Methyl p-dimethylaminobenzenesulfonate rearranges in the solid state, as a malt, and in solution to a zwitterionic product, p-trimethylammoniumbenzenesulfonate. By a combination of kinetic and field desorption mass spectrometric techniques, we have found that the reaction is intermolecular and that it proceeds at a considerably faster rate in the crystal than it does either in the melt or in solution. The structure of the starting sulfonate has been solved by single crystal x-ray diffraction, and this study revealed that the molecules in the crystal are nearly ideally oriented for reaction in the solid state. Powder diffraction studies have shown that due to the constraints of the starting crystal lattice, the product is initially formed in a metastable crystalline form which slowly reverts to its thermodynamically most stable crystalline modification.

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There exists an extensive literature on the possible roles of minerals in the prebiotic stages of the chemical evolution of life (Bernal 1951, Cairns-Smith 1982, Wächtershäuser 1992, Vieyra et al. 1995, Tessis et al. 1999, see Lahav (1994 for a review). Among the original proposals, minerals have been considered in: (a) processes that would discriminate molecular chirality; (b) condensation reactions of biomolecular precursors; (c) prebiotic catalysis; (d) biochemical templates; and (e) autocatalytic metabolism. In this communication it is emphazised the complex properties of both surface reactions and interfaces between minerals and aqueous solutions simulating Archean scenarios. The properties of pyrite surface net charge and of its interface with a solution simulating primitive seawater are discussed and their implications to the autocatalytic model (Wächtershäuser 1988a(Wächtershäuser 1992 are presented in order to demonstrate their relevance. The proposed roles of iron-sulfide minerals (mainly pyrite) as physical support for primitive bidimensional metabolism and chiral discriminator (Wächtershäuser 1988a, Huber & Wächtershäuser 1998 are revised. It is shown that: (a) the net surface charge can be modulated by the pyrite-aqueous solution interface; (b) mononucleotides attachment to pyrite require a cationic bridge; and (c) direct absorption of acetate -a molecule proposed as carbon source in primitive aqueous environments -also modulates the interface properties and would have masked pyrite's bulk structure. These results indicate that physicochemical changes of mineral surfaces -caused by environments simulating Archean aqueous scenarios -should be taken into account in the proposals of mineral prebiotic roles.

The adsorption of adenosine 5'-monophosphate (5'-AMP) onto pyrite (FeS2) and its modulation by acetate, an organic precursor of complex metabolic pathways, was studied in aqueous media that simulate primitive environments. 5'-AMP adsorption requires divalent cations, indicating that a cationic bridge mediates its attachment to negatively charged sites of the mineral surface. The isotherm of 5'-AMP adsorption exhibits a strong cooperative effect at low nucleotide concentrations in acetate-rich medium, whereas high levels of adsorption were only found at high nucleotide concentrations in a model of primitive seawater (acetate free). The modulating role of acetate is also evidenced in the presence of high dipolar moment molecules: dimethyl sulfoxide (Me2SO) and dimethyl formamide (DMF) strongly inhibit 5'-AMP adsorption in acetate-rich media, whereas no effect of DMF was found in artificial seawater. The observation that exogenous divalent cations are not needed for acetate attachment onto FeS2 reveals that organic acids can interact with the Fe2+ atoms in the mineral surface. All considered, the results show that complex and flexible ironsulfide/biomonomers interactions can be modulated by molecules that accumulate in the interface layer.

Phosphate (P(i)) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P(i) sorption whereas mild alkaline media--as well as those simulating sulfur oxidation to SO(2-) (4)--revert this capture process. Several mechanisms relevant to P(i) availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg(2+) bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO(2-) (4) trapping by the mineral interface would provoke the release of sorbed P(i) due to charge polarization. Moreover it is shown that P(i) self-modulates its sorption, a mechanism that depends on the abundance of SO(2-) (4) in the interface. The relevance of the proposed mechanisms of P(i) capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since--similarly to contemporary aqueous media--inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P(i) could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.