1. Simulation of diffuse scattering in DL-norleucine
Thomas Richard Welberry, Carl Henrik Görbitz Acta Crystallogr B Struct Sci Cryst Eng Mater. 2019 Jun 1;75(Pt 3):393-405. doi: 10.1107/S2052520619004839. Epub 2019 May 22.
The diffraction patterns of DL-norleucine (SR-2-aminohexanoic acid, DL-Nle) crystals may show obvious diffuse scattering, usually described as `streaking', between the Bragg peaks. This phenomenon is obviously related to the non-ideal behaviour of the crystal. The normal interpretation is disorder in the stacking of weakly interacting 2D layers, known also for a number of other racemates of amino acids with linear hydrophobic side chains, as well as 1:1 complexes between different L- and D-enantiomers (quasi-racemates). Presented here is the first attempt to extract the information hidden in the diffuse scattering for this group of compounds by applying Monte Carlo simulations to the site distributions of two polymorphs in a block of 48 × 48 × 48 unit cells (four sites in each unit cell, 442 368 in total). The results demonstrate that it is indeed possible to model the diffuse scattering and relate it to processes expected to take place during phase transitions, characterized by slipping of molecular bilayers (or parts of them) relative to their neighbours. The understanding of the (intermediate) mixed phases in terms of domain size and defect density is consequently brought to a new level.
2. Do solid-to-solid polymorphic transitions in DL-norleucine proceed through nucleation?
Joost A van den Ende, Mireille M H Smets, Daniël T de Jong, Sander J T Brugman, Bernd Ensing, Paul T Tinnemans, Hugo Meekes, Herma M Cuppen Faraday Discuss. 2015;179:421-36. doi: 10.1039/c4fd00214h. Epub 2015 Apr 16.
DL-Norleucine is a molecular crystal exhibiting two enantiotropic phase transitions. The high temperature α ↔ γ transition has been shown to proceed through nucleation and growth [Mnyukh et al., J. Phys. Chem. Solids, 1975, 36, 127]. We focus on the low temperature β ↔ α transition in a combined computational and experimental study. The temperature dependence of the structural and energetic properties of both polymorphic forms is nearly identical. Molecular dynamics simulations and nudged elastic band calculations of the transition process itself, suggest that the transition is governed by cooperative movements of bilayers over relatively large energy barriers.
3. Terahertz Spectroscopy and Density Functional Theory Calculations of dl-Norleucine and dl-Methionine
Jens Neu, Heinrich Nikonow, Charles A Schmuttenmaer J Phys Chem A. 2018 Jul 19;122(28):5978-5982. doi: 10.1021/acs.jpca.8b04978. Epub 2018 Jul 5.
We present terahertz (THz) measurements and density functional theory (DFT) calculations of two amino acid crystals: dl-norleucine and dl-methionine. Their molecular structures are very similar and therefore also their crystal structures. We report the absorption spectra for both amino acids, which have a strong resonance at 1.87 THz in dl-norleucine and 1.94 THz in dl-methionine. In addition, we find a higher frequency resonance at 2.49 THz in dl-methionine, which has no corresponding mode in dl-norleucine. The experimental data are supported by DFT calculations, which show that the origin of the two strongest vibrational modes in dl-norleucine and dl-methionine are based on the same underlying vibrational motions, whereas the 2.49 THz resonance in dl-methionine is due to the motion of the sulfur atom, which is not present in dl-norleucine.
