Origin of organic compounds on the primitive earth and in meteorites

The role and relative contributions of different forms of energy to the synthesis of amino acids and other organic compounds on the primitive earth, in the parent bodies or carbonaceous chondrites, and in the solar nebula are examined. A single source of energy or a single process would not account for all the organic compounds synthesized in the solar system. Electric discharges appear to produce amino acids more efficiently than other sources of energy and the composition of the synthesized amino acids is qualitatively similar to those found in the Murchison meteorite. Ultraviolet light is also likely to have played a major role in prebiotic synthesis. Although the energy in the sun's spectrum that can be absorbed by the major constituents of the primitive atmosphere is not large, reactive trace components such as H2S and formaldehyde absorb at longer wavelengths where greater amounts of energy are available and produce amino acids by reactions involving hot hydrogen atoms. The thermal reaction of CO + H2 + NH3 on Fischer-Tropsch catalysts generates intermediates that lead to amino acids and other organic compounds that have been found in meteorites. However, this synthesis appears to be less efficient than electric discharges and to require a special set of reaction conditions. It should be emphasized that after the reactive organic intermediates are generated by the above processes, the subsequent reactions which produce the more complete biochemical compounds are low temperature homogenous reactions occurring in an aqueous environment.     

The prebiotic molecules observed in the interstellar gas

Over 130 molecules have been identified in the interstellar gas and circumstellar shells, the largest among them is a carbon chain with 13 atoms and molecular weight of 147 (twice that of the simplest amino acid glycine). The high reliability of astronomical identifications, as well as the fairly accurate quantitative analysis which can often be achieved, is emphasized. Glycine itself has been claimed, but a recent analysis indicates that few, if any, of the astronomical radio lines attributed to glycine are actually from that molecule. Polycyclic aromatic hydrocarbons (PAHs) have long been proposed as the source of the unidentified infrared bands between 3 and 16 microm, but no single PAH has been identified in space, partly because PAHs generally have weak or non-existent radio spectra. A remarkable exception is the non-planar corannulene molecule (C20H10) that has a strong radio spectrum; in the rich molecular cloud TMC-1, it is found that less than 10-5 of the carbon is contained in this molecule, suggesting that PAHs are not the dominant large molecules in the interstellar gas, as has been claimed. Owing to inherent spectroscopic limitations, determining the structures of the large molecules in space may require capture of the dust grains, which are continually entering the outer Solar System.     

On the formation and observation of complex interstellar molecules

As of the present, a significant number of small molecules have been discovered in the interstellar medium. The largest molecule unambiguously detected, HC₁₁N, has only thirteen atoms. In this article, the prospects for observing far more complex species than this in interstellar clouds are discussed as are the mechanisms by which such complex species might be synthesized.     

Theoretical interstellar and prebiotic organic chemistry: A tentative methodology

A theoretical methodology for the systematic study of the interstellar molecules is proposed.Some examples, dealing with formaldehyde excited states, formyl radical and ion, reactivity of the excited states of formic acid, methyl cyanide and methyl acetylene, as well as the reaction path of formaldehyde photodecomposition are presented.Quantum chemical methods appear to be a powerful tool to study the structure and behaviour of molecules related with interstellar space and the Origin of Life.     

Lunar organic analysis: Implications for chemical evolution

The lunar samples provided some material from the early period of the solar system. These samples could have preserved in them some of the stages in the evolution of carbon compounds. The analysis, so far, has not revealed with certainty a single organic compound of biological significance. However, the finding of methane, carbon monoxide, carbides, etc. could be considered in the context of cosmic evolution.     

Effects of alpha-tocopherol and related compounds on reactions involving various organic radicals

Effects of alpha-tocopherol, PMC, and a number of the respective sulfur-containing analogues on reactions involving various organic radicals were studied. The test compounds were found to interact with alkyl radicals more effectively than with peroxyl radicals. The presence of a sulfur atom in structures of the respective analogues did not produce significant effects on reactivity. Derivatives of 5-hydroxy-1,3-benzoxathiol-2-one and 6-hydroxy-1,4-benzoxathiin-2(3H)-one displayed a high reactivity toward alpha-hydroxyalkyl radicals.     

