aim of this study was to investigate the signal characteristics of the abscess wall and tumor wall on diffusion-weighted and perfusion-weighted images and thus to evaluate the feasibility of using combined MR diffusion and perfusion imaging to differentiate pyogenic cerebral abscess from infected brain tumor. The tumor wall of various types of cystic or necrotic brain tumor was significantly hyperintense relative to that of cerebral abscess wall on both diffusion-weighted images and regional cerebral blood volume maps. Sixteen patients who had cerebral masses with large cystic or necrotic cavities were imaged to generate diffusion-weighted images and regional cerebral blood volume maps using single-shot echoplanar imaging (EPI) pulse sequences. Apart from qualitative analysis, apparent diffusion coefficients (ADC) as well as regional cerebral blood volume (rCBV) ratios were calculated from the abscess wall and peripheral tumor wall and comparison was made by using Student's t-test. The tumor wall of various types of cystic or necrotic brain tumor had significantly lower ADCs relative to those of the abscess wall (P<0.005) and thus appeared relatively hyperintense on diffusion-weighted images. The mean rCBV ratio relative to normal white matter (2.90+/-0.62) of the peripheral tumor wall of various types of cystic or necrotic brain tumor were significantly larger than the mean rCBV ratio (0.45+/-0.11) of the pyogenic cerebral abscess wall (P<0.001) by Student's t-test. It is concluded that the combined MR diffusion and perfusion imaging might be capable of differentiating an infected brain tumor from a pyogenic cerebral abscess.

Adenocarcinoma↗

PubMedDate not supplied

MR diffusion-weighted imaging of kidney: differentiation between hydronephrosis and pyonephrosis.

The objective of the study was to evaluate the capability and reliability of the magnetic resonance (MR) diffusion-weighted imaging (DWI) in differentiation between hydronephrosis and pyonephrosis. Single-shot echoplanar MR diffusion-weighted imaging was performed in 12 patients who had dilatation of the renal pelvis and calyces detected by ultrasonography (US). Microbiological tests confirmed that there were four cases of pyonephrosis and eight cases of hydronephrosis. Signal intensities of the collecting (pelvicalyceal) systems on the diffusion-weighted images and apparent diffusion coefficient (ADC) maps were noted. ADC values of the pelvicalyceal system in all patients were computed and compared using Student's t test. On diffusion-weighted images, the pelvicalyceal system of the hydronephrotic kidney was hypointense while the pelvicalyceal system of the pyonephrotic kidney was markedly hyperintense. The mean ADCs of the hydronephrotic and pyonephrotic renal pelvis were 2.98 +/- 0.65 x 10(-3) and 0.64 +/- 0.35 x 10(-3) mm(2)/s, respectively. The extremely low ADC of the renal pelvis of the pyonephrotic kidney accounted for its signal hyperintensity on diffusion-weighted images as well as signal hypointensity on ADC maps. In conclusion, the MR diffusion-weighted imaging may be a reliable tool to differentiate pyonephrosis from hydronephrosis.

Adult↗

PubMed2003

The application of the convective diffusion model and the film equilibrium model to surfactant-facilitated dissolution of gliclazide.

Gliclazide is practically insoluble in water, and has low dissolution rate. Therefore, it was of interest to improve its dissolution rate using anionic and cationic surfactants. The intrinsic dissolution rates of gliclazide in solutions of sodium dodecyl sulfate (SDS) and in solutions of tetradecyltrimethyl ammonium bromide (TDTMAB) were measured using the rotating disk method to study the convective diffusion transport of drug-loaded micelles. Two different approaches were applied to the experimental data; the convective diffusion model and the film equilibrium model. The two approaches are based on the same fundamental assumptions differing only in their interpretation of the diffusional boundary layer. The results obtained from the film equilibrium model were less satisfactory, and in case of TDTMAB the model was inapplicable (negative diffusion coefficient). While excellent results were obtained from the convective diffusion model. The free solute diffusion coefficient (D(s)) obtained experimentally was 2.47 x 10(-5) cm(2)/s, and the diffusion coefficient of the drug-loaded SDS micelle (D(sm)) estimated was 1.74 x 10(-6) cm(2)/s. The drug-loaded SDS micelle radius was 14 A. The thickness of the diffusional boundary layer was 54 and 22 microm for the free solute and the drug-loaded SDS micelle, respectively. TDTMAB showed lower effect in improving the dissolution rate of gliclazide than SDS. The drug-loaded TDTMAB micelle diffusion coefficient was 1.03 x 10(-6) cm(2)/s. The radius of the drug-loaded TDTMAB micelle and the boundary layer thickness were 24 A and 19 microm, respectively.

Diffusion↗

PubMed2000

Diffuse component of solar ultraviolet radiation in tree shade.

