Mirror symmetry breaking as a problem in dynamical critical phenomena

The critical properties of the Frank model of spontaneous chiral synthesis are discussed by applying results from the field theoretic renormalization group (RG). The long time and long wavelength features of this microscopic reaction scheme belong to the same universality class as multi-colored directed percolation processes. Thus, the following RG fixed points (FP) govern the critical dynamics of the Frank model for d<4: one unstable FP that corresponds to complete decoupling between the two enantiomers, a saddle-point that corresponds to symmetric interspecies coupling, and two stable FPs that individually correspond to unidirectional couplings between the two chiral molecules. These latter two FPs are associated with the breakdown of mirror or chiral symmetry. In this simplified model of molecular synthesis, homochirality is a natural consequence of the intrinsic reaction noise in the critical regime, which corresponds to extremely dilute chemical systems.Comment: 9 pages, 3 figure

Metastability in supersaturated solution and transition towards chirality in the crystallization of NaClO3

Analysis of the chiral composition of the crystal mixture obtained from samples of boiling solutions of NaClO3 (see picture) indicates that symmetry breaking towards homochiral compositions may begin in the metastable stage preceding crystallization, that is, at the level of subcritical clusters

Homochirality and the need of energy

The mechanisms for explaining how a stable asymmetric chemical system can be formed from a symmetric chemical system, in the absence of any asymmetric influence other than statistical fluctuations, have been developed during the last decades, focusing on the non-linear kinetic aspects. Besides the absolute necessity of self-amplification processes, the importance of energetic aspects is often underestimated. Going down to the most fundamental aspects, the distinction between a single object -- that can be intrinsically asymmetric -- and a collection of objects -- whose racemic state is the more stable one -- must be emphasized. A system of strongly interacting objects can be described as one single object retaining its individuality and a single asymmetry; weakly or non-interacting objects keep their own individuality, and are prone to racemize towards the equilibrium state. In the presence of energy fluxes, systems can be maintained in an asymmetric non-equilibrium steady-state. Such dynamical systems can retain their asymmetry for times longer than their racemization time.Comment: 8 pages, 7 figures, submitted to Origins of Life and Evolution of Biosphere

Structure vs. properties chirality, optics and shapes in amphiphilic porphyrin J-aggregates

The structure of the meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) J-aggregates could be determined by X-ray and electron diffraction methods. A sheet-like architecture reveals the relationship between structure and chirality, optics and shapes of the J-aggregate of the meso 4-sulfonatophenyl- and phenyl- substituted porphyrins. The structure of the J-aggregates of H4TPPS4 belongs to the chiral space group P21 and includes four porphyrin molecules in its unit cell. The intermolecular stabilization of the zwitterionic units by hydrogen bonding and electrostatic interactions between the positively charged central NH groups and the periphery anionic sulfonato groups results in a structure of porphyrins sheets along the [ ] plane direction. The structure of the sheet on the [ ] plane is already chiral and its molecular architecture explains the simultaneous presence of H- and J-aggregate bands in their absorption spectra. This structure also accounts for the high similarity observed between the absorption spectra of different mesophorms of the same substance and even between different members of the series of meso-4-sulfonatophenyl-and-aryl substituted diprotonated porphyrins. The possibility, or not, of the sheet-like structure on [ ] to interact with other layers, either through ionic or hydrophobic interactions, depends on the substitution pattern at the meso-positions of the porphyrin ring. Thus, the different morphologies of the particles [mono- bi- and multilayered] of this series of J-aggregates are explained taking into account the role that the fourth meso-subtituent plays in the interlayer stabilization. The results suggest that supramolecular helicity, previously detected in several J-aggregates, is not the explanation of their chirality but would be the expression of the intrinsic chirality of the packing between building blocks

Travelling waves in two-dimensional smectic-C domains

Continued irradiation of smectic-C-like domains of photosensitive Langmuir monolayers from azobenzene derivatives induces the nucleation and propagation of orientational travelling waves as observed with Brewster angle microscopy (BAM). BAM image analysis has allowed to identify different dynamical behaviors involving the generation and propagation of such waves. A model based on the coupling between an orientational and a composition field proposes a scenario for dynamic self-assembly that accounts for most of the observed phenomena, and allows to pinpoint the relevance of boundary defects in wave-emitting structures.-

Chirality: spin and gravity give a helping hand

The handedness of supramolecular helices formed from achiral monomers has been controlled by applying rotational and gravitational forces, but at the start of the assembly process only. This demonstrates that a falsely chiral influence is able to induce absolute enantioselection

Rapid sight reduction tables for navigation Volume 3; latitudes 39deg-89deg; delinations 0deg-29deg

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