Life and chirality beyond the earth.

An attempt is made to show that the phenomenon of chirality- of which optical activity is but one consequence- is by no means restricted to life on Earth, but is common throughout the universe. Several independent sources have been investigated including: statistical fluctuations; stereoselective physical factors; and energetic differences between enantiomeric molecules. It is emphasised that a search for chirality as an indicator for life elsewhere in space provides an excellent tool for the fascinating question of exobiology. Still one must be aware of the limitations of the experimental methods and their interpretations.     

Chirality as a primary switch of hierarchical levels in molecular biological systems

A synergetic law, being of common physicochemical and biological sense, is formulated: any evolving system that possesses an excess of free energy and elements with chiral asymmetry, while being within one hierarchical level, is able to change the type of symmetry in the process of self-organization increasing its complexity but preserving the sign of prevailing chirality (left — L or right — D twist). The same system tends to form spontaneously a sequence of hierarchical levels with alternating chirality signs of de novo formed structures and with an increase of the structures’ relative scales. In living systems, the hierarchy of conjugated levels of macromolecular structures that begins from the “lowest” asymmetric carbon serves as an anti-entropic factor as well as the structural basis of “selected mechanical degrees of freedom” in molecular machines. During transition of DNA to a higher level of structural and functional organization, regular alterations of the chirality sign D-L-D-L and L-D-L-D for DNA and protein structures, respectively, are observed. Sign-alternating chiral hierarchies of DNA and protein structure, in turn, form a complementary conjugated chiral pair that represents an achiral invariant that “consummates” the molecular-biological block of living systems. The ability of a carbon atom to form chiral compounds is an important factor that determined the carbon basis of living systems on the Earth as well as their development though a series of chiral bifurcations. The hierarchy of macromolecular structures demarcated by the chirality sign predetermined the possibility of the “block” character of biological evolution.     

2 The Soul's Frail Dwelling-House

Essentially, there is only one thing in life that interests us: the content of the mind. Millions of pages are filled with a portrayal of man's inner world; but the product of this labor—the laws of man's inner life—is still not in our possession.     

Circularly polarized luminescence studies of the adducts formed with Eu(III) β-diketone complexes and (—)-sparteine

The optical activity resulting from the complexation of (—)-sparteine by a series of Eu(III) β-diketone compounds has been studied by means of circularly polarized luminescence spectroscopy. It was found that the presence of at least one perfluoro group was necessary for the formation of an adduct complex. With Eu(III) complexes containing achiral β-diketone ligands, it was found that the observed chirality could be considered to result from a combination of vicinal and conformational effects. With Eu(III) complexes containing chiral β-diketone ligands, the optical activity was found to be dominated by confïgurational effects.     

Experimental attempts for the study of the origin of optical activity on earth

Optical activity of natural compounds is a characteristic of our living world which is based on the asymmetry of the molecular set-up. It is hard to realize a biological cell which would be constructed from racemic compounds alone. Yet it seems attractive to ask why nature preferred onlyone of two possible enantiomers, e.g. the L-amino-acids and D-sugars. Was there or is there a chance for an antipodic biosphere constructed on the basis of the ‘unnatural’ enantiomers like D-amino-acids and L-sugars on Earth or elsewhere?-The paper presents in its first part a review about hypotheses that would be able to explain the apparent discrepancy between the expectation from laboratory experience and the observation that biological matter consists of extremely asymmetric molecules. The speculations found in literature are divided mainly into two categories: The first one interprets the appearance of optical activity by a chance process and its amplification by suitable means, the second one postulates a cogency leading to the chirality of the biosphere observed today. The discovery of the non-conservation of parity in nuclear physics stimulated a search for related ‘asymmetry effects’ in chemistry. Experiments were undertaken by some workers to construct possible laboratory models for the evolution of optical activity, but many of them failed due to different causes. On the other hand a number of papers has been published that were not directed specifically to the problem discussed, but could be interpreted on the basis of the various hypotheses. It is particularly interesting in this context to look into papers describing the crystallisation of racemates from solutions, that were published as early as 70 yr ago. —In its second part the paper deals with the study of the polymerization of racemic amino-acids as a model that would possibly allow a decision between the hypotheses for the origin of optical activity, — mere chance or a physical driving force determining the chirality of evolution. Since great care was taken to eliminate all sources of systematical errors, one expected-form the classical standpoint-racemic poly-peptides of absolute zero optical activity. — The monomer amino-acids (α-alanine, α-amino-butyric acid, and lysine) were racemized before the polymerization in order to guarantee ‘ideally racemic’ substrates. Polymerization was achieved via the N-carboxyanhydrides of the amino-acids. Reaction vessels and measuring cells were thoroughly cleaned with boiling chromic sulfuric acid and kept sealed from the laboratory atmosphere to prevent any contamination. The optical activity was determined in a Cary 60 spectropolarimeter calibrated to detect angles of rotations in the range of 0.5 mdeg with a maximum error of ±50%. All the poly-amino-acids investigated showed negative angles of rotation at 310 nm between 0.25 and 0.84 mdeg that would correspond to an hypothetical asymmetry effect-i.e. the relative difference of the polymerization constants of L-and D-amino-acids-in the order of 8×10^?6. We believe that this result emphasises the existence of a physical force that enables a slight accumulation of the L-amino-acids within the high molecular weight polymers in excess to the D-amino-acids and could be of significance for the evolution of the biomass. At this point the experiments do not allow any conclusion about the nature of the observed ‘asymmetry effect’.     

