Highly transparent thin films that exhibit circularly polarized luminescence (CPL) and which can be prepared by simple, water-based processes are important for advanced optical devices. However, most reported CPL-active thin films contain luminophores that were carefully designed to be strongly emissive and CPL-active in the solid state. Consequently, there is a need for water-based processes that can take luminophores that are essentially non-emissive as neat solids and use their CPL in the solution state to prepare transparent CPL-active films. In the present study, clay mineral-organic cation hybrids were prepared as CPL-active materials. Hybrid films of a synthetic saponite, Sumecton SA (SSA), and a chiral binaphthyl ammonium salt, (R)- or (S)-4,4-dibutyl-2,6-bis(3,4,5-trifluorophenyl)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepinium bromide (CBNC), that shows CPL in aqueous solutions, were prepared. Aqueous dispersions of SSA-CBNC hybrids were vacuum filtered to obtain optically transparent films containing CBNC molecules. Whereas CBNC was almost non-emissive as a solid powder, the hybrid films displayed fluorescence and clear CPL signals. The dissymmetry factor (|g| value), which represents the CPL efficiency of CBNC in the hybrid films was enhanced compared with that in aqueous solution. The enhancement was estimated to originate from clay-induced changes in the molecular conformation (e.g. a change in the binaphthyl dihedral angle). These results demonstrate that clay mineral-organic cation hybrids provide a simple, water-based route to transparent CPL-active thin films. Furthermore, clay interlayers may potentially be used to control the chiroptical properties of organic luminophores without covalent modification.

The biotic scenario of the selection of biological homochirality is one of the most interesting applications of computer modelling to astrobiology. These scenarios have been studied for more than 70 years, yet there are plenty of studies to better assess them, in particular in the development of models of the selective extinction process. In this paper, we review former studies performed by biology-grounded models of this process and present a new class of computer programs: they further demonstrate the complexity of the selective extinction dynamics and the role played into it by non-trivial chemical-physical concepts. Indeed, the results display large and persistent differences between the populations of the two different chiral types, made possible by the freedom of individual populations to fluctuate wildly while the total population is stabilized by the limited availability of chemical energy. Such strong differences ultimately lead to the selective extinction of one of the two types. This way, computer simulations provide increasing evidence in favour of the biotic scenario.

The prevalent presence of a single chiral variant of molecules in live organisms is one of the most distinctive signs of life as a global phenomenon. One of the greatest ambitions of biochemistry and astrobiology is to provide an explanation of this predominance. Several mechanisms were proposed in the past, from the propagation of chirality from a homo-chiral substrate to the amplification of effects associated with electro-weak interactions. Here, a different scenario is proposed: anomalous fluctuations associated with a self-replication scenario can lead to the selective extinction of primordial organisms using one of two enantiomers as an enzyme. These fluctuations arise spontaneously under very general conditions. The idea is based on three key points: (a) the simulation of early biological processes as a ‘board game’; (b) the presence of large fluctuations during an autocatalytic process; (c) the presence of a limited source of chemical energy, inducing a form of competition in a primordial replicator population. In order to demonstrate this mechanism, a computational model is developed, describing the ‘struggle for life’ of two different kinds of primordial replicators on a ‘chessboard’ with periodic boundary conditions; each replicator employs enzymes of different chirality on a non-chiral substrate, thereby with no selective advantage. The replication occurs randomly and with a fixed probability, providing that a sufficient amount of chemical energy is locally available. For the first time, our model includes the local balance of chemical energy in a molecular form on the substrate. The correlation between the chemical energy and the local populations is shown. Results clearly show that strong fluctuations in the number of individuals of each species and subsequent selective extinction events of one of the two species are observed. These studies may contribute to shed light on the most mysterious phase transition that occurred during the biochemical evolution of our planet.

