Magnetite Mineralization inside Cross-Linked Protein Crystals
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Savchenko, Mariia; Villagrasa Sebastián, V.; López López, Modesto Torcuato; Rodríguez Navarro, Alejandro; De Cienfuegos, Luis Alvarez; Jiménez López, Concepción; Gavira Gallardo, José AntonioEditorial
ACS Publications
Date
2023-04Referencia bibliográfica
Cryst. Growth Des. 2023, 23, 4032−4040[https://doi.org/10.1021/acs.cgd.2c01436]
Sponsorship
Ministry of Science and Innovation, Spain (MICINN) PID2020-116261GB-I00 PID2020-118498GB-I00 PDC2021-121135.100; FEDER/Junta de Andalucia-Consejeria de Transformacion Economica, Industria, Conocimiento y Universidades (Spain) A-FQM-340-UGR20 UCE-PP2016-05Abstract
Crystallization in confined spaces is a widespread process in nature that also has important implications for the
stability and durability of many man-made materials. It has been reported that confinement can alter essential crystallization events,
such as nucleation and growth and, thus, have an impact on crystal size, polymorphism, morphology, and stability. Therefore, the
study of nucleation in confined spaces can help us understand similar events that occur in nature, such as biomineralization, design
new methods to control crystallization, and expand our knowledge in the field of crystallography. Although the fundamental interest
is clear, basic models at the laboratory scale are scarce mainly due to the difficulty in obtaining well-defined confined spaces allowing
a simultaneous study of the mineralization process outside and inside the cavities. Herein, we have studied magnetite precipitation in
the channels of cross-linked protein crystals (CLPCs) with different channel pore sizes, as a model of crystallization in confined
spaces. Our results show that nucleation of an Fe-rich phase occurs inside the protein channels in all cases, but, by a combination of
chemical and physical effects, the channel diameter of CLPCs exerted a precise control on the size and stability of those Fe-rich
nanoparticles. The small diameters of protein channels restrain the growth of metastable intermediates to around 2 nm and stabilize
them over time. At larger pore diameters, recrystallization of the Fe-rich precursors into more stable phases was observed. This study
highlights the impact that crystallization in confined spaces can have on the physicochemical properties of the resulting crystals and
shows that CLPCs can be interesting substrates to study this process.