Partial transfer of enantioselective chiralities from α-methylated amino acids, known to be of meteoritic origin, into normal amino acids

There is overwhelming evidence that meteorites bring α-methylated amino acids to earth with some l(S) enantiomeric excess. How does that get transferred into normal biological molecules? In this brief account, we show that an α-methylated amino acid, d(R)-α-methylvaline, can react with pyruvate and phenylpyruvate salts in dry mixtures to form alanine and phenylalanine with l enantiomeric excesses, under sensible prebiotic conditions. Thus the meteoritic l(S) excesses of this compound would produce excess d-alanine and d-phenylalanine, which are found in some organisms.     

Existence and positivity of solutions of a fourth-order nonlinear PDE describing interface fluctuations

We study the partial differential equation which arose originally as a scaling limit in the study of interface fluctuations in a certain spin system. In that application x lies in R, but here we study primarily the periodic case × R S¹. We establish existence, uniqueness, and regularity of solutions, locally in time, for positive initial data in H¹(S¹), and prove the existence of several families of Lyapunov functions for the evolution. From the latter we establish a sharp connection between existence globally in time and positivity preservation: if [0], T*) is a maximal half open interval of existence for a positive solution of the equation, with T* < ∞, then lim_tT* w(t,·) exists in C¹(S¹) but vanishes at some point. We show further that if T* > (1 + √3)/16π² √3 then T* = ∞ and lim_t∞ w(t,.) exists and is constant. We discuss also some explicit solutions and propose a generalization to higher dimensions. © 1994 John Wiley & Sons, Inc.     

Modeling spatial patterns in Dictyostelium

The life cycle of Dictyostelium discoideum provides a striking example of the transition from single cell behavior to multicellular cooperativity. In this paper the status of the attempts at making semiquantitative models of the aggregation phase of this cycle is reviewed. Specifically, it is discussed how the propagation of cAMP waves is a typical example of excitable signaling, which is then rendered unstable by coupling to cell chemotaxis. To investigate the streaming pattern that emerges from this clumping instability, we next turn to a new simulation strategy, which couples dynamical cell-like entities ("bions") to continuum chemical concentration fields. Finally, we discuss two directions for further research: One is the study of the robustness with respect to the variation of system parameters (such as the cell density) exhibited by the biological system, but not by any simple model. The other concerns going beyond the aggregation phase to tackle the three-dimensional problem of slug formation and motion.     

Development of Molecular Mechanics Torsion Parameters for alpha,beta-Cyclopropyl Ketones and Conformational Analysis of Bicyclo[m.1.0]alkan-2-ones

Conformations of cyclopropyl methyl ketone have been studied using ab initio methods in an effort to quantify the effects of conjugative overlap between the cyclopropane ring and an adjacent ketone carbonyl. Results were comparable with previous experimental and theoretical studies. Cyclopropyl methyl ketone exhibits a global energy minimum in the s-cis conformer and a local energy minimum near the s-trans conformer. The potential energy curve obtained was used to derive torsion parameters which were employed in molecular mechanics studies of the conformations of the set of bicyclo[m.1.0]alkan-2-ones having larger ring sizes from five- to 16-membered. Similar conformations for the cyclopropyl ketone substructure are observed for all the medium and large ring systems examined. Possible synthetic ramifications of local conformational anchoring by this functional group array are discussed.     

On the interpretation of fluorescence anisotropy decays from probe molecules in lipid vesicle systems

Measurements of fluorescence depolarization decays are widely used to obtain information about the molecular order and rotational dynamics of fluorescent probe molecules in membrane systems. This information is obtained by least-squares fits of the experimental data to the predictions of physical models for motion. Here we present a critical review of the ways and means of the data analysis and address the question how and why totally different models such as Brownian rotational diffusion and wobble-in-cone provide such convincing fits to the fluorescence anistropy decay curves. We show that while these models are useful for investigating the general trends in the behavior of the probe molecules, they fail to describe the underlying motional processes. We propose to remedy this situation with a model in which the probe molecules undergo fast, though restricted local motions within a slowly rotating cage in the lipid bilayer structure. The cage may be envisaged as a free volume cavity between the lipid molecules, so that its position and orientation change with the internal conformational motions of the lipid chains. This approach may be considered to be a synthesis of the wobble-in-cone and Brownian rotational diffusion models. Importantly, this compound motion model appears to provide a consistent picture of fluorescent probe behavior in both oriented lipid bilayers and lipid vesicle systems.