Biomedical subjects

J R van der Maarel

Publications and source records attributed to J R van der Maarel.

6 recordsLinked to original sources

PubMed2001

Dynamics of spin I=3/2 under spin-locking conditions in an ordered environment.

We have derived approximate analytic solutions to the master equation describing the evolution of the spin I=3/2 density operator in the presence of a radio-frequency (RF) field and both static and fluctuating quadrupolar interactions. Spectra resulting from Fourier transformation of the evolutions of the on-resonance spin-locked magnetization into the various coherences display two satellite pairs and, in some cases, a central line. The central line is generally trimodal, consisting of a narrow component related to a slowly relaxing mode and two broad components pertaining to two faster relaxing modes. The rates of the fast modes are sensitive to slow molecular motion. Neither the amplitude nor the width of the narrow component is affected by the magnitude of the static coupling, whereas the corresponding features of the broad components depend in a rather complicated manner on the spin-lock field strength and static quadrupolar interaction. Under certain experimental conditions, the dependencies of the amplitudes on the dynamics are seen to vanish and the relaxation rates reduce to relatively simple expressions. One of the promising emerging features is the fact that the evolutions into the selectively detected quadrupolar spin polarization order and the rank-two double-quantum coherence do not exhibit a slowly relaxing mode and are particularly sensitive to slow molecular motion. Furthermore, these coherences can only be excited in the presence of a static coupling and this makes it possible to discern nuclei in anisotropic from those in isotropic environment. The feasibility of the spin-lock pulse sequences with limited RF power and a nonvanishing average electric field gradient has been demonstrated through experiments on sodium in a dense lyotropic DNA liquid crystal.

Crystallization↗

PubMed2000

A model for the dynamics of spins 3/2 in biological media: signal loss during radiofrequency excitation in triple-quantum-filtered sodium MRI.

We have derived the differential equations that describe the dynamics of spin-3/2 nuclei in the presence of radiofrequency (RF) fields and both static and fluctuating quadrupolar interactions. The formalism presented was used to predict the sodium triple-quantum-filtered (TQ-filtered) signal loss in a whole-body scanner, where the widths of the hard 90 degrees RF pulses are on the same order of magnitude as the transverse relaxation times. A small piece of bovine nasal cartilage, known for exhibiting residual quadrupolar splittings, was used to test the theory. The sample was modeled as consisting of small domains, each characterized by a static quadrupolar interaction constant, with an overall Gaussian distribution across the sample. An increase of about 15% in the TQ-filtered signal strength, as the 90 degrees RF pulse width was decreased from 500 to 100 micros, was predicted and demonstrated experimentally for this particular sample.

Animals↗

PubMed1999

Effect of spatial inhomogeneity in dielectric permittivity on DNA double layer formation.

In solutions of tetramethylammonium (TMA+) DNA (double stranded) without added low-molecular-weight salt, the counterion radial density is calculated using the cylindrical Poisson-Boltzmann equation with a distance-dependent quasimacroscopic dielectric permittivity. Comparisons with small-angle neutron scattering data indicate that any inhomogeneity in dielectric permittivity is confined to one or two solvent layers from the DNA surface. At least for TMA+, which may be too large to penetrate the grooves of DNA to any significant extent, dielectric inhomogeneity modeled in this way has no detectable effect on the radial distribution.

Biophysical Phenomena↗

PubMed1998

Liquid crystal formation in DNA fragment solutions.

The critical volume fractions pertaining to the formation of DNA liquid crystals were obtained from polarization microscopy, 31P-nmr, and phase separation experiments. The DNA length (approximately one to two times the persistence length 50 nm), ionic strength, and counterion variety dependencies are reported. The cholesteric-isotropic transition is interpreted in terms of the coexistence equations, which are derived from the solution free energy including orientational entropy and excluded volume effects. With the wormlike chain as reference system, the electrostatic contribution to the free energy is evaluated as a thermodynamic perturbation in the second virial approximation with a Debye-Hückel potential of mean force. The hard core contribution has been evaluated with scaled particle theory and/or a simple generalization of the Carnahan-Starling equation of state for hard spheres. For sufficiently high ionic strengths, the agreement is almost quantitative. At lower amounts of added salt deviations are observed, which are tentatively attributed to counterion screening effects. The contour length dependence agrees with a DNA persistence length 50 nm.

Crystallization↗

PubMed1991

The charge structure function in electrolytes and polyelectrolytes.

The relation between charge and dielectric structure functions is examined in the case of electrolytes and polyelectrolytes. When the coupling constant is larger than unity, characteristic features should be observed on the dielectric structure function, in addition to the classical screening effect. We point our the existence of experimental conditions which provide direct information of the dielectric structure at shorter wavelength (lambda 1 nm). They correspond to zero average contrast in scattering experiments.

Journal Article↗

PubMed1991

Counter-ion dynamics in crosslinked poly(styrene sulfonate) systems studied by NMR.

The field dependence of the longitudinal and transverse nuclear magnetic relaxation rates of 23Na+ in aqueous crosslinked Na-poly(styrene sulfonate) (PSS) systems (ion exchange resins) has been obtained as a function of the degree of crosslinking. The relaxation is considerably enhanced relative to solutions of non-crosslinked NaPSS at equal ionizable group concentration. This is due to the dynamic constraints of the polymer chains, which render the averaging of the counter-ion chain interaction less efficient. The field dependence of the relaxation rates in the crosslinked NaPSS systems reveals two processes that are out of the extreme narrowing limit. This is in contrast to the relaxation behavior found in non-crosslinked NaPSS systems. To characterize these processes their correlation times were combined with constants of selfdiffusion to estimate the distances diffused by an ion in order to average the electric field gradient at its nucleus. These two distances are interpreted as characteristic length scales in the network. At all degrees of crosslinking it was found that the smallest of these length scales is roughly equal to the distance between two neighbouring crosslinks. The largest characteristic distance extends over several crosslinks and reflects inhomogeneities in the crosslink concentration. These conclusions were also reached from similar experiments on 7Li+ in LiPSS systems.

Journal Article↗