Crystal Growth & Design

The formulation of active pharmaceutical ingredients involves discovering stable crystal packing arrangements or polymorphs, each of which has distinct pharmaceutically relevant properties. Traditional experimental screening techniques utilizing various conditions are commonly supplemented with in silico crystal structure prediction (CSP) to inform the crystallization process and mitigate risk. Predictions are often based on advanced classical force fields or quantum mechanical calculations that model the crystal potential energy landscape but do not fully incorporate temperature, pressure, or solution conditions during the search procedure...

Heterostructures in nanoparticles challenge our common understanding of interfaces due to quantum confinement and size effects, giving rise to synergistic properties. An alternating heterostructure in which multiple and reoccurring interfaces appear in a single nanocrystal is hypothesized to accentuate such properties. We present a colloidal synthesis for perovskite layered heterostructure nanoparticles with a (PbBr2 )2 (AMTP)2 PbBr4 composition. By varying the synthetic parameters, such as synthesis temperature, solvent, and selection of precursors, we control particle size, shape, and product priority...

During the past three decades, the ability of guanidinium arenesulfonate host frameworks to encapsulate a wide range of guests has been amply demonstrated, with more than 700 inclusion compounds realized. Herein, we report crystalline inclusion compounds based on a new aliphatic host, guanidinium cyclohexanemonosulfonate, which surprisingly exhibits four heretofore unobserved architectures, as described by the projection topologies of the organosulfonate residues above and below hydrogen-bonded guanidinium sulfonate sheets...

One possible pathway toward reducing the cost of III-V solar cells is to remove them from their growth substrate by spalling fracture, and then reuse the substrate for the growth of multiple cells. Here we consider the growth of III-V cells on spalled GaAs(100) substrates, which typically have faceted surfaces after spalling. To facilitate the growth of high-quality cells, these faceted surfaces should be smoothed prior to cell growth. In this study, we show that these surfaces can be smoothed during organometallic vapor-phase epitaxy growth, but the choice of epilayer material and modification of the various surfaces by impurities/dopants greatly impacts whether or not the surface becomes smooth, and how rapidly the smoothing occurs...

The aim of this work is to shed light on the polymorphism of xanthones, a class of oxygenated molecules well known for their bioactivity, including antioxidant, anticancer, and anti-inflammatory effects. Understanding the polymorphism of xanthones can enable the design of novel solid products for pharmaceutical, nutraceutical, and agrochemical applications. Prior to this work, two entries accounting for different space groups were deposited for 9-xanthone in the Cambridge Structure Database (CSD): an orthorhombic P 21 21 21 and a monoclinic P 21 structure solved at room and low temperatures, respectively...

Mechanochemical synthesis is a powerful approach to obtain new materials, limiting costs, and times. However, defected and submicrometrical-sized crystal products make critical their characterization through classical single-crystal X-ray diffraction. A valid alternative is represented by three-dimensional (3D) electron diffraction, in which a transmission electron microscope is used, like a diffractometer. This work matches a green water-based mechanochemical synthesis and 3D electron diffraction to obtain and characterize a Cu-based protocatechuate metal-organic framework (PC-MOF)...

Precision measurement of the growth rate of individual single crystal facets ( hkl ) represents an important component in the design of industrial crystallization processes. Current approaches for crystal growth measurement using optical microscopy are labor intensive and prone to error. An automated process using state-of-the-art computer vision and machine learning to segment and measure the crystal images is presented. The accuracies and efficiencies of the new crystal sizing approach are evaluated against existing manual and semi-automatic methods, demonstrating equivalent accuracy but over a much shorter time, thereby enabling a more complete kinematic analysis of the overall crystallization process...

Three imines have been prepared by condensation of 2-nitrobenzaldehyde and 4-haloanilines (halo = Cl, Br, and I) with functionalities that enabled them to act as both halogen and pnictogen bond donors; however, both interactions were found to be absent in the solid state. The prepared imines were further cocrystallized with 1,3-diiodotetrafluorobenzene and 1,3,5-triiodotetrafluorobenzene as halogen bond donors. Six novel cocrystals were prepared by means of liquid-assisted mechanochemical synthesis and by crystallization from solution...

This study presents a comprehensive comparison of the batch cooling crystallization performance of aqueous solutions containing sugars and sugar alcohols, namely, erythritol, glucose, xylitol, and xylose. Erythritol and xylitol are commonly used alternative sweeteners to replace sucrose. They can be obtained by fermentation-based bioprocesses, where glucose and xylose are typical raw materials. These model compounds were selected based on their differing rheological nature: saturated erythritol solution has a viscosity lower than 3 mPa·s, whereas xylitol has the highest viscosity: greater than 90 mPa·s in the studied temperature range...

