Iron oxide magnetic aggregates: Aspects of synthesis, computational approaches and applications.

Superparamagnetic magnetite nanoparticles have been central to numerous investigations in the past few decades for their use in many applications, such as drug delivery, medical diagnostics, magnetic separation, and material science. However, the properties of single magnetic nanoparticles are sometimes not sufficient to accomplish tasks where a strong magnetic response is required. In light of this, aggregated magnetite nanoparticles have been proposed as an alternative advanced material, which may expand and combine some of the advantages of single magnetic nanoparticles, including superparamagnetism, with an enhanced magnetic moment and increased colloidal stability. This review comprehensively discusses the current literature on aggregates made of magnetic iron oxide nanoparticles. This review is divided into three sections. First, the current synthetic strategies for magnetite nanoparticle aggregates are discussed, together with the influence of different stabilizers on the primary crystals and the final aggregate size and morphology. The second section is dedicated to computational approaches, such as density functional methods (which permit accurate predictions of electronic and magnetic properties and shed light on the behavior of surfactant molecules on iron oxide surfaces) and molecular dynamics simulations (which provide additional insight into the influence of ligands on the surface chemistry of iron oxide nanocrystals). The last section discusses current and possible future applications of iron oxide magnetic aggregates, including wastewater treatment, water purification, medical applications, and magnetic aggregates for materials displaying structural colors.

Quantification of nanoparticles' concentration inside polymer films using lock-in thermography.

Thin nanocomposite polymer films embedding various types of nanoparticles have been the target of abundant research to use them as sensors, smart coatings, or artificial skin. Their characterization is challenging and requires novel methods that can provide qualitative as well as quantitative information about their composition and the spatial distribution of nanoparticles. In this work, we show how lock-in thermography (LIT) can be used to quantify the concentration of gold nanoparticles embedded in polyvinyl alcohol (PVA) films. LIT is an emerging and non-destructive technique that measures the thermal signature produced by an absorbing sample illuminated by modulated light with a defined frequency. Films with various concentrations of gold nanoparticles of two different sizes have been prepared by evaporation from homogeneous aqueous PVA gold nanoparticle suspensions. When the thin films were illuminated with monochromatic light at a wavelength close to the plasmonic resonance signature of the nanoparticles, the amplitude of the thermal signature emitted by the nanoparticles was recorded. The measurements have been repeated for multiple modulation frequencies of the incident radiation. We have developed a mathematical method to quantitatively relate the concentration of nanoparticles to the measured amplitude. A discussion about the conditions under which the sample thickness can be determined is provided. Furthermore, our results show how LIT measurements can easily detect the presence of concentration gradients in samples and how the model allows the measured signal to be related to the respective concentrations. This work demonstrates the successful use of LIT as a reliable and non-destructive method to quantify nanoparticle concentrations.

Iron phosphate mediated magnetite synthesis: a bioinspired approach.

The biomineralization of intracellular magnetite in magnetotactic bacteria (MTB) is an area of active investigation. Previous work has provided evidence that magnetite biomineralization begins with the formation of an amorphous phosphate-rich ferric hydroxide precursor phase followed by the eventual formation of magnetite within specialized vesicles (magnetosomes) through redox chemical reactions. Although important progress has been made in elucidating the different steps and possible precursor phases involved in the biomineralization process, many questions still remain. Here, we present a novel in vitro method to form magnetite directly from a mixed valence iron phosphate precursor, without the involvement of other known iron hydroxide precursors such as ferrihydrite. Our results corroborate the idea that phosphate containing phases likely play an iron storage role during magnetite biomineralization. Further, our results help elucidate the influence of phosphate ions on iron chemistry in groundwater and wastewater treatment.

Crystallization by particle attachment is a colloidal assembly process.

The nucleation of crystals has long been thought to occur through the stochastic association of ions, atoms or molecules to form critical nuclei, which will later grow out to crystals1. Only in the past decade has the awareness grown that crystallization can also proceed through the assembly of different types of building blocks2,3, including amorphous precursors4, primary particles5, prenucleation species6,7, dense liquid droplets8,9 or nanocrystals10. However, the forces that control these alternative pathways are still poorly understood. Here, we investigate the crystallization of magnetite (Fe3O4) through the formation and aggregation of primary particles and show that both the thermodynamics and the kinetics of the process can be described in terms of colloidal assembly. This model allows predicting the average crystal size at a given initial Fe concentration, thereby opening the way to the design of crystals with predefined sizes and properties.

