Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDI =1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes "colloidal" impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals.
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http://dx.doi.org/10.1002/chem.202002873 | DOI Listing |
J Colloid Interface Sci
February 2025
Hubei Longzhong Laboratory, Wuhan University of Technology, Xiangyang 441000, China; State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China. Electronic address:
Amorphous phases hold great promise in diverse applications and are widely used by organisms as precursors to produce biominerals with complex morphologies and excellent properties. However, the stabilization and crystallization mechanisms of amorphous phases are not fully understood, especially in the presence of additives. Here, using amorphous calcium carbonate (ACC) as the model system, we systematically investigate the crystallization pathways of amorphous phases in the presence of poly(Aspartic acid) (pAsp) with various chain lengths.
View Article and Find Full Text PDFRSC Adv
January 2024
INQUIMAE-CONICET y Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, CABA Argentina.
The design mebendazole (MBZ) multicomponent systems is important to obtain new materials that incorporate the API (active pharmaceutical ingredient) with better thermal stability, avoiding the interconversion of desmotropes. Interestingly, the presence of water molecules in the mebendazolium mesylate monohydrate prevents the formation of the (8) supramolecular synthon, found in all mebendazolium salts with polyatomic counterions. Here, we designed a new mebendazolium mesylate anhydrous salt based on statistical scrutiny of all mebendazole crystal structures identified in the literature and an exhaustive analysis of the conformational and geometrical requirements for the supramolecular assembly.
View Article and Find Full Text PDFJ Chem Phys
July 2023
Department of Chemical Engineering, Indian Institute of Technology, Kanpur, Uttar Pradesh 208016, India.
Understanding the nucleation behavior of water in dilute polymeric solutions is quintessential for the development of suitable artificial ice recrystallization inhibition (IRI) agents. Although poly(vinyl alcohol) (PVA) is found to be one of the most potent biomimetic IRI agents, the molecular understanding of the nucleation behavior of water in the presence of PVA is still lacking. Here, we use molecular dynamics to elucidate the role of concentration, degree of supercooling, degree of polymerization, and amphiphilicity of PVA and PVA-like polymers on the homogeneous nucleation of water in dilute polymeric solutions using the seeding method.
View Article and Find Full Text PDFActa Biomater
May 2023
Institute of Paleobiology, Polish Academy of Sciences, Twarda 51/55, PL-00-818 Warsaw, Poland.
Different non-classical crystallization mechanisms have been invoked to explain structural and compositional properties of biocrystals. The identification of precursor amorphous nanoparticle aggregation as an onset process in the formation of numerous biominerals (crystallization via particle attachment) constituted a most important breakthrough for understanding biologically mediated mineralization. A comprehensive understanding about how the attached amorphous particles transform into more stable, crystalline grains has yet to be elucidated.
View Article and Find Full Text PDFCryst Growth Des
January 2023
Department of Chemical and Metallurgical Engineering, Aalto University, FI-00076 Aalto (Espoo), Finland.
Liquid-liquidphase separation (LLPS) or dense liquid intermediates during the crystallization of pharmaceutical molecules is common; however, their role in alternative nucleation mechanisms is less understood. Herein, we report the formation of a dense liquid intermediate followed by a core-shell structure of ibuprofen crystals via nonclassical crystallization. The Raman and SAXS results of the dense phase uncover the molecular structural ordering and its role in nucleation.
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