Colloidal quantum dot (CQD) infrared (IR) photodetectors can be fabricated and operated with larger spectral tunability, fewer limitations in terms of cooling requirements and substrate lattice matching, and at a potentially lower cost than detectors based on traditional bulk materials. Silver selenide (Ag2 Se) has emerged as a promising sustainable alternative to current state-of-the-art toxic semiconductors based on lead, cadmium, and mercury operating in the IR. However, an impeding gap in available absorption bandwidth for Ag2 Se CQDs exists in the short-wave infrared (SWIR) region due to degenerate doping by the environment, switching the CQDs from intrinsic interband semiconductors in the near-infrared (NIR) to intraband absorbing CQDs in the mid-wave infrared (MWIR)...

A novel monoacylglycerol, 7.10 MAG, has been produced for use in the in meso (lipid cubic phase) crystallization of membrane proteins and complexes. 7.10 MAG differs from monoolein, the most extensively used lipid for in meso crystallization, in that it is shorter in chain length by one methylene and its cis olefinic bond is two carbons closer to the glycerol headgroup. These changes in structure alter the phase behavior of the hydrated lipid and the microstructure of the corresponding mesophases formed. Temperature-composition phase diagrams for 7...

[This corrects the article DOI: 10.1021/acs.cgd.3c01374.].

Gallium phosphide (GaP) is a III-V semiconductor with remarkable optoelectronic properties, and it has almost the same lattice constant as silicon (Si). However, to date, the monolithic and large-scale integration of GaP devices with silicon remains challenging. In this study, we present a nanoheteroepitaxy approach using gas-source molecular-beam epitaxy for selective growth of GaP islands on Si nanotips, which were fabricated using complementary metal-oxide semiconductor (CMOS) technology on a 200 mm n-type Si(001) wafer...

Porous coordination networks (PCNs) sustained by inorganic anions that serve as linker ligands can offer high selectivity toward specific gases or vapors in gas mixtures. Such inorganic anions are best exemplified by electron-rich fluorinated anions, e.g., SiF6 2- , TiF6 2- , and NbOF5 2- , although sulfate anions have recently been highlighted as inexpensive and earth-friendly alternatives. Herein, we report the use of a rare copper sulfate dimer molecular building block to generate two square lattice, sql , coordination networks which can be prepared via solvent layering or slurrying, CuSO4 (1,4-bib)1...

A series of cocrystals of halogen bond donors 1,4-diiodotetrafluorobenzene ( p -F4 DIB) and tetraiodoethylene (TIE) with five aromatic heterocyclic diazine mono- N -oxides based on pyrazine, tetramethylpyrazine, quinoxaline, phenazine, and pyrimidine as halogen bonding acceptors were studied. Structural analysis of the mono- N -oxides allows comparison of the competitive occurrence of N···I vs O···I interactions and the relative strength and directionality of these two types of interactions...

Potassium carbonate sesquihydrate has previously been identified as a promising material for thermochemical energy storage. The hydration and cyclic behavior have been extensively studied in the literature, but detailed investigation into the different processes occurring during dehydration is lacking. In this work, a systematic investigation into the different dehydration steps is conducted. It is found that at higher temperatures, dehydration of pristine material occurs as a single process since water removal from the pristine crystals is difficult...

Savolitinib is a compound that can crystallize in an undesirable, high aspect ratio needle morphology. This morphology type may cause issues in downstream processing. This paper demonstrates a unique method to alter the crystal morphology of savolitinib to make it more processable, resulting in the active pharmaceutical ingredient (API) crystallizing out in considerably more processable stellates. The volatile deep eutectic solvent technique presents a simple and scalable method for changing the crystal morphology while maintaining the polymorph of the API in this case, confirmed via powder X-ray diffraction and differential scanning calorimetry analysis...

The morphology of zeolite crystals strongly affects their textural, catalytic, and mechanical attributes. However, controlling zeolite crystal morphology without using modifiers or structure-directing agents remains a challenging task because of our limited understanding of the relationships between zeolite crystal shape, crystallization mechanism, and composition of the starting synthesis mixture. In this study, we aimed at developing a general method for controlling the morphology of zeolites by assessing the impact of the Si/T molar ratio of the synthesis gel on the growth rate of zeolite crystals in various crystallographic directions and on the final crystal morphology of the UTL germanosilicate with a 2D system of intersecting 14- and 12-ring pores...

The efficiency of layer melt crystallization for the selective separation of glycerol from a glycerol-diethylene glycol mixture containing 4 wt % of diethylene glycol was evaluated using solvent-free and solvent-aided approaches. The effect of 1-butanol and the binary solvent of 1-butanol and acetone with a total molar composition of 25 mol % on the crystal growth kinetics and the purity of the final product was studied at different undercooling degrees and crystallization yields. The melting point temperature of the mixtures was predicted by using the modified UNIFAC Dortmund model...

Metal-organic frameworks (MOFs), formed by the combination of both inorganic and organic components, have attracted special attention for their tunable porous structures, chemical and functional diversities, and enormous applications in gas storage, catalysis, sensing, etc. Recently, electronic applications of MOFs like electrocatalysis, supercapacitors, batteries, electrochemical sensing, etc., have become a major research topic in MOF chemistry. However, the low electrical conductivity of most MOFs represents a major handicap in the development of these emerging applications...