An Extended Model for the Evolution of Prebiotic Homochirality: A Bottom-Up Approach to the Origin of Life

A generalized autocatalytic model for chiral polymerization is investigated in detail. Apart from enantiomeric cross-inhibition, the model allows for the autogenic (non-catalytic) formation of left and right-handed monomers from a substrate with reaction rates epsilon L and epsilon R, respectively. The spatiotemporal evolution of the net chiral asymmetry is studied for models with several values of the maximum polymer length, N. For N = 2, we study the validity of the adiabatic approximation often cited in the literature. We show that the approximation obtains the correct equilibrium values of the net chirality, but fails to reproduce the short time behavior. We show also that the autogenic term in the full N = 2 model behaves as a control parameter in a chiral symmetry-breaking phase transition leading to full homochirality from racemic initial conditions. We study the dynamics of the N--> infinity model with symmetric (epsilon L = epsilon R) autogenic formation, showing that it only achieves homochirality for epsilon > epsilon c, where epsilon c is an N-dependent critical value. For epsilon 相似文献   

Thermal Energy and the Origin of Life

Life has evolved on Earth with electromagnetic radiation (light), fermentable organic molecules, and oxidizable chemicals as sources of energy. Biological use of thermal energy has not been observed although heat, and the thermal gradients required to convert it into free energy, are ubiquitous and were even more abundant at the time of the origin of life on Earth. Nevertheless, Earth-organisms sense thermal energy, and in suitable environments may have gained the capability to use it as energy source. It has been proposed that the first organisms obtained their energy by a first protein named pF₁ that worked on a thermal variation of the binding change mechanism of today's ATP sythase enzyme. Organisms using thermosynthesis may still live where light or chemical energy sources are not available. Possible suitable examples are subsurface environments on Earth and in the outer Solar System, in particular the subsurface oceans of the icy satellites of Jupiter and Saturn.     

Question 1: Origin of Life and the Living State

The aim of this article is to discuss four topics: First, the origin of molecular reproduction. Second, the origin of agency – the capacity of a system to act on its own behalf. Agency is a stunning feature of human and some wider range of life. Third, to discuss a still poorly articulated feature of life noticed by the philosopher Immanuel Kant over 200 years ago: A self propagating organization of process. We have no theory for this aspect of life, yet it is central to life. Fourth, I will discuss constraints, as in Schroedinger’s aperiodic crystal (Schroedinger E, What is life? The physical aspect of the living cell, 1944), as information, part of the total non-equilibrium union of matter, energy, work, work cycles, constraints, and information that appear to comprise the living state.     

Question 4: Basic Questions About the Origin of Life: On Chirobiogenesis

Some experimental aspects concerning either the enantio-enrichment of α-amino acids starting from non-racemic mixtures or the formation of homochiral oligopeptides and oligonucleotides starting from racemic precursors are described. In principle, it is possible that more than one of these processes had played a role in chirobiogenesis. Presented at the International School of Complexity – 4th Course: Basic Questions on the Origins of Life; “Ettore Majorana” Foundation and Centre for Scientific Culture, Erice, Italy, 1–6 October 2006.     

Question 1: Peptide Nucleic Acids and the Origin and Homochirality of Life

The possibilities of pseudo peptide DNA mimics like PNA (peptide nucleic acid) having a role for the prebiotic origin of life prior to an RNA world is discussed. In particular a scenario is proposed in which protocells with an achiral genetic material through several generations stepwise is converted into a chiral genetic material, e.g., by incorporation of RNA units. Provided that a sufficiently large sequence space is occupied, a selection process based on catalytic function in which a single cell (first common ancestor) has a definite evolutionary advantage, selection of this cell would by contingency also lock it into homochirality. Presented at: International School of Complexity – 4th Course: Basic Questions on the Origins of Life; “Ettore Majorana” Foundation and Centre for Scientific Culture, Erice, Italy, 1–6 October 2006.     

