Biocatalyst immobilization on magnetic nano-architectures for potential applications in condensation reactions.

In this review article, a perspective on the immobilization of various hydrolytic enzymes onto magnetic nanoparticles for synthetic organic chemistry applications is presented. After a first part giving short overview on nanomagnetism and highlighting advantages and disadvantages of immobilizing enzymes on magnetic nanoparticles (MNPs), the most important hydrolytic enzymes and their applications were summarized. A section reviewing the immobilization techniques with a particular focus on supporting enzymes on MNPs introduces the reader to the final chapter describing synthetic organic chemistry applications of small molecules (flavour esters) and polymers (polyesters and polyamides). Finally, the conclusion and perspective section gives the author's personal view on further research discussing the new idea of a synergistic rational design of the magnetic and biocatalytic component to produce novel magnetic nano-architectures.

Memory and superposition in a superspin glass.

The non-equilibrium dynamics of the superspin glass state of a dense assembly of ~ 2 nm MnFe2O4 nanoparticles was investigated by means of magnetization, ac susceptibility and Mössbauer spectroscopy measurements and compared to the results of Monte Carlo simulations for a mesoscopic model that includes particles morphology and interparticle interactions. The zero-field cooled (ZFC), thermoremanent (TRM), and isothermal remanent magnetization (IRM) were recorded after specific cooling protocols and compared to those of archetypal spin glasses and their dimensionality. The system is found to display glassy magnetic features. We illustrate in detail, by a number of experiments, the dynamical properties of the low-temperature superspin glass phase. We observe that these glassy features are quite similar to those of atomic spin glasses. Some differences are observed, and interestingly, the non-atomic nature of the superspin glass is also reflected by an observed superspin dimensionality crossover. Monte Carlo simulations-that explicitly take into account core and surface contributions to the magnetic properties of these ultrasmall nanoparticles in direct contact, as well as interparticle interactions-evidence effects of the interplay between (intraparticle) core/surface exchange coupling and (interparticle) dipolar and exchange interactions.

The role of chemical and microstructural inhomogeneities on interface magnetism.

The study of interfacing effects arising when different magnetic phases are in close contact has led to the discovery of novel physical properties and the development of innovative technological applications of nanostructured magnetic materials. Chemical and microstructural inhomogeneities at the interfacial region, driven by interdiffusion processes, chemical reactions and interface roughness may significantly affect the final properties of a material and, if suitably controlled, may represent an additional tool to finely tune the overall physical properties. The activity at the Nanostructured Magnetic Materials Laboratory (nM2-Lab) at CNR-ISM of Italy is aimed at designing and investigating nanoscale-engineered magnetic materials, where the overall magnetic properties are dominated by the interface exchange coupling. In this review, some examples of recent studies where the chemical and microstructural properties are critical in determining the overall magnetic properties in core/shell nanoparticles, nanocomposites and multilayer heterostructures are presented.

Interplay between inter- and intraparticle interactions in bi-magnetic core/shell nanoparticles.

The synthesis strategy and magnetic characterisation of two systems consisting of nanoparticles with core/shell morphology are presented: an assembly of hard/soft nanoparticles with cores consisting of magnetically hard cobalt ferrite covered by a magnetically soft nickel ferrite shell, and the inverse system of almost the same size and shape. We have successfully designed these nanoparticle systems by gradually varying the magnetic anisotropy resulting in this way in the modulation of the magnetic dipolar interactions between particles. Both nanoparticle systems exhibit high saturation magnetisation and display superparamagnetic behaviour at room temperature. We have shown strong exchange coupling at the core/shell interface of these nanoparticles systems which was also confirmed by mesoscopic modelling. Our results demonstrate the possibility of modulating magnetic anisotropy not only by chemical composition but also by adopting the proper nano-architecture.

On the detection of surface spin freezing in iron oxide nanoparticles and its long-term evolution under ambient oxidation.

