Probing Crystal Nucleation of Fenoxycarb from Solution through the Effect of Solvent

Abstract

Induction time experiments, spectroscopic and calorimetric analysis, and molecular modeling were used to probe the influence of solvent on the crystal nucleation of fenoxycarb (FC), a medium-sized, flexible organic molecule. A total of 800 induction times covering a range of supersaturations and crystallization temperatures in four different solvents were measured to elucidate the relative ease of nucleation. To achieve similar induction times, the required thermodynamic driving force, RT ln S, increases in the order: ethyl acetate < toluene < ethanol < isopropanol. This is roughly matched by the order of interfacial energies calculated using the classical nucleation theory. Solvent–solute interaction strengths were estimated using three methods: solvent–solute enthalpies derived from calorimetric solution enthalpies, solvent–solute interactions from molecular dynamics simulations, and the FTIR shifts in the carbonyl stretching corresponding to the solvent–solute interaction. The three methods gave an overall order of solvent–solute interactions increasing in the order toluene < ethyl acetate < alcohols. Thus, with the exception of FC in toluene, it is found that the nucleation difficulty increases with stronger binding of the solvent to the solute.

Unveiling the self-association and desolvation in crystal nucleation

“…In recent years, a number of works focused on building a link between the nucleation rate and the solvation strength, such as risperidone (Mealey et al, 2015), tolbutamide (-Zeglinski et al, 2018), fenoxycarb (Zeglinski et al, 2019), salicylic acid (Khamar et al, 2014) and PABA (Sullivan et al, 2014). A similar approach was also taken in this study.…”

“…Recent advances in computational and analytical techniques have also facilitated investigations of larger molecular clusters more efficiently (Sosso et al, 2016). Therefore, several attempts have been made to explain the evolution of the so-called 'growth unit' during nucleation (Gavezzotti et al, 1997;Di Tommaso, 2013;Zeglinski et al, 2018). By studying the molecular structure evolution pathways from solute molecules to supramolecular arrangements, the structure correlation between the solution aggregates and crystal syntheses can be explained (Byrn et al, 1976;Bernstein & Hagler, 1978;Habgood, 2012).…”

Effects of solvent‐induced morphology evolution of Zn2GeO4 on photocatalytic activities of g‐C3N4/Zn2GeO4 composites

“…Moreover, g-C 3 N 4 has been demonstrated to be an excellent substrate material for fabricating heterojunction photocatalysts, and many g-C 3 N 4 -based photocatalysts, composites including ZnO-C 3 N 4 , 17 BiVO 4 -C 3 N 4 , 18 TiO 2 -C 3 N 4 , 19 and BiOX-C 3 N 4 (X = Br, or I) 20,21 have been developed and used to degrade organic pollutants. [25][26][27][28] We demonstrated here the morphology evolution of Zn 2 GeO 4 particles under different solvothermal conditions, as well as the mass ratio of the components toward the optimization of the photocatalytic activity of g-C 3 N 4 /Zn 2 GeO 4 hybrids. Meanwhile, morphologycontrolled synthesis of semiconductor has been demonstrated to be another effective strategy in promoting photocatalytic activity.…”

“…[22][23][24] The reaction medium of solvents with different polarity and solubility greatly influence the growth behaviors of crystalline materials. [25][26][27][28] We demonstrated here the morphology evolution of Zn 2 GeO 4 particles under different solvothermal conditions, as well as the mass ratio of the components toward the optimization of the photocatalytic activity of g-C 3 N 4 /Zn 2 GeO 4 hybrids. Methylene blue (MB) was selected as the typical contaminant to evaluate the photocatalytic performance of composites.…”

Review and Modeling of Crystal Growth of Atropisomers from Solutions

“…Solvents can also stabilize conformers by dimerization [80][81][82][109][110][111], in particular, at elevated concentrations [112] and for molecules of low molecular weight [80]. Recently, it was reported that for Fenoxycarb, which exhibits several conformers with calculated E b ranging from 1.2 to 7.2 kcal/mol, solutions conformers were all different from four crystal conformers [113]. This result implicitly indicates a negligible effect of crystal surface on modifying the conformation upon crystallization when E b is below 10 kcal/mol.…”