Studies in chiral symmetry breaking crystallization I: The effects of stirring and evaporation rates

Chiral symmetry breaking can be realized in stirred crystallization of Na-ClO₃. We present experimental and theoretical studies of the random distribution of crystal enantiomeric excess (cee) for various stirring and solvent evaporation rates. For a fixed solvent evaporation rate, as the stirring RPM is increased, the probability distribution of cee initially broadens and subsequently develops a sharp peak close to cee = 1. On further increase of stirring rate, the probability distribution once again broadens. This broad probability distribution becomes narrow, with a sharp peak near cee = 1, if the solvent evaporation rate is decreased. Thus we show some ways in which the probability distribution of cee can be controlled in stirred crystallization. In particular, our study shows that the stirring rate and the solvent evaporation rate can be adjusted to maximize crystal enantiomeric excess. © 1995 Wiley-Liss, Inc.     

Chiral asymmetry in spiral galaxies?

Spiral galaxies are chiral entities when coupled with the direction of their recession velocity. As viewed from the Earth, the S‐shaped and Z‐shaped spiral galaxies are two chiral forms. What is the nature of chiral symmetry in spiral galaxies? In the Carnegie Atlas of Galaxies that lists photographs of a total of 1,168 galaxies, we found 540 galaxies, classified as normal or barred spirals, that are clearly identifiable as S‐ or Z‐ type. The recession velocities for 538 of these galaxies could be obtained from this atlas and other sources. A statistical analysis of this sample reveals no overall asymmetry but there is a significant asymmetry in certain subclasses: dominance of S‐type galaxies in the Sb class of normal spiral galaxies and a dominance of Z‐type in the SBb class of barred spiral galaxies. Both S‐ and Z‐type galaxies seem to have similar velocity distribution, indicating no spatial segregation of the two chiral forms. Chirality 13:351–356, 2001. © 2001 Wiley‐Liss, Inc.     

A new theoretical model for the origin of amino acid homochirality

Amino acid homochirality, as a unique behavior of life, could have originated synchronously with the genetic code. In this paper, phosphoryl amino-acid-5′-nucleosides with P-N bond are postulated to be a chiral origin model in prebiotic molecular evolution. The enthalpy change in the intramolecular interaction between the nucleotide base and the amino-acid side-chain determines the stability of the particular complex, resulting in a preferred conformation associated with the chirality of amino acids. Based on the theoretical model, our experiments and calculations show that the chiral selection of the earliest amino acids for L-enantiomers seems to be a strict stereochemical/physicochemical determinism. As other amino acids developed biosynthetically from the earliest amino acids, we infer that the chirality of the later amino acids was inherited from the precursor amino acids. This idea probably goes far back in history, but it is hoped that it will be a guide for further experiments in this area.     

A new theoretical model for the origin of amino acid homochirality

Amino acid homochirality, as a unique behavior of life, could have originated synchronously with the genetic code. In this paper, phosphoryl amino-acid -5′-nucleosides with P－N bond are postulated to be a chiral origin model in prebiotic molecular evolution. The enthalpy change in the intramolecular interaction between the nucleotide base and the amino-acid side-chain determines the sta-bility of the particular complex, resulting in a preferred conformation associated with the chirality of amino acids. Based on the theoretical model, our experiments and calculations show that the chiral selection of the earliest amino acids for L-enantiomers seems to be a strict stereochemi-cal/physicochemical determinism. As other amino acids developed biosynthetically from the earliest amino acids, we infer that the chirality of the later amino acids was inherited from the precursor amino acids. This idea probably goes far back in history, but it is hoped that it will be a guide for further ex-periments in this area.     

Actin polymerization or myosin contraction: two ways to build up cortical tension for symmetry breaking

Cells use complex biochemical pathways to drive shape changes for polarization and movement. One of these pathways is the self-assembly of actin filaments and myosin motors that together produce the forces and tensions that drive cell shape changes. Whereas the role of actin and myosin motors in cell polarization is clear, the exact mechanism of how the cortex, a thin shell of actin that is underneath the plasma membrane, can drive cell shape changes is still an open question. Here, we address this issue using biomimetic systems: the actin cortex is reconstituted on liposome membranes, in an ‘outside geometry’. The actin shell is either grown from an activator of actin polymerization immobilized at the membrane by a biotin–streptavidin link, or built by simple adsorption of biotinylated actin filaments to the membrane, in the presence or absence of myosin motors. We show that tension in the actin network can be induced either by active actin polymerization on the membrane via the Arp2/3 complex or by myosin II filament pulling activity. Symmetry breaking and spontaneous polarization occur above a critical tension that opens up a crack in the actin shell. We show that this critical tension is reached by growing branched networks, nucleated by the Arp2/3 complex, in a concentration window of capping protein that limits actin filament growth and by a sufficient number of motors that pull on actin filaments. Our study provides the groundwork to understanding the physical mechanisms at work during polarization prior to cell shape modifications.     

Symmetry breaking and polarity establishment during mouse oocyte maturation

Mammalian oocyte meiosis encompasses two rounds of asymmetric divisions to generate a totipotent haploid egg and, as by-products, two small polar bodies. Two intracellular events, asymmetric spindle positioning and cortical polarization, are critical to such asymmetric divisions. Actin but not microtubule cytoskeleton has been known to be directly involved in both events. Recent work has revealed a positive feedback loop between chromosome-mediated cortical activation and the Arp2/3-orchestrated cytoplasmic streaming that moves chromosomes. This feedback loop not only maintains meiotic II spindle position during metaphase II arrest, but also brings about symmetry breaking during meiosis I. Prior to an Arp2/3-dependent phase of fast movement, meiotic I spindle experiences a slow and non-directional first phase of migration driven by a pushing force from Fmn2-mediated actin polymerization. In addition to illustrating these molecular mechanisms, mathematical simulations are presented to elucidate mechanical properties of actin-dependent force generation in this system.     

Symmetry Breaking by Spontaneous Crystallization – Is it the Most Plausible Source of Terrestrial Handedness we have Long Been Looking for? – A Reappraisal

In the light of recent and controversial findings on spontaneous resolution of racemates and their implications in the origin of homochirality on earth, we present here a detailed review of this important topic. Although spontaneous resolution cannot at this moment be reliably predicted, there has also been considerable progress in crystal structure prediction and, not only thermodynamic factors, but also kinetic ones, play important roles in the efficiency of packing and crystallization. In addition, self-association and supramolecular control phenomena may be identified in cases where spontaneous resolution of enantiomers is actually occurring. While this contribution summarizes our current understanding of this intriguing phenomena, it is hoped that future work on crystalline conglomerates (or homochiral crystals) of prebiotic importance will be of further help to understand the general problem of terrestrial chirogenesis.