Adaptation to developmental diet influences the response to selection on age at reproduction in the fruit fly

Experimental evolution (EE) is a powerful tool for addressing how environmental factors influence life‐history evolution. While in nature different selection pressures experienced across the lifespan shape life histories, EE studies typically apply selection pressures one at a time. Here, we assess the consequences of adaptation to three different developmental diets in combination with classical selection for early or late reproduction in the fruit fly Drosophila melanogaster. We find that the response to each selection pressure is similar to that observed when they are applied independently, but the overall magnitude of the response depends on the selection regime experienced in the other life stage. For example, adaptation to increased age at reproduction increased lifespan across all diets; however, the extent of the increase was dependent on the dietary selection regime. Similarly, adaptation to a lower calorie developmental diet led to faster development and decreased adult weight, but the magnitude of the response was dependent on the age‐at‐reproduction selection regime. Given that multiple selection pressures are prevalent in nature, our findings suggest that trade‐offs should be considered not only among traits within an organism, but also among adaptive responses to different—sometimes conflicting—selection pressures, including across life stages.     

Septins and a formin have distinct functions in anaphase chiral cortical rotation in the Caenorhabditis elegans zygote

Many cells and tissues exhibit chirality that stems from the chirality of proteins and polymers. In the Caenorhabditis elegans zygote, actomyosin contractility drives chiral rotation of the entire cortex circumferentially around the division plane during anaphase. How contractility is translated to cell-scale chirality, and what dictates handedness, are unknown. Septins are candidate contributors to cell-scale chirality because they anchor and cross-link the actomyosin cytoskeleton. We report that septins are required for anaphase cortical rotation. In contrast, the formin CYK-1, which we found to be enriched in the posterior in early anaphase, is not required for cortical rotation but contributes to its chirality. Simultaneous loss of septin and CYK-1 function led to abnormal and often reversed cortical rotation. Our results suggest that anaphase contractility leads to chiral rotation by releasing torsional stress generated during formin-based polymerization, which is polarized along the cell anterior–posterior axis and which accumulates due to actomyosin network connectivity. Our findings shed light on the molecular and physical bases for cellular chirality in the C. elegans zygote. We also identify conditions in which chiral rotation fails but animals are developmentally viable, opening avenues for future work on the relationship between early embryonic cellular chirality and animal body plan.     

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.     

Cosmic Chirality both True and False

The discrete symmetries of parity P, time reversal T, and charge conjugation C may be used to characterize the properties of chiral systems. It is well known that parity violation infiltrates into ordinary matter via an interaction between the nucleons and electrons, mediated by the Z⁰ particle, that lifts the degeneracy of the mirror‐image enantiomers of a chiral molecule. Being odd under P but even under T, this P‐violating interaction exhibits true chirality and so may induce absolute enantioselection under all circumstances. It has been suggested that CP violation may also infiltrate into ordinary matter via a P‐odd, T‐odd interaction mediated by the (as yet undetected) axion. This CP‐violating interaction exhibits false chirality and so may induce absolute enantioselection in processes far from equilibrium. Both true and false cosmic chirality should be considered together as possible sources of homochirality in the molecules of life. Chirality 24:957‐958, 2012.© 2012 Wiley Periodicals, Inc.     

