1. Understanding the growth mechanism of L-cystine using three-dimensional Monte-Carlo simulation
- Author
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Al Harthi, Zulaikha and Attfield, Martin
- Subjects
modifier ,stress ,tetragonal L-cystine ,CrystalGrower ,L-cystine ,Monte-Carlo - Abstract
Despite their fascinating beauty, crystals may encounter a pathogenic perspective that can be deadly in many cases. For instance, L-cystine is responsible for a type of kidney stone called Cystinuria, and the growth of L-cystine crystals is a critical step in stone pathogenesis. Atomic Force Microscopy provided the crystal growth research field with a treasury amount of information. With the incorporation of computational modelling, a more detailed understanding of growth and inhibition mechanisms at the molecular level had been revealed. CrystalGrower is a Kinetic Monte Carlo simulation tool launched by the Centre for Nanoporous Materials (CNM) at the university of Manchester. This study used CG to gain a better understanding of the growth and inhibition mechanisms of L-cystine crystals. Herein, the code relies on the experimental findings collected by Scanning Electron Microscope, Atomic Force Microscope and X-rays diffractometer. Using those data, the crystal structure had been partitioned into Voronoi-Dirichlet polyhedra (VDP) varying in the type and number of interactions that are intimated from the crystallography and thermodynamics of the crystal. Each set of interactions is called a site that is assigned an energy relative to a zero- level which is the kink site identified by the crystallography of the growing crystal. By imitating a thermodynamic driving force, the potential growth (or dissolution) on each site can be assigned a probability, allowing the crystal to be modelled using a kinetic Monte Carlo algorithm. Recently, the code had been improved to elucidate more features in experimental crystal growth. Varying the probability of growth and dissolution mimics the effect of the growth modifier in the wet lab. Herein, the code allows the user to prob the growth at molecular level by varying those probabilities. Also, the compatibility between the modifier and the growing crystal can be modelled by identifying the number of iterations at which the modifier remained attached to the growing crystal. This study showed that L-cystine crystallizes in P6122 and grows predominantly via screw dislocation in . However, the slowest step in , containing weak interaction, controls the propagation of faster-advancing steps in the layers above, resulting in the bunching of the minor steps to form major steps flanking the hexagonal islands. The screw dislocation in accelerates the growth in the corresponding facet by 70% compared to a negligible increment in {100}. It also showed the effect of stress around the dislocation centre in decreasing the local supersaturation that in turn increases the step bunch separation. The study showed that the stress affects the growth rate slightly while decreasing the dissolution rate considerably. It also showed that the stress effect is more pronounced in (001) compared to (100). Controlling the crystallization of L-cystine crystal with growth-modifying additives had opened a new treatment line defeating the side effect of the current treatment. Revealing the mechanisms of crystal-additive interaction is one of the primary tasks of crystal growth science and is crucial for various practical applications. This study showed that the sites in [100] planes involve vital hydrogen bonding that is essential for crystal growth. The modifiers disrupting the formation of these bonding are a good candidate for inhibiting crystal growth. These modifiers will block the growth in and redirect the nutrient species to . Consequently, the crystal habit will change from hexagon disc to hexagon prism ultimately changing the crystal polymorphism to P41 which is more soluble than P6122 polymorphism.
- Published
- 2023