Exchange bias (EB) effects linked to surface spin freezing (SSF) are commonly found in iron oxide nanoparticles, while signatures of SSF in low-field temperature-dependent magnetization curves have been much less frequently reported. Here, we present magnetic properties of dense assemblies of similar-sized (∼8 nm diameter) particles synthesized by a magnetite (sample S1) and a maghemite (sample S2) method, and the influence of long-term (4 year) sample aging under ambient conditions on these properties. The size of the EB field of the different sample (fresh or aged) states is found to correlate with (a) whether a low-temperature hump feature signaling the SSF transition is detected in out-of-phase ac susceptibility or zero-field-cooled (ZFC) dc magnetization recorded at low field and with (b) the prominence of irreversibility between FC and ZFC curves recorded at high field. Sample S1 displays a lower magnetization than S2, and it is in S1 where the largest SSF effects are found. These effects are significantly weakened by aging but remain larger than the SSF effects in S2, where the influence of aging is considerably smaller. A non-saturating component due to spin disorder in S1 also weakens with aging, accompanied by, we infer, an increase in the superspin and the radius of the ordered nanoparticle cores. X-ray diffraction and Mössbauer spectroscopy provide indication of maghemite-like stoichiometry in both aged samples as well as thicker disordered particle shells in aged-S1 relative to aged-S2 (crystallographically-disordered and spin-disordered according to diffraction and Mössbauer, respectively). The pronounced diminution in SSF effects with aging in S1 is attributed to a (long-term) transition, caused by ambient oxidation, from magnetite-like to maghemite-like stoichiometry, and a concomitant softening of the spin-disordered shell anisotropy. We assess the impact of this anisotropy on the nature of the blocking of the nanoparticle superspins.

Magnetic mesoporous silica nanostructures: investigation of magnetic properties.

Magnetic mesoporous silica (MS) nanocomposites provide the possibility of generating multi-functional objects for application in different technological areas. This paper focuses on the magnetic properties of nanocomposites constituted by spinel iron oxide nanoparticles (magnetic nanoparticles (MNPs), < D > ≈ 8-9 nm) embedded in an MS matrix. The mesoporous structure of the silica matrix and the presence of the nanoparticles inside clearly emerge from transmission electron microscopy (TEM) measurements. Low temperature (5 K) field-dependent magnetization measurements reveal saturation magnetization (MS ) close to bulk value (M S bulk ∼ 90 emu g-1) for both MNPs and MNP/MS nanocomposites, indicating that the presence of silica does not affect the magnetic features of the single MNPs. Moreover, the dependence of the remanent magnetization on field (i.e. δM plots) at low temperature has shown a small but evident decrease of interaction in an MNP/MS sample with respect to MNP samples A m2 Kg-1. Finally, a partial orientation of the easy axis is observed when the MNPs are embedded in the silica matrix.

Symbiotic, low-temperature, and scalable synthesis of bi-magnetic complex oxide nanocomposites.

Functional oxide nanocomposites, where the individual components belong to the family of strongly correlated electron oxides, are an important class of materials, with potential applications in several areas such as spintronics and energy devices. For these materials to be technologically relevant, it is essential to design low-cost and scalable synthesis techniques. In this work, we report a low-temperature and scalable synthesis of prototypical bi-magnetic LaFeO3-CoFe2O4 nanocomposites using a unique sol-based synthesis route, where both the phases of the nanocomposite are formed during the same time. In this bottom-up approach, the heat of formation of one phase (CoFe2O4) allows the crystallization of the second phase (LaFeO3), and completely eliminates the need for conventional high-temperature annealing. A symbiotic effect is observed, as the second phase reduces grain growth of the first phase, thus yielding samples with lower particle sizes. Through thermogravimetric, structural, and morphological studies, we have confirmed the reaction mechanism. The magnetic properties of the bi-magnetic nanocomposites are studied, and reveal a distinct effect of the synthesis conditions on the coercivity of the particles. Our work presents a basic concept of significantly reducing the synthesis temperature of bi-phasic nanocomposites (and thus also the synthesis cost) by using one phase as nucleation sites for the second one, as well as using the heat of formation of one phase to crystallize the other.

Co/Pd-Based synthetic antiferromagnetic thin films on Au/resist underlayers: towards biomedical applications.

Thin film stacks consisting of multiple repeats M of synthetic antiferromagnetic (SAF) [Co/Pd]N/Ru/[Co/Pd]N units with perpendicular magnetic anisotropy were explored as potential starting materials to fabricate free-standing micro/nanodisks, which represent a promising candidate system for theranostic applications. The films were directly grown on a sacrificial resist layer spin-coated on SiOx/Si(100) substrates, required for the preparation of free-standing disks after its dissolution. Furthermore, the film stack was sandwiched between two Au layers to allow further bio-functionalization. For M ≤ 5, the samples fulfill all the key criteria mandatory for biomedical applications, i.e., zero remanence, zero field susceptibility at small fields and sharp switching to saturation, together with the ability to vary the total magnetic moment at saturation by changing the number of repetitions of the multi-stack. Moreover, the samples show strong perpendicular magnetic anisotropy, which is required for applications relying on the transduction of a mechanical force through the micro/nano-disks under a magnetic field, such as the mechanical cell disruption, which is nowadays considered a promising alternative to the more investigated magnetic hyperthermia approach for cancer treatment. In a further step, SAF microdisks were prepared from the continuous multi-stacks by combining electron beam lithography and Ar ion milling, revealing similar magnetic properties as compared to the continuous films.

