Competitive adsorption of glycine and water on the fluorapatite (100) surface.

The atomic structure of the aqueous glycine-fluorapatite (100) interface was investigated using grazing incidence X-ray diffraction. Experimental data analysis of crystal truncation rod intensities revealed detailed information on lateral as well as perpendicular ordering of the adsorbate molecules and the nature of atomic relaxations in the fluorapatite (FAp) (100) surface. Glycine and water molecules are arranged in two periodically ordered layers at the aqueous glycine-mineral interface. The adsorption process on the mineral surface is site competitive as both the glycine and water molecules show equal affinity toward surface Ca2+ cations. The glycine molecules interact directly with the FAp (100) surface, where one of their carboxylate groups coordinates with the surface Ca2+ cations. From the surface structure refinement, atomic positions of one glycine and four water molecules per unit cell were determined, along with the atomic relaxations in the FAp (100) surface. Molecular dynamic simulations were used to determine the long-range order of the adsorbate layers by investigating the hydrogen bonds.

Structure of interfacial water on fluorapatite (100) surface.

The structure relaxation mechanism of the fluorapatite (100) surface under completely hydrated ambient conditions has been investigated with the grazing incidence X-ray diffraction (GIXRD) technique. Detailed information on lateral as well as perpendicular ordering corresponding to the water molecules and atomic relaxations of the (100) surface of fluorapatite (FAp) crystal was obtained from the experimental analysis of the CTR intensities. Two laterally ordered water layers are present at the water/mineral interface. The first layer consists of four water molecules located at 1.6(1) A above the relaxed fluorapatite (100) surface while the second shows the presence of only two water molecules at a distance of 3.18(10) A from the mineral surface. Thus, the first layer water molecules complete the truncated coordination sites of the topmost surface Ca atoms, while the second water layer molecules remain bonded by means of H-bonding to the first layer molecules and the surface phosphate groups. Molecular mechanics simulations using force field techniques are in good agreement with this general structural behavior determined from the experiment.

Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface.

For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.

Why are BINOL-based monophosphites such efficient ligands in Rh-catalyzed asymmetric olefin hydrogenation?

Whereas recent synthetic studies concerning Rh-catalyzed olefin hydrogenation based on BINOL-derived monodentate phosphites have resulted in an efficient and economically attractive preparative method, very little is known concerning the source of the unexpectedly high levels of enantioselectivity (ee often 90-99%). The present mechanistic study, which includes the NMR characterization of the precatalysts, kinetic measurements with focus on nonlinear effects, and DFT calculations, constitutes a first step in understanding this hydrogenation system. The two most important features which have emerged from these efforts are the following: (1) two monodentate P-ligands are attached to rhodium, and (2) the lock-and-key mechanism holds, in which the thermodynamics of Rh/olefin complexation with formation of the major and minor diastereomeric intermediates dictates the stereochemical outcome. The major diastereomer leads to the favored enantiomeric product, which is opposite to the state of affairs in classical Rh-catalyzed olefin hydrogenation based on chiral chelating diphosphines (anti lock-and-key mechanism as proposed by Halpern).