Biomedical subjects

Rainer Kimmich

Publications and source records attributed to Rainer Kimmich.

9 recordsLinked to original sources

PubMed2004

Polymer dynamics under nanoscopic constraints: the "corset effect" as revealed by NMR relaxometry and diffusometry.

A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined in nanoscopic strands, which in turn are embedded in a quasi-solid methacrylate matrix impenetrable to PEO. Both the molecular weight of the PEO and the mean diameter of the strands are variable to a certain degree. Chain dynamics of the PEO in the molten state were examined with the aid of field-gradient NMR diffusometry and field-cycling NMR relaxometry. The dominating mechanism for translational displacements in the nanoscopic strands is shown to be reptation. A formalism for the evaluation of NMR diffusometry is presented, which permits the estimation of the mean PEO strand diameter. Samples of different composition revealed diameters in the range 9-58 nm, in reasonable agreement with electron micrographs. The time scale of the diffusion measurements was 10-300 ms. On the much shorter time scale of field-cycling NMR relaxometry, 10(-9)-10(-4)s, a frequency dispersion of the spin-lattice relaxation time characteristic for reptation clearly showed up in all samples. An effective tube diameter of only 0.6 nm was found even when the strand diameter was larger than the radius of gyration of the PEO chain random coils. The finding that the tube diameter effective on the short time scale of field-cycling NMR relaxometry is much smaller than the diameter of the confining structure is termed the "corset effect", and is traced back to the lack of local free-volume fluctuation capacity under nanoscale confinements. The order of magnitude of the 'pore' diameter, at which the cross-over from confined to bulk chain dynamics is expected, is estimated.

Diffusion↗

PubMed2004

Nuclear magnetic resonance study of the vapor contribution to diffusion in silica glasses with micrometer pores partially filled with liquid cyclohexane or water.

The contribution of the vapor phase to molecular diffusion in porous silica glass (Vitrapor#5; mean pore diameter 1 micrometer) partially filled with cyclohexane (nonpolar) or water (polar) was investigated with the aid of field-gradient NMR diffusometry. Due to the vapor phase, the effective diffusion coefficient of cyclohexane increased up to ten times relative to the value in bulk liquid upon reduction of the pore space filling factor. On the other hand, the effective diffusion coefficient of water first decreases and then increases when the liquid content is reduced. A two-phase exchange theory is presented accounting well for all experimental diffusion features. The diffusion behavior in the samples with micrometer pores under investigation here is in contrast to previous findings for the same solvents in a material with nanometer pores (Vycor; mean pore diameter 4 nm) where the fast-exchange limit had to be assumed [Ardelean et al., J. Chem. Phys. 119, 10358 (2003)]. It is concluded that the pore size plays a crucial role for the relevance of molecular exchange limits relative to the experimental diffusion/exchange time.

Journal Article↗

PubMed2004

Constant time steady gradient NMR diffusometry using the secondary stimulated echo.

A pulse sequence producing a second stimulated echo is suggested for the compensation of relaxation and residual dipolar interaction effects in steady gradient spin echo diffusometry. Steady field gradients of considerable strength exist in the fringe field of NMR magnets, for instance. While the absolute echo time of the second stimulated echo is kept constant throughout the experiment, the interval between the first two radiofrequency pulses is augmented leading to a modulation of the amplitude of that second stimulated echo by self-diffusion only. The unique feature of this technique is that it is of a single-scan/single-echo-signal nature. That is, no reference signals neither of the same pulse sequence nor of separate experiments are needed. The new method was tested with poly(ethylene oxide) melts and proved to provide reliable data for (time dependent) self-diffusion coefficients down to the physical limit (D approximately 10(-15)m(2)/s) when flip-flop spin diffusion starts to become effective.

Journal Article↗

PubMed2004

NMR acceleration mapping in percolation model objects.

An NMR microscopy technique is described that permits direct mapping of local accelerations. The method is tested with water flow through a random site percolation model object and compared with computational fluid dynamics simulations. A general formalism, the "polygon rule," is reported for the design of gradient pulse sequences for phase encoding of higher order motions, or, in other words, for compensation of phase shifts by lower motional orders.

Journal Article↗

PubMed2004

Visualization of transport: NMR microscopy experiments with model objects for porous media with pore sizes down to 50 microm.

Hydrodynamic flow and electric currents through model porous media were investigated. The transport rates through the individual pathways of the pore network are determined by the local width of the pore channels and by the driving mechanism. The model objects represent quasi two-dimensional random site percolation clusters. The calculated design was realized by milling the structure in polystyrene sheets. Velocity maps of stationary flow and current density maps of stationary currents through the cluster were acquired by magnetic resonance imaging methods. The findings were compared to the results of numerical simulations based on the same structure. Since the difference in the transport patterns of the different driving mechanisms are expected to be more pronounced in smaller pore spaces, ultra deep X-ray lithography has been used for the fabrication of downsized model objects with a spatial resolution of better than 50 microm and an aspect ratio as large as 20. First results obtained with these objects are reported.