Fitness in the universe: Choices and necessities

We live in a universe of chance, but not of accident. Repeatedly in the course of its development choices have been made for which one can ask the reasons. One such choice is fundamental: if the proton had not so much greater mass than the electron, all matter would be fluid; and if the proton did not have exactly the same numerical charge as the electron — or some simple multiple of that charge — virtually all matter would be charged. If a universe were started with charged hydrogen, it could expand, but probably nothing more. Hydrogen, carbon, nitrogen and oxygen play as fundamental — and irreplaceable — roles in the metabolism of stars as of living organisms. Both metabolisms are coupled, through radiation from the stars providing the energy on which life must come ultimately to run on the planets. In the course of their evolution on the Earth, living organisms have found their way repeatedly and exclusively to certain types of organic molecule to perform specific functions; so, for example, the chlorophylls for photosynthesis, and carotenoids for plant phototropism and for vision. It is argued that some measure of necessity has governed these choices; and that an extended principle of natural selection has operated at all levels of material organization to produce such elements of order and compatibility in the universe.     

A new definition of life

Chirality is often glossed over in theoretical or experimental discussions concerning the origin of life, but the ubiquity of homochiral building blocks in known biological systems demands explanation. Information theory can provide a quantitative framework for understanding the role of chirality in biology. Here I show how conclusions derived from information theory, in particular the concept of equivocation, can explain not only why chiral building blocks are necessary in living systems but also why a homochiral set of building blocks is necessary. These results lead to a new definition of life, and to the conclusion that the simplest form of life exists in the form of self-amplifying, autocatalytic reactions such as the Soai reaction.     

Chirality and life

The crucial role of homochirality and chiral homogeneity in the self-replication of contemporary biopolymers is emphasized, and the experimentally demonstrated advantages of these chirality attributes in simpler polymeric systems are summarized. The implausibility of life without chirality and hence of a biogenic scenario for the origin of chiral molecules is stressed, and chance and determinate abiotic mechanisms for the origin of chirality are reviewed briefly in the context of their potential viability on the primitive Earth. It is concluded that all such mechanisms would be non-viable, and that the turbulent prebiotic environment would require an ongoing extraterrestrial source for the accumulation of chiral molecules on the primitive Earth. A scenario is described wherein the circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae engenders asymmetric photolysis of the racemic constituents in the organic mantles on interstellar dust grains, whereupon these chiral constituents are transported repetitively to the primative Earth by direct accretion of the interstellar dust or through impacts of comets and asteroids.     

Life-History Inference in the Early Hominins Australopithecus and Paranthropus

The life histories of early hominins are commonly characterized as being like those of great apes. However, the life histories of the extant great apes differ considerably from one another. Moreover, the extent to which their life histories correlate with the two aspects of morphology used to infer the life histories of fossil species, brain size and dental development, has remained subject to debate. Increased knowledge of great ape life histories and, more recently, dental development —in particular ages at first molar emergence— now make it clearer that the latter is strongly associated with important life-history attributes, whereas brain size, as reflected by cranial capacity, is less informative. Here we estimate ages at M1 emergence in several infant/juvenile individuals of Australopithecus and Paranthropus based on previous estimates of ages at death, determined through dental histology. These are uniformly earlier than would be predicted either by adult cranial capacity or by comparison to ages at M1 emergence in free-living extant great apes. This suggests that either, 1) the life histories of the early hominins were faster than those of all extant great apes; 2) there was selection for rapid initial dental development and presumably early weaning, but that early hominin life histories were otherwise more prolonged and consistent with adult cranial capacities; or 3) the ages at death have been systematically underestimated, resulting in underestimates of the ages at M1 emergence. We investigate the implications of each of these alternatives and, where possible, explore evidence that might support one over the others.     

Chirality: A Relational Geometric‐Physical Property

The definition of the term chirality by Lord Kelvin in 1893 and 1904 is analyzed by taking crystallography at that time into account. This shows clearly that chirality is a relational geometric‐physical property, i.e., two relations between isometric objects are possible: homochiral or heterochiral. In scientific articles the relational term chirality is often mistaken for the two valued measure for the individual (absolute) sense of chirality, an arbitrary attributive term. Chirality 25:684–685, 2013. © 2013 Wiley Periodicals Inc.     

Diene chirality and cotton effects of nonhomoannular cisoid conjugated dienes: circular dichroism and crystal structure of a steroidal 19-nor-1(10),9(11)-diene derived from Westphalen's diol diacetate

Nonhomoannular cisoid conjugated dienes exhibit negative lowest energy pi-->pi* Cotton effects when they have P diene chirality and positive CEs when they have M diene chirality. We investigated this relationship further with a variety of such dienes by MM2 conformational energy-minimization calculations and by an X-ray crystal structure of a steroidal 19 nor 1(10),9(11) diene. CEs are stronger when each double bond of the diene is endocyclic in a different ring and weaker when only one of the double bonds is endocyclic or when neither double bond is endocyclic. They are also stronger when axial allylic and homoallylic substituents with CH/pi interactions are present that exert consignate chirality contributions.     

