Cosmic dust and our origins

The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized.     

Book Reviews

Unsigned book reviews are by the Book Review Editor.     

A two-stage nonlinear cochlear model possesses automatic gain control

A model of the cochlea is explored using as stimuli two simultaneously presented sinusoids of equal amplitude. The model consists of two stages: a linear bandpass filter, followed by a reservoir-type representation of the hair-cell/nerve-fiber complex. Fast Fourier transforms of the model's output were computed. While the amplitudes of the individual response components were strongly nonlinear functions of intensity, the ratio of the magnitudes of the response components at the frequencies of the two stimulating sinusoids was found to be nearly equal, over a wide intensity range, to the ratio of the amplitudes which those stimulating sinusoids possessed at the output of the filter. Thus the reservoir stage exerts "automatic gain control".     

Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

Relative energies of substituted benzene valence isomers

Ab initio calculations employing the STO-3G basis set are used to obtain the relative energies of the benzene valence isomers and some selected monosubstituted derivatives. We find that 3,3'-bicyclopropenyl, the least stable of the five (CH)₆ examined, is slightly more stable in the anti conformation than the gauche (Φ = 45°) conformation in agreement with experiment. Substituents are calculated to produce significant changes in the relative energies of the benzene valence isomers. The ground-state isomerization of 1-Dewar benzeneearbinyl cation to benzyl cation is more exothermic than the aromatization of Dewar benzene, but is, in contrast to the latter, symmetry-allowed.     

Preparation and analysis of oligonucleotides containing the c4'-oxidized abasic site and related mechanistic probes

The C4'-oxidized abasic site (C4-AP) is produced by a variety of DNA damaging agents. This alkali labile lesion can exist in up to four diastereomeric cyclic forms, in addition to the acyclic keto-aldehyde. Synthetic oligonucleotides containing the lesion were prepared from a stable photochemical precursor. Chemical integrity of the lesion containing oligonucleotides was probed using phosphodiesterase lability. Analysis of the 3',5'-phosphate diester of the monomeric lesion released from single diastereomers of photolabile precursors by 1H NMR indicates that isomerization of the hemiacetal and/or hemiketal is rapid. The syntheses and characterization of oligonucleotides containing configurationally stable analogues of C4-AP, which serve as mechanistic probes for deciphering the structural basis of the biochemical and biological effects of the C4'-oxidized abasic lesion, are also described.     

On the role of solvent in complexation equilibria. I. The acid-base chemistry of some α,ω-diaminocarboxylic acids in water-dioxane mixed solvents

The macroscopic and microscopic acid-base chemistry of a series of α,ω-diaminocarboxylic acids, H₂N(CH₂)_nCH(NH₂)COOH [n=4, lysine (LYS);n=3, ornithine (ORN);n=2, 2,4-diaminobutyric acid (DAB);n=1, 2,3-diaminopropionic acid (DAP)], was determined in water and its binary mixtures with dioxane (20.5, 40.7, 60.7, and 80.5 mass % dioxane) using carbon-13 nuclear magnetic resonance spectroscopy. The macroscopic acid dissociation constants for the titration of the two ammonium groups decrease uniformly with increasing dioxane composition. The microscopic constants, however, which characterize the relative concentrations of the two tautomers of singly protonated amino acid (I and II) $$\begin{gathered} H_3 \mathop N\limits^ + (CH_2 )_n CHCOO^ - H_2 N(CH_2 )_n CHCOO^ - \hfill \\ || \hfill \\ NH_2 \mathop N\limits_ + H_3 \hfill \\ III \hfill \\ \end{gathered}$$ reveal that while tautomer I is favored in aqueous solution, tautomer II becomes more important with increasing dioxane composition for LYS and ORN. The relative concentrations of I and II remain unchanged with solvent composition for DAP. These results are explained in terms solute-solvent and solvent-solvent interactions.