Structural studies of decavanadate compounds with organic molecules and inorganic ions in their crystal packing

The formation of decavanadates containing amine counter-ions is explored to get a better insight into the resulting crystal packing. From mixtures containing the Schiff base H₂(SO₃-sal)₂en and vanadate, two different compounds containing decavanadate units have been characterised by X-ray diffraction. The structure of 1 consists of [V₁₀O₂₈]⁶⁻ monomers united by K⁺, ethylenediamine cations and H₂O molecules, which act as bridging atoms between the layers, forming a three-dimensional array. The structure of 2 contains vanadium triprotonated decavanadate anions, [H₃V₁₀O₂₈]³⁻, in one-dimensional vertical chains, bonded by interdecavanadate hydrogen bonds. The interchain region is populated by (H₂en)²⁺ cations and H₂O molecules, which form a network of hydrogen bonds. From the filtrate solution of the reaction mixture containing V^IVOSO₄, d,l-diaminopropionic acid and salicylaldehyde, which also contained triethylamine, a diprotonated decavanadate 3 was obtained. Compound 3 consists of decavanadate vertical dimers, surrounded by triethylamonium cations that preclude the interaction between the dimers. Bond valence calculations were used to confirm the degree of protonation of the decavanadate anions.     

Molecular dynamics simulations on the aggregation behavior of indole type organic dye molecules in dye-sensitized solar cells

In Ti0₂ nanostructured dye-sensitized solar cells indole based organic dyes D149, D205 exhibits greater power conversion efficiency. Such organic dye molecules are easily undergone for aggregation. Aggregation in dye molecules leads to reduce electron transfer process in dye-sensitized solar cells. Therefore, anti-aggregating agents such as chenodeoxycholic acid are commonly added to organic dye solution in DSSCs. Studying aggregation of such dye molecules in the absence of semiconductors gives a detailed influence of anti-aggregating agents on dye molecules. Atomistic level of molecular dynamics (MD) simulations were performed on aggregation of indole type dye molecules D149, D205 and D205-F with anti-aggregating agent chenodeoxy cholic acid using AMBER program. The trajectories of the MD simulations were analyzed with order parameters such as radial atom pair distribution functions g(r), diffusion coefficients and root mean square deviations values. MD results suggest that addition of chenodeoxy cholic acid to dyes significantly reduces structural arrangement and increases conformational flexibility and mobility of dye molecules. The influence of semi-perfluorinated alkyl chains in indole dye molecules was analyzed. The parameters such as open-circuit voltage (V_oc) and power conversion efficiency (η) of dye-sensitized solar cells are corroborated with flexibility and diffusion values of dye molecules.     

有机物生物降解性评价方法综述

评价有机物生物降解性的方法和文献很多,但缺乏系统性介绍评价方法及指导方法选择的综述性文献.本文围绕有机物的生物降解性评价,简要介绍了评价有机物生物降解性的指示性参数及厌、好氧有机物生物降解性评价方法,着重介绍了评价方法选择的标准和原则,并详细分析了不同试验方法使用过程中产生有机物生物降解率差异的原因.最后,以世界经济合作与发展组织(OECD)制定的标准为例,全面介绍了该评价方法的选择使用过程并整合这一评价体系绘制了方法选择路线图,指出了各项试验方法的优越性.     

Homodesmotic reactions in helicene and phenacene molecules

Helicene molecules were analysed on the basis of their intrinsic aromaticity, and compared with the corresponding phenacene. The analysis of aromaticity was performed by homodesmotic reactions, and by the nucleus independent chemical shifts (NICS) index in the centre of the aromatic rings as well as in the centre of the helix. The results are very interesting, because the NICS shows that there is a strong antiaromatic zone in the centre of the molecule, and a strong aromatic zone in the strip. Therefore, these molecules represent a medley of electronic effects.     

Bioactive compounds in legumes: pronutritive and antinutritive actions. Implications for nutrition and health

Legume seeds are employed as a protein source for animal and human nutrition not only for their nutritional value (high in protein, lipids and dietary fibre), but also their adaptability to marginal soils and climates. Human consumption of legumes has been increased in recent years, being regarded as beneficial food ingredients. Legume seeds contain a great number of compounds which qualify as bioactive compounds with significant potentials benefits to human health. These compounds vary considerably in their biochemistry and they can be proteins, glycosides, tannins, saponins, alkaloids, etc. Hence, methods for their extraction, determination and quantification are specific of each compound. They do not appear equally distributed in all legumes, and their physiological effects are diverse. Some of these compounds are important in plant defence mechanisms against predators or environmental conditions. Others are reserve compounds, accumulated in seeds as energy stores in readiness for germination. Processing generally improves the nutrient profile of legume seed by increasing in vitro digestibility of proteins and carbohydrates and at the same time there are reductions in some antinutritional compounds. Most antinutritional factors are heat-labile, such as protease inhibitors and lectins, so thermal treatment would remove any potential negative effects from consumption. On the other hand tannins, saponins and phytic acid are heat stable but can be reduced by dehulling, soaking, germination and/or fermentation. New directions in bioactive compounds research in the last decade have led to major developments in our understanding of their role in nutrition. The scientific interest in these compounds is now also turning to studies of their possible useful and beneficial applications as gut, metabolic and hormonal regulators and as probiotic/prebiotic agents.