Evolution of butterfly seasonal plasticity driven by climate change varies across life stages

Photoperiod is a common cue for seasonal plasticity and phenology, but climate change can create cue–environment mismatches for organisms that rely on it. Evolution could potentially correct these mismatches, but phenology often depends on multiple plastic decisions made during different life stages and seasons that may evolve separately. For example, Pararge aegeria (Speckled wood butterfly) has photoperiod-cued seasonal life history plasticity in two different life stages: larval development time and pupal diapause. We tested for climate change-associated evolution of this plasticity by replicating common garden experiments conducted on two Swedish populations 30 years ago. We found evidence for evolutionary change in the contemporary larval reaction norm—although these changes differed between populations—but no evidence for evolution of the pupal reaction norm. This variation in evolution across life stages demonstrates the need to consider how climate change affects the whole life cycle to understand its impacts on phenology.     

Cuticle chirality and body handedness in Caenorhabditis elegans

Caenorhabditis elegans adult animals exhibit an inherent chirality of fiber orientation in the basal layer of the cuticle, as well as a naturally invariant but experimentally reversible handedness in the left-right (L-R) asymmetry of the body plan. We have examined the relationship between cuticle chirality and body handedness in normal and L-R reversed animals, using Roller (Rol) mutants and transmission electron microscopy to monitor cuticle properties. Rol phenotypes, several of which have been shown to result from mutations in cuticle collagen genes, are characterized by an invariant, allele-specific handedness in their direction of rolling. We show for several alleles that this direction is not affected by L-R reversal of the body plan. We further show, by electron microscopy, that the chiral orientation of cuticle fibers in animals with normal cuticle is not reversed by L-R body-plan reversal. We conclude that cuticle chirality must be established independently of body-plan handedness. The cues that establish cuticle chirality are still unknown, as are the causes for different rolling directions in different Roller mutants. We discuss the question of how cuticle chirality maintains its independence, and how the orientations of the fiber layers may be determined. Dev. Genet. 23:164–174, 1998. © 1998 Wiley-Liss, Inc.     

146 Amyloid fibril polymorphism probed by advanced vibrational spectroscopy

Amyloid fibrils are associated with many neurodegenerative diseases. All known amyloids including pathogenic and nonpathogenic forms display functional and structural heterogeneity (polymorphism) which determines the level of their toxicity. Despite a significant biological and biomedical importance, the nature of the amyloid fibril polymorphism remains elusive. We utilized for the first time three most advanced vibrational techniques to probe the core, the surface, and supramolecular chirality of fibril polymorphs. A new type of folding, aggregation phenomenon, spontaneous refolding from one polymorph to another, was discovered (Kurouski, Lauro et al., 2010). Hydrogen–deuterium exchange deep UV resonance Raman spectroscopy (Oladepo, Xiong et al., 2012) combined with advanced statistical analysis (Shashilov & Lednev, 2010) allowed for structural characterization of the highly ordered cross-β core of amyloid fibrils. We reported several examples showing significant variations in the core structure for fibril polymorphs. Amyloid fibrils are generally composed of several protofibrils and may adopt variable morphologies, such as twisted ribbons or flat-like sheets. We discovered the existence of another level of amyloid polymorphism, namely, that associated with fibril supramolecular chirality. Two chiral polymorphs of insulin, which can be controllably grown by means of small pH variations, exhibit opposite signs of vibrational circular dichroism (VCD) spectra (Kurouski, Dukor et al. 2012). VCD supramolecular chirality is correlated not only by the apparent fibril handedness but also by the sense of supramolecular chirality from a deeper level of chiral organization at the protofilament level of fibril structure. A small pH change initiates spontaneous transformation of insulin fibrils from one polymorph to another. As a result, fibril supramolecular chirality overturns both accompanying morphological and structural changes (Kurouski, Dukor et al. 2012). No conventional methods could probe the fibril surface despite its significant role in the biological activity. We utilized tip-enhanced Raman spectroscopy (TERS) to characterize the surface structure of an individual fibril due to a high depth and lateral spatial resolution of the method in the nanometer range (Kurouski, Deckert-Gaudig et al. 2012). It was found that the surface is strongly heterogeneous and consists of clusters with various protein conformations and amino acid composition.