The first set of quantitative data of diffuse erythemal UV and UV-A radiation in tree shade at a sub-tropical Southern Hemisphere latitude is presented. Over the summer, approximately 60% of the erythemal UV radiation in tree shade is due to the diffuse component. Similarly, approximately 56% of the UV-A radiation in tree shade is due to the diffuse component. In tree shade these diffuse UV percentages are relatively constant from the morning to noon to afternoon periods. In comparison, in full sun, there is a decrease in the percentage of diffuse UV from morning to noon to afternoon. The exposures to diffuse UV on a horizontal plane in tree shade between 9:00 EST and 15:00 EST are of the order of 4 MED (minimum erythemal dose) and 14 J cm(-2) for erythemal UV and UV-A, respectively. The high diffuse UV component in the shade may result in high UV exposures not only to unprotected parts of the body on a horizontal plane, but also in equally high UV irradiances to parts of the body, including the eyes and face, that are not UV protected.

Diffusion↗

PubMed2004

Comparison of single-shot echo-planar and line scan protocols for diffusion tensor imaging.

RATIONALE AND OBJECTIVES: Both single-shot diffusion-weighted echo-planar imaging (EPI) and line scan diffusion imaging (LSDI) can be used to obtain magnetic resonance diffusion tensor data and to calculate directionally invariant diffusion anisotropy indices, ie, indirect measures of the organization and coherence of white matter fibers in the brain. To date, there has been no comparison of EPI and LSDI. Because EPI is the most commonly used technique for acquiring diffusion tensor data, it is important to understand the limitations and advantages of LSDI relative to EPI. MATERIALS AND METHODS: Five healthy volunteers underwent EPI and LSDI diffusion on a 1.5 Tesla magnet (General Electric Medical Systems, Milwaukee, WI). Four-mm thick coronal sections, covering the entire brain, were obtained. In addition, one subject was tested with both sequences over four sessions. For each image voxel, eigenvectors and eigenvalues of the diffusion tensor were calculated, and fractional anisotropy (FA) was derived. Several regions of interest were delineated, and for each, mean FA and estimated mean standard deviation were calculated and compared. RESULTS: Results showed no significant differences between EPI and LSDI for mean FA for the five subjects. When intersession reproducibility for one subject was evaluated, there was a significant difference between EPI and LSDI in FA for the corpus callosum and the right uncinate fasciculus. Moreover, errors associated with each FA measure were larger for EPI than for LSDI. CONCLUSION: Results indicate that both EPI- and LSDI-derived FA measures are sufficiently robust. However, when higher accuracy is needed, LSDI provides smaller error and smaller inter-subject and inter-session variability than EPI.

Adult↗

PubMed2004

Chronoamperometry at micropipet electrodes for determination of diffusion coefficients and transferred charges at liquid/liquid interfaces.

Chronoamperometry was carried out at liquid/liquid interfaces supported at the tip of micropipet electrodes for direct determination of the diffusion coefficient of a species in the outer solution. The diffusion coefficient was used for subsequent determination of the transferred charges per species from the diffusion-limited steady-state current. A large tip resistance of the micropipets causes prolonged charging current so that the faradic current can be measured accurately only at a long-time regime (typically t > 5 ms). At the same time, the long-time current response at the interfaces surrounded by a thin glass wall of the pipets is enhanced by diffusion of the species from behind the pipet tip. Therefore, numerical simulations of the long-time chronoamperometric response were carried out using the finite element method for accurate determination of diffusion coefficients. Validity of the simulation results was confirmed by studying simple transfer of tetraethylammonium ion. The technique was applied for transfer/adsorption reactions of the natural polypeptide protamine and also for Ca2+ and Mg2+ transfers facilitated by ionophore ETH 129. With the diffusion coefficient of protamine determined to be (1.2 +/- 0.1) x 10(-6) cm(2)/s, the ionic charge transferred by each protamine molecule was obtained as +20 +/- 1, which is close to the excess positive charge of protamine. Also, the diffusion coefficient of ETH 129 was determined to demonstrate that each ionophore molecule transfers +0.67 and +1 charge per Ca2+ and Mg2+ transfer, respectively, which corresponds to formation of 1:3 and 1:2 complexes with the respective ions.

Calcium↗

PubMed2005

Trace metal measurements in low ionic strength synthetic solutions by diffusive gradients in thin films.

In view of conflicting reports regarding the performance of DGT in low ionic strength solutions (I < 1 mM), further investigations have been carried out. Minimal washing of the diffusive gel and deployment in 1.0 and 10 mM NaNO3 solutions containing Cu and Cd gave the theoretical response of 1 for [C](DGT)/[C](SOLN), where [C](DGT) is the concentration of metal measured by DGT and [C](SOLN) is the concentration of metal measured directly in the solution by an appropriate analytical method. Erroneously high values for [C](DGT)/[C](SOLN) were obtained when these same gels were deployed at I = 0.1 mM, presumably due to a net negative charge on the gel, attributable to the presence of initiation products of polymerization. However, washing the diffusive gels completely, where the storage solution pH equaled that of deionized water, gave values of approximately 0.5 for [C](DGT)/[C](SOLN) from deployments at I = 0.1 mM, consistent with the lower measured value of the diffusion coefficients at this ionic strength. These results can be explained by the presence of a net positive charge on the gel when it is exhaustively washed, which reduces the effective diffusion coefficient of metal ions by changing their concentration at the gel-solution interface (Donnan partitioning). Diffusive gel equilibration experiments showed the presence of low capacity sites capable of binding metals irrespective of ionic strength. This binding within the diffusive gel does not affect most DGT measurements, as short (4 h) deployments at concentrations of 10 ppb gave theoretical results. Incomplete washing of the resin-gel caused a 5-15% measurement error and a decrease in precision, even at ionic strengths of 10 mM. A high level of accuracy and precision (typically <5%) was maintained during all aspects of this work, even at ionic strengths of 0.1 mM, in contrast to previous results. This is attributable to three factors: (1) exhaustive washing and conditioning protocols, (2) improvements to the DGT sampling device, and (3) low and reproducible blanks due to ultraclean handling procedures. Provided effective diffusion coefficients measured at the same ionic strength are used, the established DGT theory is obeyed irrespective of ionic strength.

