A diborane(6) bridged diiron hexacarbonyl: preparation of B2H6Fe2(CO)

A diborane(6) bridged diiron hexacarbonyl: preparation of B2H6Fe2(CO)6 ... nido-Metalloborane Complexes: Synthesis and Structural Characterization of ...
0 downloads 0 Views 319KB Size
Journal of the American Chemical Society

4606

mation on clays was rationalized only in terms of eq 1 and a terminating step which involved the formation of an inactive adenylate ester bond (A-P).20-24 Equation 1 is likely to describe the polymerization of adenylates on clays since the adenylate binds to them while amino acids do not. In reversed micelles, however, eq 2 cannot be ignored since amino acids formed from the hydrolysis of the amino acyl adenylates remain in the aqueous core of the reversed micelle in close contact with other adenylates. The chain termination step of the clay mediated polymerization (ester formation, A-P) rested upon the observed high percentages of peptides which contained terminal adenylic acid.20 Our inability to detect terminal adenylic acid in the peptides in the present work (either by absorption or 252Cfplasma desorption mass spectroscopy) may imply different mechanisms in the clay and micellar systems. Alternatively, inactive amino acid esters of A M P (A-P) could have been present as impurities in the amino acyl adenylates (A-P) used in the clay experiment^.^^^^^ A-P could react, of course, with A-P to give A*-P and P. It has been shown that the dicyclyhexylcarbodiimide,DCC, mediated synthesis of amino acyl adenylates, the method used to prepare A-P in the clay contained up to 20% A-P irnpurity.l7 The reaction of this ester impurity with the amino acyl adenylates (or peptide acyl adenylates) would result in peptides with a terminal A M P ester. Conversely, the method of preparation used in this work for A-P does not lead to A-P contamina-

+

The micelle performs a t least three functions which result in the formation of high molecular weight peptides: (1) they concentrate A-P, (2) they maintain the reaction a t a p H >7, and (3) they minimize competing hydrolysis. The kinetics and mechanism of the condensation of amino acyl adenylates to high molecular weight peptides is the subject of our current and intensive investigation. The use of more complex functional micelles and colloidal aggregates is expected to result in even more efficient polycondensations.

References and Notes J. H. Fendler and E. J. Fendler, "Catalysis in Micellar and Macromolecular Systems", Academic Press, New York, N.Y., 1975. J. H. Fendler, Acc. Chem. Res., 9, 153 (1976). M. Calvin, "Chemical Evolution: Molecular Evolution Towards the Origins of Living Systems on Earth and Elsewhere", Clarendon Press, Oxford, 1969. J. Nagyvary and J. H. Fendler, Origins Life, 5, 357 (1974). E. H. Cordes and C. Gitler, Prog. Bioorg. Chem., 2, 1 (1973). C. A. Bunton, Prog. Solid State Chem., 8, 239 (1973). J. H. Fendier, F. Nome, and J. Nagyvary. J. Mol. Evol., 6, 215 (1975). J. Nagyvary, J. H. Harvey, F. Nome, D. W. Armstrong, and J. H. Fendler, Precambrian Res., 3, 509 (1976). D. W. Armstrong and J. H. Fendler, Biochim. Biophys. Acta, 478, 75 (1977). D. W. Armstrong, R . Seguin, and J. H. Fendler, J. Mol. Evol., 10, 241 (1977). D. W. Armstrong, F. Nome, J. H. Fendier, and J. Nagyvary, J. Mol. Evol., 9, 213 (1977). Analogous polymerization experiments have been done on clays; however, the results are not always reproducible. See, for example, J. T. Warden, J. J. McCuliough, R . Lemmon, and M. Calvin, J. Mol. Evoi., 4, 189 (1974). R . D. Macfariane and D. F. Torgerson, Science, 191, 920 (1976). [14C] Alanyl and alanyl adenylate were synthetized using the tert-butoxycarbonyl protected amino acids in anhydrous solvents: D. W. Armstrong. R. Seguin and J. H. Fendler, submitted for publication. In water at pH