Computer Simulation↗

PubMed2002

Rayleigh-Bénard percolation transition of thermal convection in porous media: computational fluid dynamics, NMR velocity mapping, NMR temperature mapping.

Stationary thermal convection and heat conduction were studied in random-site percolation clusters in a Rayleigh-Bénard configuration experimentally by NMR microscopy techniques and numerically with the aid of a finite volume method. The porosity of the percolation clusters, and the temperature difference applied to the convection cell were varied. Two-dimensional percolation networks were generated with the aid of a random-number algorithm. The resulting clusters were used as templates for the fabrication of model objects. The convective velocity distribution of silicon oil or ethylene glycol filled into the pore space was mapped and evaluated in the form of histograms. The flow patterns visualized in the simulated and the measured velocity maps show good coincidence. In the histograms, two velocity regimes can be distinguished and attributed to local convection rolls responsible for the low-velocity part, and cluster-spanning flow loops characterized by a high-velocity cut-off, respectively. The maximum velocity as a function of the porosity and the overall temperature difference is shown to be indicative for the hydro-thermodynamic Rayleigh-Bénard instability and the geometrical percolation threshold. The coincidence of the Rayleigh-Bénard instability (modified for porous media) and the percolation transition (modified for closed loops) gives rise to a new critical phenomenon termed the Rayleigh-Bénard percolation transition. It occurs at a certain combination of the porosity and the overall temperature difference in the cell. Temperature maps were recorded with the aid of a relaxation-based NMR technique. The consequence of different thermal conductivities in the matrix and in the fluid is that horizontal-temperature gradients arise even in the absence of flow. This leads to a superposition of uncritical convective flow driven by the horizontal-temperature gradients whenever closed-loop pathways are possible and the critical Rayleigh-Bénard convection based on vertical-temperature gradients.

Journal Article↗

PubMed2002

Maps of electric current density and hydrodynamic flow in porous media: NMR experiments and numerical simulations.

The electric current density in percolation clusters was mapped with the aid of a NMR microscopy technique monitoring the spatial distribution of spin precession phase shifts caused by the currents. A test structure and a quasi-two-dimensional random-site percolation model object filled with an electrolyte solution were examined and compared with numerical simulations based on potential theory. The current density maps permit the evaluation of histograms and of volume-averaged current densities as a function of the probe volume radius as relationships characterizing transport in the clusters. The current density maps are juxtaposed to velocity maps acquired in flow NMR experiments in the same objects. It is demonstrated that electric current and hydrodynamic flow lead to transport patterns deviating in a characteristic way due to the different dependencies of the transport resistances on the pore channel width.

Journal Article↗

PubMed2002

Diffusion on random-site percolation clusters: theory and NMR microscopy experiments with model objects.

Quasi-two-dimensional random-site percolation model objects were fabricated based on computer-generated templates. Samples consisting of two compartments, a reservoir of H2O gel attached to a percolation model object, which was initially filled with D2O, were examined with nuclear magnetic resonance microscopy for rendering proton spin density maps. The propagating proton/deuteron interdiffusion profiles were recorded and evaluated with respect to anomalous diffusion parameters. The deviation of the concentration profiles from those expected for unobstructed diffusion directly reflects the anomaly of the propagator for diffusion on a percolation cluster. The fractal dimension of the random walk d(w) evaluated from the diffusion measurements on the one hand and the fractal dimension d(f) deduced from the spin density map of the percolation object on the other permits one to experimentally compare dynamical and static exponents. Approximate calculations of the propagator are given on the basis of the fractional diffusion equation. Furthermore, the ordinary diffusion equation was solved numerically for the corresponding initial and boundary conditions for comparison. The anomalous diffusion constant was evaluated and is compared to the Brownian case. Some ad hoc correction of the propagator is shown to pay tribute to the finiteness of the system. In this way, anomalous solutions of the fractional diffusion equation could experimentally be verified.

Journal Article↗

PubMed2002

1H detected (13)C echo planar imaging.

Cyclic J cross polarisation (CYCLCROP) is a sensitive method for the noninvasive monitoring of (13)C distributions and fluxes. The PRAWN rotating frame Hartmann-Hahn mixing sequence ameliorates problems associated with sensitivity to Hartmann-Hahn mismatch and reduces RF power deposition. The combination of CYCLCROP with echo planar imaging (EPI) for spatial encoding of the proton detected carbon signal allows efficient use of the available signal to be made, permitting a significant improvement in the temporal resolution of any study. We report here on some initial experiments to demonstrate the feasibility of echo planar proton detected (13)C imaging using CYCLCROP based upon the PRAWN module, including the application of the technique to the measurement of transport and accumulation of (13)C-labelled sucrose in a castor bean seedling. Two methods that can be used to eliminate the effect of the J-splitting in the EP images are presented. In addition, a fast, image-based B(1) field-mapping method which may be used to quantitatively map the low frequency RF field in a dual resonant ((13)C/(1)H) probe is presented. The technique utilises the above described imaging method, permitting fully quantitative, 64x64 axial field maps to be generated in about a minute.

Carbon Isotopes↗