Cadmium↗

PubMed1993

Localized interaction of the polyamine methylspermidine with double-helical DNA as monitored by 1H NMR self-diffusion measurements.

The 1H NMR pulsed field gradient self-diffusion method has been used to measure the diffusion coefficient of the polyamine analogue methylspermidine (completely N-methylated spermidine) in DNA solution, as a function of the concentration ratio of methylspermidine to DNA phosphate. Three different DNA's have been investigated: d(GC)4 (8 base pairs), core length calf thymus DNA (approximately 120 base pairs), and sonicated high molecular weight calf thymus DNA (average 7500 base pairs). For a constant ratio of methylspermidine to DNA phosphate, the diffusion coefficient decreases with increasing DNA length. Moreover, at low concentration ratios the diffusion coefficient of methylspermidine approaches a limiting value that is close to that of the DNA molecule. The experimental data are well reproduced by a two-state diffusion model. In this model the diffusion coefficient of the polyamine is a population-weighted average of polyamine associated with DNA (with a diffusion coefficient given by that of the DNA molecule) and polyamine free in solution.

Animals↗

PubMed1984

Lateral diffusion of cytochrome P-450 in phospholipid bilayers.

The lateral diffusion coefficient (D) of cytochrome P-450 (P-450) has been measured in lipid multibilayers with the method of fluorescence recovery after photobleaching. In the liquid-crystal phase of egg phosphatidylcholine (EPC) and dimyristoylphosphatidylcholine (DMPC), the diffusion of P-450 is fast with D about 2 X 10(-8) cm2/s. In DMPC multibilayers, P-450 diffusion dropped by a factor of 20 near the liquid crystal to gel phase transition region, and D is about 5 X 10(-10) cm2/s in the gel phase. A value of 50 mol % of cholesterol reduced the diffusion of P-450 in the liquid-crystal phase only slightly but enhanced the diffusion of P-450 in the gel phase significantly. In EPC membranes, P-450 diffusion underwent a stepwise drop as the cholesterol contents increased from 20 to 30 mol %. With the assumption of a lateral diffusion mediated electron transfer between P-450 and NADPH-P-450 reductase and with D = 2.5 X 10(-8) cm2/s for both enzymes, the reduction rate for P-450 in liposomes was calculated and compared with the reported experimental value.

Cytochrome P-450 Enzyme System↗

PubMed1988

Rotational diffusion of a steroid molecule in phosphatidylcholine membranes: effects of alkyl chain length, unsaturation, and cholesterol as studied by a spin-label method.

Rotational diffusion of cholestane spin-label (CSL), a sterol analogue, in various phosphatidylcholine (PC)-cholesterol membranes was systematically studied by computer simulation of steady-state ESR spectra as a function of chain length and unsaturation of alkyl chains, cholesterol mole fraction, and temperature for better understanding of phospholipid-cholesterol and cholesterol-cholesterol interactions. CSL motion in the membrane was treated as Brownian rotational diffusion of a rigid rod within the confines of a cone imposed by the membrane environment. The wobbling rotational diffusion constant of the long axis, its activation energy, and the cone angle of the confines are obtained for various membranes in the liquid-crystalline phase. The wobbling diffusion constant decreases in the order dilauroyl-PC greater than dimyristoyl-PC greater than dioleoyl-PC approximately dipalmitoyl-PC greater than distearoyl-PC greater than dioleoyl-PC/cholesterol = 3/1 greater than dioleoyl-PC/cholesterol = 1/1 membranes. Activation energy for the wobbling diffusion of the long axis of CSL is strongly dependent on alkyl chain length, unsaturation, and cholesterol mole fraction. It decreases with decrease in alkyl chain length and by introduction of unsaturation in the alkyl chains. In dioleoylphosphatidylcholine membranes, activation energy decreases by a factor of approximately 3 in the presence of 50 mol % cholesterol. Activation energy for wobbling diffusion of CSL in phosphatidylcholine membranes is smaller than the activation energy for translational diffusion of a phospholipid. The former is more dependent on alkyl chain length and unsaturation.(ABSTRACT TRUNCATED AT 250 WORDS)

Alkanes↗