Colloidal nanocrystals are nanometer-sized, solution-grown inorganic particles stabilized by a layer of surfactants attached to their surface. The inorganic cores exhibit useful properties controlled by composition as well as size and shape, while the surfactant coating ensures that these structures are easy to fabricate and process. It is this combination of features that makes colloidal nanocrystals attractive and promising building blocks for advanced materials and devices. But their full potential can only be exploited if we achieve exquisite control over their composition, size, shape, crystal structure and surface properties. Here we review what is known about nanocrystal growth and outline strategies for controlling it.

Colloidal nanocrystal synthesis and the organic-inorganic interface

Among iron oxide phases, magnetite (Fe3O4) is often the preferred one for nanotechnological and biomedical applications because of its high saturation magnetization and low toxicity. Although there are several synthetic routes that attempt to reach magnetite nanoparticles (NPs), they are usually referred as "IONPs" (iron oxide NPs) due to the great difficulty in obtaining the monophasic and stoichiometric Fe3O4 phase. Added to this problem is the common increase of size/shape polydispersity when larger NPs (D > 20 nm) are synthesized. An unequivocal correlation between a nanomaterial and its properties can only be achieved by the production of highly homogeneous systems, which, in turn, is only possible by the continuous improvement of synthesis methods. There is no doubt that solving the compositional heterogeneity of IONPs while keeping them monodisperse remains a challenge for synthetic chemistry. Herein, we present a methodical optimization of the iron oleate decomposition method to obtain Fe3O4 single nanocrystals without any trace of secondary phases and with no need of postsynthetic treatment. The average dimension of the NPs, ranging from 20 to 40 nm, has been tailored by adjusting the total volume and the boiling point of the reaction mixture. Mossbauer spectroscopy and DC magnetometry have revealed that the NPs present a perfectly stoichiometric Fe3O4 phase. The high saturation magnetization (93 (2) A·m2/kg at RT) and the extremely sharp Verwey transition (at around 120 K) shown by these NPs have no precedent. Moreover, the synthesis method has been refined to obtain NPs with octahedral morphology and suitable magnetic anisotropy, which significantly improves the magnetic hyperthemia performance. The heating power of properly PEGylated nano-octahedrons has been investigated by AC magnetometry, confirming that the NPs present negligible dipolar interactions, which leads to an outstanding magnetothermal efficiency that does not change when the NPs are dispersed in environments with high viscosity and ionic strength. Additionally, the heat production of the NPs within physiological media has been directly measured by calorimetry under clinically safe conditions, reasserting the excellent adequacy of the system for hyperthermia therapies. To the best of our knowledge, this is the first time that such bulklike magnetite NPs (with minimal size/shape polydispersity, minor agglomeration, and exceptional heating power) are chemically synthesized.

https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.1c02654

A Milestone in the Chemical Synthesis of Fe3O4 Nanoparticles: Unreported Bulklike Properties Lead to a Remarkable Magnetic Hyperthermia.

Transition metal ion-doped ferrites nanoparticles for bioimaging and cancer therapy.

The possibility to precisely control important properties of nanoparticles (NPs) such as their size, morphology, surface charge, or doping content is crucial for enhancing the performance of existing solutions beyond the state-of-the-art and for enabling novel applications. In this work, custom-tailored Znx Fe3- x O4 NPs are synthesized at different Zn doping concentrations to augment and expand their usefulness for high-performance applications in nanomedicine. By precisely increasing the Zn2+ content in the range of 0 ≤ x ≤ 2.0, the discussed NPs can sequentially acquire valuable properties enabling magnetic resonance imaging, near-infrared (NIR) photothermal effects, NIR photocatalytic and photoelectric effects, depending on the variation of substitution position of the Zn2+ in the magnetite structure and the emergence of a ZnO/ZnFe2 O4 heterostructure at high doping concentrations. The presented work demonstrates and explainsa facile route for the synthesis and modulation of multifunctional nanomaterials with manifold roles in disease diagnostics and therapy, and provides helpful guidance in designing divalent transition metal ion-doped nanomaterials.

Multifunctional Modulation of High-Performance Znx Fe3-x O4 Nanoparticles by Precisely Tuning the Zinc Doping Content.

Transition metal ion-doped ferrites nanoparticles for bioimaging and cancer therapy

The currently existing magnetic hyperthermia treatments usually need to employ very large doses of magnetic nanoparticles (MNPs) and/or excessively high excitation conditions (H × f > 1010 A/m s) t...

Shaping Up Zn-Doped Magnetite Nanoparticles from Mono- and Bimetallic Oleates: The Impact of Zn Content, Fe Vacancies, and Morphology on Magnetic Hyperthermia Performance.

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A Milestone in the Chemical Synthesis of Fe3O4 Nanoparticles: Unreported Bulklike Properties Lead to a Remarkable Magnetic Hyperthermia.

Shaping Up Zn-Doped Magnetite Nanoparticles from Mono- and Bimetallic Oleates: The Impact of Zn Content, Fe Vacancies, and Morphology on Magnetic Hyperthermia Performance.