In nature, abiotically formed amino acids are usually racemic. However, this is not true for the α,α-dialkyl amino acid isovaline (Iva), which has an L-enantiomeric excess in some specimens of carbonaceous meteorites. On the early Earth and Mars, such meteorites were sources of amino acids, including Iva. Therefore, a connection may exist between the possible chiral influence of non-racemic Iva and the origin of biological homochirality. On the surface of a young terrestrial planet, amino acids can be chemically altered in many ways. For example, high temperatures from geothermal heating can lead to racemization. Four billion years ago, active volcanism and volcanic islands provided suitable conditions for such reactions and perhaps even for early microbial life on Earth. In the current study, we investigated the influence of D- and L-Iva on the thermal racemization of L-alanine (L-Ala) and L-2-aminobutyric acid (L-Abu) in a simulated hot volcanic environment. The amino acids were intercalated in the clay mineral calcium montmorillonite (SAz-1). While Iva was resistant to racemization, partial racemization was observed for Ala and Abu after 8 weeks at 150°C. The experimental results – for example, accelerated racemization in the presence of Iva and different influences of the Iva enantiomers – suggest that the amino acid molecules interacted with each other, possibly in hydrogen-bonded dimers. Accelerated racemization of amino acids could have been an obstacle to the development of homochirality. Besides, it is also detrimental to the use of homochirality as a biosignature, for example, in the search for microbial life on Mars.

In the present work, it is shown that thermodynamically feasible polymerization of cyanomethanol, which can be formed from formaldehyde and hydrogen cyanide, can lead to synthesis of polypeptides as well as to the previously reported synthesis of RNA. If the polymerization takes place on a one-dimensional feature of a mineral, such as for example a crack on its surface, the concept of quasi-chirality is introduced to describe the adsorbed polypeptide. This, in principle, would lead to formation of proteins that are completely homochiral in their alpha carbon groups. The concept of quasi-chirality can also be introduced in the condensation of glycine under similar conditions to form a polypeptide. This again leads to proteins completely chiral in their alpha carbon groups.

The origin of the enantiomeric excess found in the amino acids present in the organic matter of carbonaceous meteorites is still unclear. Selective adsorption of one of the two enantiomers existing after a racemic formation could be part of the answer. Hereafter we report a comparative study of the adsorption of the R and S enantiomers of α-alanine and lactic acid on the hydroxylated {$10\bar 10$} chiral surface of α-quartz using numerical simulation techniques. Structurally different adsorption sites were found with opposite R versus S selectivity for the same molecule–surface couple, raising the problem of whether to consider adsorption as a local property or as a global response characteristic of the whole surface. To deal with the second term of this alternative, a statistical approach was designed, based on the occurrence of each adsorption site whose energy was calculated using first principle periodic density functional theory. It was found that R-alanine and S-lactic acid are the enantiomers preferentially adsorbed, even if the adsorption process on the quartz {$10\bar 10$} surface stays with a disappointingly poor enantio-selectivity. Nevertheless, it highlighted the important point that considering adsorption as a global property changes perspectives in the search for more efficient enantio-selective supports and more generally changes the way to apprehend adsorption processes in astro-chemistry/biology.

A key open question in the study of life is the origin of biomolecular homochirality: almost every life-form on Earth has exclusively levorotary amino acids and dextrorotary sugars. Will the same handedness be preferred if life is found elsewhere? We review some of the pertinent literature and discuss recent results suggesting that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events. In one scenario, autocatalytic prebiotic reactions undergo stochastic fluctuations due to environmental disturbances, in a mechanism reminiscent of evolutionary punctuated equilibrium: short-lived destructive events may lead to long-term enantiomeric excess. In another, chiral-selective polymerization reaction rates influenced by environmental effects lead to substantial chiral excess even in the absence of autocatalysis. Applying these arguments to other potentially life-bearing platforms has implications to the search for extraterrestrial life: we predict that a statistically representative sampling of extraterrestrial stereochemistry will be racemic (chirally neutral) on average.