Controlling magnetic coupling in bi-magnetic nanocomposites.

Magnetic nanocomposites constitute a vital class of technologically relevant materials, in particular for next-generation applications ranging from biomedicine, catalysis, and energy devices. Key to designing such materials is determining and controlling the extent of magnetic coupling in them. In this work, we show how the magnetic coupling in bi-magnetic nanocomposites can be controlled by the growth technique. Using four different synthesis strategies to prepare prototypical LaFeO3-CoFe2O4 and LaFeO3-Co0.5Zn0.5Fe2O4 nanocomposite systems, and by performing comprehensive magnetic measurements, we demonstrate that the final material exhibits striking differences in their magnetic coupling that is distinct to the growth method. Through structural and morphological studies, we confirm the link between the magnetic coupling and growth methods due to distinct levels of particle agglomeration at the very microscopic scale. Our studies reveal an inverse relationship between the strength of magnetic coupling and the degree of particle agglomeration in the nanocomposites. Our work presents a basic concept of controlling the particle agglomeration to tune magnetic coupling, relevant for designing advanced bi-magnetic nanocomposites for novel applications.

Structural and Magnetic Properties of Spinel Ferrite Nanoparticles.

In this paper we review the magnetic properties of spinel ferrite nanoparticles pointing out the primary role of the crystalline structure besides finite size and surface/interface effects. The details of the spinel crystal structure of bulk spinel ferrite materials and their influence on both the magnetization and magnetocrystalline anisotropy are recalled. Moreover, we review some results published in the literature over the last years about how the structure of magnetic nanoparticles influences their magnetic features. Perspectives about the challenges to improve the applications in several fields are finally reported.

Tunable single-phase magnetic behavior in chemically synthesized AFeO3-MFe2O4 (A = Bi or La, M = Co or Ni) nanocomposites.

The properties of magnetic nanocomposites rely strongly on the interplay between those of the constituent components. When the individual components themselves are complex systems belonging to the family of correlated electron oxide systems which typically exhibit exotic physical properties, it becomes nontrivial to customize the properties of the nanocomposite. In this paper, we demonstrate an easy, but effective method to synthesize and tune the magnetic properties of nanocomposites consisting of correlated electron oxide systems as the individual components. Our method is based on a novel synthesis technique by which the two components of the nanocomposite can be directly integrated with each other, yielding homogeneous samples on the nanoscale with magnetic behavior reminiscent of a single phase. We illustrate our method using multiferroic BiFeO3 (BFO) and LaFeO3 (LFO) as the major phase (i.e., matrix), and MFe2O4 (M = Co2+ or Ni2+) as the embedded magnetic phase. Furthermore, we show that by a proper selection of the second phase in the nanocomposite, it is possible to customize the magnetic properties of the matrix. We illustrate this by choosing CoFe2O4 and NiFe2O4, two oxides with widely differing magnetic anisotropies, as the embedded phase, and demonstrate that the coercivity of BFO and LFO can be increased or decreased depending on the choice of the embedded phase in the nanocomposite.

The interplay between single particle anisotropy and interparticle interactions in ensembles of magnetic nanoparticles.

This paper aims to analyze the competition of single particle anisotropy and interparticle interactions in nanoparticle ensembles using a random anisotropy model. The model is first applied to ideal systems of non-interacting and strongly dipolar interacting ensembles of maghemite nanoparticles. The investigation is then extended to more complex systems of pure cobalt ferrite CoFe2O4 (CFO) and mixed cobalt-nickel ferrite (Co,Ni)Fe2O4 (CNFO) nanoparticles. Both samples were synthetized by the polyol process and exhibit the same particle size (DTEM ≈ 5 nm), but with different interparticle interaction strengths and single particle anisotropy. The implementation of the random anisotropy model allows investigation of the influence of single particle anisotropy and interparticle interactions, and sheds light on their complex interplay as well as on their individual contribution. This analysis is of fundamental importance in order to understand the physics of these systems and to develop technological applications based on concentrated magnetic nanoparticles, where single and collective behaviors coexist.

Optimising the magnetic performance of Co ferrite nanoparticles via organic ligand capping.