Breaking the Nanoparticle Loading-Dispersion Dichotomy in Polymer Nanocomposites with the Art of Croissant-Making.

The intrinsic properties of nanomaterials offer promise for technological revolutions in many fields, including transportation, soft robotics, and energy. Unfortunately, the exploitation of such properties in polymer nanocomposites is extremely challenging due to the lack of viable dispersion routes when the filler content is high. We usually face a dichotomy between the degree of nanofiller loading and the degree of dispersion (and, thus, performance) because dispersion quality decreases with loading. Here, we demonstrate a potentially scalable pressing-and-folding method (P & F), inspired by the art of croissant-making, to efficiently disperse ultrahigh loadings of nanofillers in polymer matrices. A desired nanofiller dispersion can be achieved simply by selecting a sufficient number of P & F cycles. Because of the fine microstructural control enabled by P & F, mechanical reinforcements close to the theoretical maximum and independent of nanofiller loading (up to 74 vol %) were obtained. We propose a universal model for the P & F dispersion process that is parametrized on an experimentally quantifiable " D factor". The model represents a general guideline for the optimization of nanocomposites with enhanced functionalities including sensing, heat management, and energy storage.

Bioinspired synthesis of magnetite nanoparticles.

Magnetite (Fe3O4) is a widespread magnetic iron oxide encountered in many biological and geological systems, and also in many technological applications. The magnetic properties of magnetite crystals depend strongly on the size and shape of its crystals. Hence, engineering magnetite nanoparticles with specific shapes and sizes allows tuning their properties to specific applications in a wide variety of fields, including catalysis, magnetic storage, targeted drug delivery, cancer diagnostics and magnetic resonance imaging (MRI). However, synthesis of magnetite with a specific size, shape and a narrow crystal size distribution is notoriously difficult without using high temperatures and non-aqueous media. Nevertheless, living organisms such as chitons and magnetotactic bacteria are able to form magnetite crystals with well controlled sizes and shapes under ambient conditions and in aqueous media. In these biomineralization processes the organisms use a twofold strategy to control magnetite formation: the mineral is formed from a poorly crystalline precursor phase, and nucleation and growth are controlled through the interaction of the mineral with biomolecular templates and additives. Taking inspiration from this biological strategy is a promising route to achieve control over the kinetics of magnetite crystallization under ambient conditions and in aqueous media. In this review we first summarize the main characteristics of magnetite and what is known about the mechanisms of magnetite biomineralization. We then describe the most common routes to synthesize magnetite and subsequently will introduce recent efforts in bioinspired magnetite synthesis. We describe how the use of poorly ordered, more soluble precursors such as ferrihydrite (FeH) or white rust (Fe(OH)2) can be employed to control the solution supersaturation, setting the conditions for continued growth. Further, we show how the use of various organic additives such as proteins, peptides and polymers allows for either the promotion or inhibition of magnetite nucleation and growth processes. At last we discuss how the formation of magnetite-based organic-inorganic hybrids leads to new functional nanomaterials.

Bioinspired magnetite synthesis via solid precursor phases.

Living organisms often exploit solid but poorly ordered mineral phases as precursors in the biomineralization of their inorganic body parts. Generally speaking, such precursor-based approaches allow the organisms - without the need of high supersaturation levels - to accumulate significant quantities of mineral material at the desired place and time, where they can be molded and crystallized into the right morphology and structure. This strategy is also of interest in the field of bioinspired materials science, as it potentially enables the bottom-up creation of novel materials with equal or improved functionality as compared to Nature, in water and at ambient temperatures. Also for the biomineralization of magnetite (Fe3O4) such a strategy has been reported: ferrihydrite, a poorly crystalline iron oxide, has been identified as a precursor for the final magnetite phase in the magnetosomes of magnetotactic bacteria as well as in the outer layers of chiton teeth. In this perspective, we discuss the efforts of us and others to understand and tune the nucleation and growth of magnetite crystals to date, in aqueous, room-temperature syntheses and employing different solid precursor phases. The various examples demonstrate the importance of the precursor approach in controlling the different properties of magnetite nanoparticles.