Ni20[(C6H8O4)20(H2O)8]∙33H2O, a new nickel(II) 3-methylglutarate, was prepared hydrothermally (180 °C, 48 h, autogenous pressure) from a 1:1.5:2:180 mixture of nickel (II) sulphate hexahydrate, 3-methylglutaric acid, sodium hydroxide, and water. It crystallizes in the cubic system (space group P4332, Z=1) with a=16.8488(5) Å and V=4783.1(4) Å3. Its structure was solved from conventional X-ray powder diffraction data. It presents a three-dimensional network of edge-sharing nickel octahedra, lined by deprotonated organic anions. This remarkable oxide network with corrugated 20-membered rings is constructed from homochiral helices. The rings intersect each other to generate large crossing channels full of water along [111].

Mechanisms of interstellar panspermia have recently been identified whereby life, wherever it has originated, will disperse throughout the habitable zone of the Galaxy within a few billion years. This re-opens the question of where life originated. The interiors of comets, during their aqueous phase, seem to provide environments no less favourable for the origin of life than that of the early Earth. Their combined mass throughout the Galaxy overwhelms that of suitable terrestrial environments by about 20 powers of ten, while the lifetimes of friendly prebiotic environments within them exceeds that of localized terrestrial regions by another four or five powers of ten. We propose that the totality of comets around G-dwarf Sun-like stars offers an incomparably more probable setting for the origin of life than any that was available on the early Earth.

The action of high-energy radiation on prebiotic chiral molecules plays against the preservation of chirality. Chiral molecules incorporated in comets and meteorites are bombarded for billions of years by cosmic rays and by the high-energy radiation due to the decay of naturally occurring radionuclides. The action of cosmic rays on the surface of comets and meteorites causes the complete radiation processing of the surface of these bodies, but at depths of 20 m or so the cosmic rays are completely shielded and the radiation should derive only from the decay of radionuclides. In 4.6×109 yr the radiation dose supplied by the radionuclide decay to the organic molecules present inside the cometary or meteoritic body is equivalent to 14000 kGy. Our studies on the radiolysis of a series of naturally occurring chiral molecules, the terpenes, have shown that although all undergo the radioracemization reaction, the extent of radioracemization is such that a significant fraction of chiral excess and chiral molecules can survive a radiation dose equivalent to 14000 kGy. A unique exception is represented by the terpene β-(−)-pinene which, instead of the expected radioracemization reaction, undergoes a radiation-induced polymerization. The resulting poly-β-pinene, having an highly ordered supramolecular structure, displays an optical activity which is 1.7 times higher than the starting monomer. Thus, in this specific case, the optical activity is not reduced but enhanced by the action of radiation and remains locked into a polymer which displays a considerable radiation resistance and may act as a chiral template and as a chiral surface for prebiotic chemistry.

This article outlines the content of the April 2004 issue of MRS Bulletin on Advances in Carbon Nanotubes. Essentially, carbon nanotubes are self-assembling nanostructures constructed of sheets of hexagonal-shaped carbon atoms rolled up into cylinders. Carbon nanotubes have attracted a great deal of attention as model systems for nanoscience and for potential applications. The special interest in carbon nanotubes stems from their unique structure and properties: their very small size (down to ∼0.42 nm in diameter); the possibility for carbon nanotubes to be metallic or semiconducting, depending on their geometrical structure; their exceptional properties of ballistic transport; their extremely high thermal conductivity and high optical polarizability; and the possibilities of high structural perfection. Research in the carbon nanotube field has now advanced to the stage where a good understanding of the structure and many of the basic properties are in place, together with much appreciation of their interrelation. On the other hand, major gaps in basic knowledge remain, with the major obstacles confronting the carbon nanotube field being the lack of a detailed understanding of the nanotube growth mechanism and control of the synthesis process to produce nanotubes with a desired diameter and chirality. The brief review of the carbon nanotube field by leading experts in this issue comes at an opportune time. Many exciting results on the structural, electronic, optical, and transport properties of these tiny well-ordered structures have already been achieved, and the research is well enough developed to assess present progress and identify new research directions waiting to be explored.