Ferrofluids of CoFe2O4 nanoparticles are gaining increasing interest due to their enhanced heating performance in biomedical applications (e.g. in magnetic hyperthermia as mediators for cancer treatment) or in energy applications (e.g. magneto-thermo-electric applications). Until now, the effect of an organic surfactant on the magnetic particle behaviour has been unintentionally overlooked. Here, we present the counterintuitive magnetic effect of two representative organic ligands: diethylene glycol (DEG) and oleic acid (OA) bonded at the surface of small (∼5 nm in size) CoFe2O4 particles. The combined results of the bulk dc susceptibility, local-probe Mössbauer spectroscopy and physical modelling, which is based on electronic structure calculations and Monte Carlo simulations, reveal the effect of different ionic distributions of the particles due to the different surfactant layers on their magnetic behaviour. They result in an unexpected increase of the saturation magnetisation and the blocking temperature, and a decrease of the coercive field of DEG coated CoFe2O4 nanoparticles. Our work provides a pathway for the production of colloidal assemblies of nanocrystals for the engineering of functional nano-materials.

Magnetic Metal-Organic Framework Composite by Fast and Facile Mechanochemical Process.

Magnetic porous metal-organic framework nanocomposite was obtained by an easy, efficient, and environmentally friendly fabrication method. The material consists in magnetic spinel iron oxide nanoparticles incorporated in an iron(III) carboxylate framework. The magnetic composite was fabricated by a multistep mechanochemical approach. In the first step, iron oxide nanoparticles were obtained via ball milling inducing mechanochemical reaction between iron chlorides and NaOH using NaCl as dispersing agent. Magnetic nanoparticles (MNs) were functionalized by neat grinding with benzene-1,3,5-tricarboxylic acid (1, 3, 5 BTC) and were then subjected to liquid assisted milling using hydrated FeCl3, water, and ethanol to obtain a magnetic framework composite (MFC) consisting of iron oxide nanoparticles encapsulated in a MOF matrix. We report, for the first time, the applicability of the grinding method to obtain a magnetic composite of metal-organic frameworks. The synthesized material exhibits magnetic characteristics and high porosity, and it has been tested as carrier for targeted drug delivery studying loading and release of a model drug (doxorubicin). Developed systems can associate therapeutics and diagnostics properties with possible relevant impact for theranostic and personalized patient treatment. Furthermore, the material properties make them excellent candidates for several other applications such as catalysis, sensing, and selective sequestration processes.

From Mn3O4/MnO core-shell nanoparticles to hollow MnO: evolution of magnetic properties.

Manganese oxide nanoparticles (MNOPs), when dispersed in a water solution, show a magnetic behavior that drastically changes after an aging process. In this paper, the variation in the magnetic properties has been correlated with the structural evolution of the nanoparticles: in particular, the as prepared Mn3O4/MnO core/shell system manifests a low temperature magnetization reversal that is strongly affected by the presence of the MnO shell and, in particular, by the existence of a frustrated interfacial region playing a key role in determining the low temperature irreversibility, the finite coercivity slightly above the Curie temperature of the Mn3O4 phase and the horizontal displacement of the FC-hysteresis loop. On the other hand, the magnetic behavior of the aged system results dominated by the presence of Mn3O4 whose highly anisotropic character (i.e. high coercivity and high magnetization remanence) is attributed to the presence of a large fraction of surface spins. Such a result is consistent with the structural evolution, from core/shell to hollow nanoparticles, as shown by TEM observation.

Superspin glass state in a diluted nanoparticle system stabilized by interparticle interactions mediated by an antiferromagnetic matrix.

In nanoparticle systems consisting of two magnetic materials (bi-magnetic nanoparticles or nanoparticles embedded in a magnetic matrix), there is a constantly growing interest in the investigation of the interplay between interparticle interactions and the nanoparticle-matrix interface exchange coupling, because of its enormous impact on a number of technological applications. The understanding of the mechanisms of such interplay is a great challenge, as it would allow controlling equilibrium and non-equilibrium magnetization dynamics of exchange coupled nanoparticles systems and finely tuning their anisotropy. Here, we provide evidence that this interplay leads to a collective superspin glass (SSG) behavior in a system of diluted ferromagnetic (FM) nanoparticles embedded in an antiferromagnetic (AFM) matrix (5% volume fraction of Co particles in Mn film matrix). We have developed a novel mesoscopic model to study the influence of interparticle interaction on the exchange bias (EB) and the dynamical behavior of assemblies of FM nanoparticles embedded in a granular AFM matrix. Our mesoscopic model is based on reducing the amount of simulated spins to the minimum number necessary to describe the magnetic structure of the system and introducing the adequate exchange parameters between the different spins. The model replicates remarkably well the observed static and dynamical SSG properties as well as the EB behavior. In addition, the proposed model well explains the role of the significant Co/Mn alloying and of the granularity of the matrix in mediating interparticle interactions through exchange and dipole-dipole coupling between the uncompensated moments of its grains and the exchange interaction at the Co/Mn interface.

