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Biomedical subjects

Marieke Kranenburg

Publications and source records attributed to Marieke Kranenburg.

5 recordsLinked to original sources

Phase behavior of model lipid bilayers.

We investigated the phase behavior of double-tail lipids, as a function of temperature, headgroup interaction and tail length. At low values of the head-head repulsion parameter a(hh), the bilayer undergoes with increasing temperature the transitions from the subgel phase L(c) via the flat gel phase L(beta) to the fluid phase L(alpha). For higher values of a(hh), the transition from the L(c) to the L(alpha) phase occurs via the tilted gel phase L(beta)(') and the rippled phase P(beta)('). The occurrence of the L(beta)(') phase depends on tail length. We find that the rippled structure (P(beta)(')) occurs if the headgroups are sufficiently surrounded by water and that the ripple is a coexistence between the L(c) or L(beta)(') phase and the L(alpha) phase. The anomalous swelling, observed at the P(beta)(') --> L(alpha) transition, is not directly related to the rippled phase, but a consequence of conformational changes of the tails.

Biophysical Phenomena↗

Simulating the effect of alcohol on the structure of a membrane.

Adsorption of alcohol molecules or other small amphiphilic molecules in the cell membrane can induce significant changes in the structure of the membrane. To understand the molecular mechanisms underlying these structural changes, we developed a mesoscopic membrane model. Molecular simulations on this model nicely reproduce the experimental phase diagrams. We find that alcohol can induce an interdigitated structure in which the normal bilayer structure changes into a monolayer in which the alcohol molecules screen the hydrophobic tails from the water phase. We compute the effect of the chain length of the alcohol on the phase behaviour of the membrane. At low concentrations of alcohol, the membrane has domains of the interdigitated phase that are in coexistence with the normal membrane phase. We use our model to clarify some of the experimental questions related to the structure of the interdigitated phase and put forward a simple model that explains the alcohol chain length dependence of the stability of this interdigitated phase.

Alcohols↗

Simulating induced interdigitation in membranes.

In this study we introduce a mesoscopic lipid-water-alcohol model. Dissipative particle dynamics (DPD) simulations have been used to investigate the induced interdigitation of bilayers consisting of double-tail lipids by adding alcohol molecules to the bilayer. Our simulations nicely reproduce the experimental phase diagrams. We find that alcohol can induce an interdigitated structure where the common bilayer structure changes into monolayer in which the alcohol molecules screen the hydrophobic tails from the water phase. At low concentrations of alcohol the membrane has domains of the interdigitated phase that are in coexistence with the common membrane phase. We compute the effect of the chain length of the alcohol on the phase behavior of the membrane and show that the stability of the interdigitated phase depends on the length of the alcohol. We show that we can reproduce the experimental hydrophobic thickness of the bilayer for various combinations of lipids and alcohols. We use our model to clarify some of the experimental questions related to the structure of the interdigitated phase and put forward a simple model that explains the alcohol chain length dependence of the stability of this interdigitated phase.

Alcohols↗

Molecular simulations of mesoscopic bilayer phases.

Dissipative particle dynamics simulations are used to study the self-assembly of lipids into bilayers. With a simple mesoscopic lipid-water model, we observe the formation of the liquid crystalline phase L(alpha) and gel phases in which the tails are interdigitated L(betaI) or noninterdigitated L(beta). For double-tail lipids experiments show all three phases, while for single-tail lipids only L(beta) and L(alpha) are observed. We show that at sufficiently high head-head repulsion the L(betaI) is stable for single-tail lipids. This suggests that it might be possible to induce an L(beta)-->L(betaI) transition by adding chaotropic salts.

Biophysics↗

The Reactivity of o-Hydroxybenzyl Alcohol and Derivatives in Solution at Elevated Temperatures.

The reactivity of o-hydroxybenzyl alcohol (o-HBA, 1), as a model compound for lignin, has been studied in various solvents between 390 and 560 K. Both in polar and apolar solvents the benzylic cation is the reactive intermediate. In alcoholic solvents, the benzylic cation reacts with the solvent to give the corresponding ethers. Relative reaction rates have been determined for different alcohols; a factor of 14 is encountered between the most (methanol) and least (tert-butyl alcohol) reactive ones. The etherification is reversible, in contrast to the electrophilic aromatic substitution with phenol and anisole, for which k(PhOH) = 1 x 10(5) M(-)(1) s(-)(1) and k(anisole) = 1 x 10(4) M(-)(1) s(-)(1), at 424 K. In apolar hydroaromatic solvents, 7H-benz[de]anthracene, 9,10-dihydroanthracene, and 9,10-dihydrophenanthrene, the formation of o-cresol proceeds via hydride transfer from the solvent to the benzylic cation; rate constants at 555 K are 2 x 10(6), 5 x 10(4), and 5 x 10(3) M(-)(1) s(-)(1), respectively.

Journal Article↗