Biomedical subjects

Thomas Buhse

Publications and source records attributed to Thomas Buhse.

3 recordsLinked to original sources

PubMed2003

Kinetic analysis of artificial peptide self-replication. Part I: the homochiral case.

Computational kinetic analysis of a lately discovered homochiral peptide self-replicator is presented. A 6-step kinetic model was designed that addresses the main reactions and hydrophobic interactions involved in this template-directed, autocatalytic system and that gave rise to excellent fitting of 4 previously published independent experimental series. The model sheds light on the mechanistic principle of the reaction system and illustrates directly a number of dynamic properties such as the observed autocatalytic efficiency. It was found that the dynamics are basically governed by two reversible hydrophobic interactions: between the template and a peptide fragment and between two template species. The later association was determined to be considerably more favored, which leads to the predominant presence of the catalytically inactive template dimer in the reaction system. Our results show that the involvement of a template trimer is not necessary to obtain the observed fittings.

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PubMed2003

Kinetic analysis of artificial peptide self-replication. Part II: the heterochiral case.

A kinetic model has been designed to describe and to analyze the stereoselective behavior of a recently discovered heterochiral template-directed peptide self-replicator by Ghadiri and co-workers [Nature 409 (2001) 797-801]. It turned out that previous assumptions stating that exclusively homochiral species participate in a stereoselective and autocatalytic pathway and that heterochiral species originate only from uncatalyzed background reactions could not be validated by our model. On the contrary, excellent fitting of experimental data indicated that the whole combinatorial variety of possible cross-catalytic processes involving L- and D- peptide species play an important role and need to be taken into account. The system shows no net creation of chiral matter but only a redistribution of the initially present chiral material. Both, the separation of an optically inactive meso-type template dimer and a slight chiroselective autocatalytic effect, contribute to a predicted amplification of enantiomeric excess that, in some cases, can simultaneously result in a substantial amount of optically active matter.

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PubMed2002

Viscoelasticity in the diffuse electric double layer.

The electroacoustical impedance of the quartz crystal microbalance (QCM) in contact with aqueous electrolyte solutions was measured using the transfer function method in a flow injection system . Measurements of both components of the impedance of the QCM, the resistance R and the inductive reactance XL, have been performed for modified and bare gold and silver surfaces and for different concentrations of several aqueous electrolyte solutions. For the experimental concentration range of 0-50 mM, unexpectedly the QCM impedance does not follow the Kanazawa equation, as is usual for bulk newtonian liquids. This behavior indicates the presence of a nanometric sized viscoelastic layer between the piezoelectric crystal and the bulk electrolyte solution. This layer can only be identified as the Gouy-Chapman diffuse double layer (DDL). Its elasticity and viscosity have been estimated by the measurement of R and XL. The viscoelasticity of the DDL appears to be independent of the chemical nature of the surface and of the solution viscosity but strongly dependent on the surface charge, the bulk electrolyte concentration and the dielectric constant of the solvent.

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