Studying nanoparticles' 3D shape by aspect maps: Determination of the morphology of bacterial magnetic nanoparticles.

Magnetic nanoparticles (MNPs) are widely investigated due to their potential use in various applications, ranging from electronics to biomedical devices. The magnetic properties of MNPs are strongly dependent on their size and shape (i.e., morphology), thus appropriate tools to investigate their morphology are fundamental to understand the physics of these systems. Recently a new approach to study nanoparticle morphology by Transmission Electron Microscopy (TEM) analysis has been proposed, introducing the so-called Aspect Maps (AMs). In this paper, a further evolution of the AM method is presented, allowing determination of the nanoparticles' 3D shape by TEM image. As a case study, this paper will focus on magnetite nanoparticles (Fe3O4), with a mean size of ∼45 nm extracted from Magnetospirillum gryphiswaldense magnetostatic bacteria (MTB). The proposed approach gives a complete description of the nanoparticles' morphology, allowing estimation of an average geometrical size and shape. In addition, preliminary investigation of the magnetic properties of MTB nanoparticles was performed, giving some insight into interparticle interactions and on the reversal mechanism of the magnetization.

Studying the effect of Zn-substitution on the magnetic and hyperthermic properties of cobalt ferrite nanoparticles.

The possibility to finely control nanostructured cubic ferrites (M(II)Fe2O4) paves the way to design materials with the desired magnetic properties for specific applications. However, the strict and complex interrelation among the chemical composition, size, polydispersity, shape and surface coating renders their correlation with the magnetic properties not trivial to predict. In this context, this work aims to discuss the magnetic properties and the heating abilities of Zn-substituted cobalt ferrite nanoparticles with different zinc contents (ZnxCo1-xFe2O4 with 0 < x < 0.6), specifically prepared with similar particle sizes (∼7 nm) and size distributions having the crystallite size (∼6 nm) and capping agent amount of 15%. All samples have high saturation magnetisation (Ms) values at 5 K (>100 emu g(-1)). The increase in the zinc content up to x = 0.46 in the structure has resulted in an increase of the saturation magnetisation (Ms) at 5 K. High Ms values have also been revealed at room temperature (∼90 emu g(-1)) for both CoFe2O4 and Zn0.30Co0.70Fe2O4 samples and their heating ability has been tested. Despite a similar saturation magnetisation, the specific absorption rate value for the cobalt ferrite is three times higher than the Zn-substituted one. DC magnetometry results were not sufficient to justify these data, the experimental conditions of SAR and static measurements being quite different. The synergic combination of DC with AC magnetometry and (57)Fe Mössbauer spectroscopy represents a powerful tool to get new insights into the design of suitable heat mediators for magnetic fluid hyperthermia.

Designing new ferrite/manganite nanocomposites.

Two kinds of nanocomposites of transition metal oxides were synthesized and investigated. Each nanocomposite comprises nanoparticles of La0.67Ca0.33MnO3 and CoFe2O4 in similar volume fractions, however arranged with different morphologies. The temperature-dependent magnetic and electrical properties of the two systems are found to greatly differ, suggesting different degrees of interaction and coupling of their constituents. This is confirmed by magnetic field-dependent experiments, which reveal contrasted magnetization reversal and magnetoresistance in the systems. We discuss this morphology-physical property relationship, and the possibility to further tune the magnetism and magneto-transport in such nanocomposites.

Evolution of the magnetic structure with chemical composition in spinel iron oxide nanoparticles.

Magnetic properties of iron oxide nanoparticles with spinel structure are strictly related to a complex interplay between cationic distribution and the presence of a non-collinear spin structure (spin canting). With the aim to gain better insight into the effect of the magnetic structure on magnetic properties, in this paper we investigated a family of small crystalline ferrite nanoparticles of the formula CoxNi1-xFe2O4 (0 ≤x≤ 1) having equal size (≈4.5 nm) and spherical-like shape. The field dependence of magnetization at low temperatures indicated a clear increase of magnetocrystalline anisotropy and saturation magnetization (higher than the bulk value for CoFe2O4: ∼130 A m(2) kg(-1)) with the increase of cobalt content. The magnetic structure of nanoparticles has been investigated by Mössbauer spectroscopy under an intense magnetic field (8 T) at a low temperature (10 K). The magnetic properties have been explained in terms of an evolution of the magnetic structure with the increase of cobalt content. In addition a direct correlation between cationic distribution and spin canting has been proposed, explaining the presence of a noncollinear spin structure in terms of superexchange interaction energy produced by the average cationic distribution and vacancies in the spinel structure.