Hydrogen cyanide polymers from the impact of comet P/Shoemaker-Levy 9 on Jupiter.

Hydrogen cyanide polymers--heterogeneous solids ranging in color from yellow to orange to brown to black--may be among the organic macromolecules most readily formed within the Solar System. The non-volatile black crust of comet Halley, for example, as well as the extensive orange-brown streaks in the atmosphere of Jupiter, might consist largely of such polymers synthesized from HCN formed by photolysis of methane and ammonia. Laboratory studies of these ubiquitous compounds point to the presence of polyamidine structures synthesized directly from hydrogen cyanide. These would be converted by water to polypeptides which can be further hydrolyzed to alpha-amino acids. Other polymers and multimers with ladder structures derived from HCN would also be present and might well be the source of the many nitrogen heterocycles, adenine included, detected by thermochemolytic analysis. The dark brown color arising from the impacts of comet P/Shoemaker-Levy 9 on Jupiter could therefore be mainly caused by the presence of HCN polymers, whether originally present, deposited by the impactor or synthesized from freshly formed HCN. Spectroscopic detection of these predicted macromolecules and their hydrolytic and pyrolytic by-products would strengthen significantly the hypothesis that cyanide polymerization is a preferred pathway for prebiotic and extraterrestrial chemistry.

Hydrogen cyanide polymers on comets.

The original presence on cometary nuclei of frozen volatiles such as methane, ammonia and water makes them ideal sites for the formation and condensed-phase polymerization of hydrogen cyanide. We propose that the non-volatile black crust of comet Halley consists largely of such polymers. Dust emanating from Halley's nucleus, contributing to the coma and tail, would also arise partly from these solids. Indeed, secondary species such as CN have been widely detected, as well as HCN itself and particles consisting only of H, C and N. Our continuing investigations suggest that the yellow-orange-brown-black polymers are of two types: ladder structures with conjugated -C=N- bonds, and polyamidines readily converted by water to polypeptides. These easily formed macromolecules could be major components of the dark matter observed on the giant planets Jupiter and Saturn, as well as on outer solar system bodies such as asteroids, moons and other comets. Implications for prebiotic chemistry are profound. Primitive Earth may have been covered by HCN polymers either through cometary bombardment or by terrestrial happenings of the kind that brought about the black crust of Halley. The resulting proteinaceous matrix could have promoted the molecular interactions leading to the emergence of life.

Organic analysis of hydrogen cyanide polymers: prebiotic and extraterrestrial chemistry.

Hydrogen cyanide polymerizes readily to a black solid from which a yellow-brown powder can be extracted by water and further hydrolyzed to alpha-amino acids. These macromolecules could be major components of the dark matter observed on many bodies in the outer solar system, including comets and asteroids. Primitive Earth might therefore have been covered with HCN polymers through bolide bombardment or be terrestrial synthesis. Several instrumental methods were used for the separation and identification of these intriguing polymeric materials, including photoacoustic Fourier transform infrared spectroscopy, supercritical fluid extraction chromatography and pyrolysis mass spectrometry. Our integrated analytical approach revealed fragmentation patterns and chemical functionalities consistent with the presence of polymeric peptide precursors both in HCN polymers and in the Murchison meteorite.

Hydrogen cyanide polymerization: a preferred cosmochemical pathway.

Current research in cosmochemistry shows that crude organic solids of high molecular weight are readily formed in planetary, interplanetary and interstellar environments. Underlying much of this ubiquitous chemistry is a low energy route leading directly to the synthesis of hydrogen cyanide and its polymers. Evidence from laboratory and extraterrestrial investigations suggests that these polymers plus water yield heteropolypeptides, a truly universal process that accounts not only for the past synthesis of protein ancestors on Earth but also for reactions proceeding elsewhere today within our solar system, on planetary bodies and satellites around other stars and in the dusty molecular clouds of spiral galaxies. The existence of this preferred pathway - hydrogen cyanide polymerization - surely increases greatly the probability that carbon-based life is widespread in the universe.

The origin of proteins: Heteropolypeptides from hydrogen cyanide and water.

Evidence from laboratory and extraterrestrial chemistry is presented consistent with the hypothesis that the original heteropolypeptides on Earth were synthesized spontaneously from hydrogen cyanide and water without the intervening formation of chi-amino acids, a key step being the direct polymerization of atmospheric hydrogen cyanide to polyaminomalononitrile (IV) via dimeric HCN. Molecular orbital calculations (INDO) show that the most probable structure for (HCN)2 is azacyclopropenylidenimine. Successive reactions of hydrogen cyanide with the reactive nitrile side chains of IV then yield heteropolyamidines which are converted by water to heteropolypeptides. To study this postulated modification of a homopolymer to a heteropolymer, poly-chi-cyanoglycine (IX) was prepared from the N-carboxyanhydride of chi-cyanoglycine. Hydrolysis of IX, a polyamide analog of the polyamidine IV, yielded glycine. However, when IX was hydrolysed after being treated with hydrogen cyanide, other chi-amino acids were also obtained including alanine, serine, aspartic acid and glutamic acid, suggesting that the nitrile groups of IX (and therfore of IV) are indeed readily attacked by hydrogen cyanide as predicted. Further theoretical and experimental studies support the view that hydrogen cyanide polymerization along these lines is a universal process that accounts not only for the past formation of primitive proteins on Earth, but also for the yellow-brown-orange colors of Jupiter today and for the presence of water-soluble compounds hydrolyzable to chi-amino acids in materials obtained from environments as diverse as the moon, carbonaceous chondrites and the reaction chambers used to simulate organic synthesis in planetary atmospheres.

'Fiddler's neck'.

'Fiddler's neck' is a condition affecting violin and viola players. Although well known to musicians it is not well recognized by dermatologists. Clinically the lesions usually consist of a localized area of lichenification of the left side of the neck--just below the angle of the jaw. Pigmentation, erythema and inflammatory papules or pustules are frequently present, while severe inflammatory induration, cyst formation and scarring occur in more severely affected subjects. The aetiology of the skin changes is probably due to a combination of factors; friction giving rise to lichenification, while local pressure, shearing stress and occlusion may play a part in producing the acne-like changes and cyst formation. In addition, poor hygiene may predispose to local sepsis.

Structural investigations of hydrogen cyanide polymers: new insights using TMAH thermochemolysis/GC-MS.

Hydrogen cyanide polymers form spontaneously from HCN and traces of base catalysts. It is probable that these polymers played an important role in the early stages of chemical evolution. Nevertheless, their full structural characterization has still not been accomplished. A number of mass spectrometric methods have now been applied to this structural problem including FAB-MS, thermal desorption EI-MS, ESI-MS, APCI-MS and off-line TMAH thermochemolysis/GC-MS. This latter method causes bond cleaveage and in situ methylation producing a suite of products which provides valuable insight into the substructural features of HCN polymers and also promises to serve as a sensitive diagnostic tool for detecting the presence of HCN polymers in samples from diverse sources.