Articles by Marye Anne Fox

MARYE ANNE FOX Department of Chemistry University of Texas Austin The design of short monomeric peptides with stable helical secondary structure can be achieved by complexation with ap- propriate metal ions. The unusual stability of the resulting helix may relate to the enhanced entropy of the cross-linked peptide. F.Q. Ruan, Y.Q. Chen, P.B. Hopkins, "Metal ion enhanced helicity in synthetic peptides containing unnatural, metal-ligating residues," Journal of the American Chemical Society (J

Department of Chemistry University of Texas Austin Single-junction photoelectrochemical devices suffer four unavoidable losses: lack of absorption of incident light, thermalization of ultra-band gap photons, differences between available and internal energy of thermalized excited states, and radiative decay. A recent article shows how a consideration of the absorption and transport properties of molecular chromophores and semiconductors can usefully predict optimal conditions for efficient so

Progress toward attaining an accurate solution of the Schr”dinger equation has occurred in spurts, with fully convergent solutions of a number of systems having appeared recently. One approach that has made this achievement possible is described: the use of the generalized Newton variational principle in which the reactive amplitude density is expanded variationally in a basis set of integral functions. D.G. Truhlar, D.W. Schwenke, D.J. Kouri, "Quantum dynamics of chemical reactions by c

Department of Chemistry University of Texas Austin Suitably arranged molecular components can be used to probe fundamental photochemical principles and to discover new functions and applications of photochemistry. A paper, presented at the 13th IUPAC Symposium on Organic Photochemistry in Coventry, England, in July, considers systems made of covalently linked components, ion pairs, host-guest interactions, and caged complexes. V. Balzani, L. De Cola, L. Prodi, F. Scandola, "Photochemistry of

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Texas The prediction of ab initio calculations that a C 18 cyclocarbon would possess alternating single and triple bonds seems to be verified in a recent study, which reports the laser flash pyrolysis of a well-characterized precursor to the title compound. Structural evidence for its formation via a retro-Diels-Alder reaction of an appropriate [18] annulene is presented. F. Diederich, Y Rubin, C.B. Knob

CHEMISTRY BY MARYE ANNE FOXBR> Department of Chemistry University of Texas, Austin Austin, Texas " Sequence-specific binding of pyrimidine oligonucleotides can block recognition of double helical DNA, and analogous binding of other oligonucleotides may make possible sequencespecific protein binding. L.J. Maher III, B. Wold, P.B. Dervan, “Inhibition of DNA binding proteins by oligonucleotide directed triple helix formation,” Science, 245,725-30, 18 August 1989. (California Instit

CHEMISTRY BY MARY E. ANNE FOX Department of Chemistry University of Texas, Austin Austin, Texas The hypothesis that nothing in biology makes sense except in light of evolution is appliedto selective and nonselective behaviors in enzymology. Merely distinguishing between these types of behavior is quite a challenge. S.A. Benner, “Enzyme kinetics and molecular evolution,” Chemical Reviews, 89, 789-806, June 1989. (Laboratory of Organic Chemistry, ETH-Zentrum, Zurich, Switzerland)

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " Alkoxide ligands, acting as pi donors to stabilize early transition metals in high oxidation states, and carbonyls, acting as pi acceptors to stabilize late transition elements in low oxidation states, provide complementary ligand effects to inorganic clusters. A recent article summarizes the effect of such ligands in controlling substrate binding; electronic saturation, and stenc control in organo

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " Acyl transfer, hydrolysis, carbon-carbon and amide bond formation, and redox reactions can be catalyzed by antibodies (abzymes). A recently published article demonstrates that specific hydrolysis of unactivated esters by bound antibodies can occur with rate accelerations of 10^3 to 10^5 above background. K.D. Janda, S.J. Benkovic, R.A. Lerner, “Catalytic antibodies with lipase activity and R

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " The assignment of the resonance Raman spectra in the fingerprint region for the initial picosecond interval of the bacteriorhodopsin photocycle establishes the primary event as involving a configurational change in the retinal chromophore. G.H. Atkinson, T.L. Brack, D. Blanchard, G. Rumbles, “Picosecond time-resolved resonance Raman spectroscopy of the initial trans to cis isomerization in th

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " " Selective interactions through properly oriented functionalities allow for molecular recognition. The surface properties of this chiral monolayer show strongly temperature-dependent chiral recognition attributable to long range order. N.G. Harvey, D. Mirajovsky, P.L. Rose, R. Verbiar, E.M. Arnett, “Molecular recognition in chiral monolayers of stearoylserine methyl ester,” Journal of

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " Organolithiums exhibit a wide range of structures, in which interconversions are so fast as to obviate methods. This paper describes the structure of a chiral monomeric tridentately coordinated complex that is conformationally locked into one rotamer such that bond exchange is slow relative to the NMR time scale. G. Fraenkel, W.R. Winchester, “Chiral lithium: conformation and dynamic behavior

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " Effective planning of strategy represents the most important intellectual attainment of synthetic organic chemistry. One of the masters has provided an overview in a recently published Robert Robinson lecture. E.J. Corey, “Retrosynthetic thinking, Essentials and exam- pels," Chemical Society Reviews, 17 (2), 111-34, June 1988. " The ability to cleave DNA at will at a specific position is a m

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " Host-guest chemistry is an important vehicle for characterizing the factors involved as molecules react. Two recently published Nobel lectures presents fascinating overview that takes the reader from Pedersen’s original discovery of macrocyclic ethers through the preorganization and structural recognition in Cram’s early studies to more recent uses of hosts as enzyme mimics and synthe

CHEMISTRY BY MARYE ANNE FOX Department of Chemistry University of Texas, Austin Austin, Tex. " Organoboranes can be readily converted to other functional groups under mild conditions, making them versatile intermediates of organic synthesis. Their use in optically active compounds has been reviewed recently. H.C. Brown, B. Singaram, “Development of a simple general procedure for synthesis of the pure enantiomers via chiral organoboranes,” Accounts of Chemical Research, 21 (8), 2