An Open Question on the Origin of Life: The First Forms of Metabolism

The general framework of the origin of life on Earth is outlined, emphasizing that the so‐called prebiotic ‘RNA world’ is as yet on shaky scientific ground, and that one should any way ask the question of the structure of the first protocellular compartments capable of the initial forms of metabolism. This question is the basis of the research project on the minimal cells, containing the minimal and sufficient complexity capable of leading to life. Such research is briefly summarized, highlighting experiments with liposome‐based semisynthetic cells which are capable of ribosomal protein synthesis with a very minimal number of enzymes. The most recent finding in this area of research is the unexpected observation that the formation and closure of liposomes in situ acts as an attractor for the solute molecules in solution, bringing about a very high local concentration in some of the liposomes. It is argued that this spontaneous overcrowding, which permits reactions which are not possible in the original dilute solution, might be the origin of cellular metabolism for the origin of life on Earth.     

Kinetics of Organic Transformations under Mild Aqueous Conditions: Implications for the Origin of Life and its Metabolism

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.     

The Unique Adaptation of the Life Cycle of the Coelomic Gregarine Diplauxis hatti to its Host Perinereis cultrifera (Annelida,Polychaeta): an Experimental and Ultrastructural Study

ABSTRACT. The coelomic gregarine Diplauxis hatti exhibits a unique adaptation of its life cycle to its polychaete host Perinereis cultrifera. Experimental and ultrastructural observations on natural populations from the English Channel showed that release of parasite spores is concomitant with the polychaete spawning. As the development of P. cultrifera is direct, the notochete larva ingest parts of the jelly coat covered with numerous sporocysts of D. hatti during hatching. Transepithelial migration of the sporozoites takes place in the gut of three‐ or four‐segment notochete larvae and syzygies of about 20 μm are observed in the coelom. Growth of these young syzygies is slow: after 18–24 mo they reach only 60–70 μm. They exhibit active pendular movements. In the English Channel, female and male gametogenesis of P. cultrifera begins at 19 mo and 2 yr, respectively; the somatic transformations (epitoky) in the last 4 mo of their 3‐year life. During epitoky, the syzygies undergo an impressive growth and reach 700–800 μm within a few weeks. A shift from pendular to active peristaltic motility is observed when the syzygies reach 200–250 μm. When gamogony occurs, syncytial nuclear divisions are initiated and cellularization produces hundred to thousands of male and female gametes of similar size. The male gametes exhibit a flagellum with 3+0 axoneme. The mixing of the gametes (“danse des gametes”) and fertilization are observed during 4–5 h. Zygotes differentiate sporoblasts with eight sporozoites. The sporozoites exhibit the canonical structure of Apicomplexa, a polarized cell with micronemes and rhoptries.     

Enhancing the Adoption of Life Cycle Assessment by Small and Medium Enterprises Grouped in an Industrial Cluster: A Case Study of the Tanning Cluster in Tuscany (Italy)

Greenhouse gas emissions from small and medium enterprises (SMEs) account for 70% of the industrial pollution in the European Union. Owing to limited economic and human resources, only a few SMEs start procedures to evaluate the environmental impact of processes and products through life cycle assessment (LCA). In this work, a cluster life cycle assessment (Cluster‐LCA) is proposed as an instrument for the diffusion and realization of LCA analysis in clustered SMEs. This methodology is illustrated with a case study in the tanning cluster in Tuscany. The different characteristics of the methodology are analyzed by identifying the intrinsic strengths, weaknesses, opportunities, and threats. The application of this methodology in a particular cluster is then discussed in order to gather some helpful insight for the application of this methodology in different clusters.     

Determination of the Enantiomerization Barrier of the Residual Enantiomers of C3‐Symmetric Tris[3‐(1‐Methyl‐2‐Alkyl)Indolyl]Phosphane Oxides: Case Study of a Multitasking HPLC Investigation Based on an Immobilized Polysaccharide Stationary Phase

The residual enantiomers of three tris‐(3‐indolyl)‐phosphane oxides bearing different alkyl groups (methyl, ethyl or i‐propyl) in position 2 of the indole rings constituting the blades were separated on the immobilized type Chiralpak IC column in polar organic and reversed‐phase modes. The good enantioselectivity and versatility of the IC CSP allowed easy isolation of the enantiomerically highly enriched samples suitable for configurational stability studies. The enantiomerization barriers of residual phosphane oxides were evaluated both by off‐column techniques (CD signal and enantiomeric purity decay kinetics) and by dynamic enantioselective high‐performance liquid chromatography (HPLC). Chirality 27:888–899, 2015. © 2015 Wiley Periodicals, Inc.