Surface X-ray Scattering Study of Stereospecific Adsorption of Additives onto the Surface of a Molecular Crystal Grown from Solution

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 9, 1997, Pages 959-962

  Gidalevitz, David ^a,c   Feidenhans'l, Robert ^b   Leiserowitz, Leslie ^a  

^a WEIZMANN INSTITUTE OF SCIENCE   (Israel)

^b TECHNICAL UNIVERSITY OF DENMARK   (Denmark)

^c UNIVERSITY OF PENNSYLVANIA   (United States)

Author keywords

Amino acids; Crystal growth; Surface analysis

Indexed keywords

EID: 0030916213     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199709591     Document Type: Article

References (30)

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7. For "tailor-made" additives the stereospecific adsorption onto particular crystal faces was also established by methods that showed that the additives occupied crystallographically appropriate sites within the crystal. This was only possible by stereospecific adsorption at molecular sites on the growing crystal faces. These methods included optical birefringence [8], second harmonic generation, solid state-photochemistry, and X-ray and neutron diffraction of the bulk crystals [5.6].
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15. The symbol {hkl} represents all symmetry-related faces, whereas (hkl) refers only to faces pertaining to h, k, and l. Therefore {010} represents the faces (010) and (01̄0).
16. An X-ray wavelength of 1.31 Å was used. For the nonspecular CTR measurements the surface was vertical and aligned with a laser such that the surface normal was parallel with the ω axis of the diffractometer, which ensures a constant angle of incidence throughout the experiments. The angle of incidence was set at 0.2°. The CTR scans were measured by a rocking scan around the surface normal at each momentum transfer in the direction perpendicular to the surface in order to measure the integrated intensity. For the specular reflection the sample was remounted with the surface nearly horizontal in order to keep a vertical scattering plane. The scan along the specular rod was performed along the ridge of scattering. The background was measured along a slightly off-specular direction by off-setting the ω angle to lower the radiation damage, which is much more severe in the specular than the nonspecular case due to the larger intersection of the crystal with the beam. The intensities were corrected for Lorentzian and polarization factors and variations in active area in order to achieve a structure factor intensity for both specular and nonspecular CTRs.
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19. D. Gidalevitz, R. Feidenhans'l, S. Matlis, D. M. Smilgies, M. J. Christensen, L. Leiserowitz, Angew. Chem. 1997, 109, 991; Angew. Chem. Int. Ed. Engl. 1997, 36, 955.
20. D. Gidalevitz, R. Feidenhans'l, S. Matlis, D. M. Smilgies, M. J. Christensen, L. Leiserowitz, Angew. Chem. 1997, 109, 991; Angew. Chem. Int. Ed. Engl. 1997, 36, 955.
21. The peak at k = 3.15 in the CTRs for the (010) and (01̄0) surfaces (red rhombs of Figure 3, top) corresponds to the (004) reflection of (S)-methionine. The platelike crystals of methionine were deposited onto both the (010) and (01̄0) faces of α-glycine but were not attached stereospecifically. In a separate experiment on growth of α-glycine in the presence of (S)-methionine under similar experimental conditions, we observed very small (≈0.1 mm) methionine plates randomly distributed on both the glycine surface and the bottom of the vessel. These plates could be easily removed and, therefore, were not structurally attached to glycine. These methionine crystallites do not contribute to the nonspecular diffraction patterns.
22. When the relative occupancies were varied by more than 0.1 from the best value, the fit became significantly worse.
23. 3 torsion angles yielded six possible methionine conformations. We tested all of them in different combinations with varying occupancies for X-ray structure factors calculations. The best fit to the observed data was obtained for the molecular conformations A (trans-gauche) and B (gauche-gauche), which are similar to those in the three-dimensional crystal structures of (S)- and (R,S)-methionine [22], with occupancies of 0.5 and 0.3, respectively.
24. 2, a molecular modeling software package for materials research, BIOSYM Molecular Simulations, Cambridge, UK.
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26. The A:B occupancy ratio for methionine was kept at 0.5:0.3 [20]. Furthermore, the two conformers appear to pack in separate domains. Models with A and B within the same crystal domain (coherent addition) yielded poorer agreement to the observed data than the model in which they pack in separate domains (incoherent addition).
27. -1. In the latter system the two bilayers lie in the central plane of the crystal and are each composed of heterodimers of glycine and (S)-leucine in an arrangement similar to that of the glycine/(S)-methionine heterobilayer (Figure 4B).
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30. GID results on the (010) face do not contradict the experimental observations of stereospecific inhibition of the {010} faces of glycine with enantiomerically pure α-amino acids as additives. Our experiments were performed with cleaved crystals of glycine and concentrations of α-amino acid additive as high as 9 wt %.