On the Role of Solvent in the Formation of Vacancies on Ibuprofen Crystal Facets

Surface defects play a crucial role in the process of crystal growth, as the incorporation of growth units generally takes place on under-coordinated sites on the growing crystal facet. In this work, we use molecular dynamics simulations to obtain information on the role of the solvent in the roughening of three morphologically-relevant crystal faces of form I of racemic ibuprofen. To this aim, we devise a computational strategy based on combining independent Well Tempered Metadynamics with Mean Force Integration. This approach enables us to evaluate the energetic cost associated with the formation of a surface vacancy for a set of ten solvents, covering a range of polarities and hydrogen-bonding ability. We find that both the mechanism of defect formation on these facets and the work associated with the process are indeed markedly solvent-dependent. The methodology developed in this work has been designed with the aim of capturing solvent effects at the atomistic scale while maintaining the computational efficiency necessary for implementation in high-throughput computational screenings of crystallization solvents.

Porous Covalent Organic Nanotubes and Toroids: A Carbon Nanotube Analogue

Despite the noteworthy progress made in the nanotubular architectures with well-defined lengths and diameter, the synthesis of a purely covalent bonded organic nanotube, so far, proved to be elusive. Our work includes a hitherto unavailable structure, "Covalent Organic Nanotubes (CONTs)," to the repertoire. Strong covalent bonds between C, N, and O imparts high thermal and chemical stability of CONTs. This novel bottom-up approach provides an edge over the carbon nanotubes (CNTs) in functionalization, synthetic conditions, and porosity. CONT-1 exhibits a BET surface area of 321 m2g-1. These flexible CONTs intertwine with each other. The computational studies establish the role of solvent as the critical driving force for this type of convolution. Upon ultrasonication, the intertwined CONT-1 coil to form the toroidal superstructure.