Magnetic Nanoparticle Composites: Synergistic Effects and Applications

Composite materials are made from two or more constituent materials with distinct physical or chemical properties that, when combined, produce a material with characteristics which are at least to some degree different from its individual components. Nanocomposite materials are composed of different materials of which at least one has nanoscale dimensions. Common types of nanocomposites consist of a combination of two different elements, with a nanoparticle that is linked to, or surrounded by, another organic or inorganic material, for example in a core-shell or heterostructure configuration. A general family of nanoparticle composites concerns the coating of a nanoscale material by a polymer, SiO2 or carbon. Other materials, such as graphene or graphene oxide (GO), are used as supports forming composites when nanoscale materials are deposited onto them. In this Review we focus on magnetic nanocomposites, describing their synthetic methods, physical properties and applications. Several types of nanocomposites are presented, according to their composition, morphology or surface functionalization. Their applications are largely due to the synergistic effects that appear thanks to the co-existence of two different materials and to their interface, resulting in properties often better than those of their single-phase components. Applications discussed concern magnetically separable catalysts, water treatment, diagnostics-sensing and biomedicine

Interaction of ZnO Nanostructures with Proteins: In Vitro Fibrillation/Antifibrillation Studies and in Silico Molecular Docking Simulations

Protein amyloidosis is related to many neurological disorders. Nanoparticles (NPs) due to their small size can regulate both the polypeptide monomers/oligomers assembly into amyloid fibrils/plaques and the disintegration of the existent plaques. Herein, we have synthesized ZnO nanoflowers and polyol-coated ZnO NPs of relatively small size (40 nm) with cylindrical shape, through solvothermal and microwave-assisted routes, respectively. The effect of the different morphology of nanostructures on the fibrillation/antifibrillation process was monitored in bovine serum albumin (BSA) and human insulin (HI) by fluorescence Thioflavin T (ThT) measurements. Although both nanomaterials affected the amyloid formation mechanism as well as their disaggregation, ZnO nanoflowers with their sharp edges exhibited the greatest amyloid degradation rate in both model proteins (73% and 35%, respectively) and inhibited the most the insulin fibril growth, while restrained also the fibrillation process in the case of albumin solution. In silico molecular docking simulations on the crystal structure of BSA and HI were performed to analyze further the observed in vitro activity of ZnO nanostructures. The binding energy of ZnO NPs was found lower for BSA (−5.44), highlighting their ability to act as catalysts in the fibrillation process of albumin monomers

Dimpled SiO₂@γ-Fe₂O₃ nanocomposites – fabrication and use for arsenic adsorption in aqueous medium

We report the synthesis of nanocomposites made of silica nanoparticles whose six surface dimples are decorated with magnetic maghemite nanoparticles and their use for detection and recovery of arsenic in aqueous media. Precursor silica nanoparticles have aminated polystyrene chains at the bottom of their dimples and the maghemite nanoparticles are surface functionalized with carboxylic acid groups in two steps: amination with 3-aminopropyltrimethoxysilane, then derivatization with succinic anhydride in the presence of triethylamine. In the end, the colloidal assembly consists of the regioselective grafting of the carboxylic acid-modified iron oxide nanoparticles onto the 6-dimple silica nanoparticles. Several characterization techniques such as transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) are employed to assess the grafting process and study the influence of the maghemite functional groups on the quality of the composites formed. The resulting magnetic nanocomposites are used for the environmentally benign detection and removal of arsenic from aqueous medium, being readily extracted through means of magnetic separation

Characterization techniques for nanoparticles: comparison and complementarity upon studying nanoparticle properties

Nanostructures have attracted huge interest as a rapidly growing class of materials for many applications. Several techniques have been used to characterize the size, crystal structure, elemental composition and a variety of other physical properties of nanoparticles. In several cases, there are physical properties that can be evaluated by more than one technique. Different strengths and limitations of each technique complicate the choice of the most suitable method, while often a combinatorial characterization approach is needed. In addition, given that the significance of nanoparticles in basic research and applications is constantly increasing, it is necessary that researchers from separate fields overcome the challenges in the reproducible and reliable characterization of nanomaterials, after their synthesis and further process (e.g. annealing) stages. The principal objective of this review is to summarize the present knowledge on the use, advances, advantages and weaknesses of a large number of experimental techniques that are available for the characterization of nanoparticles. Different characterization techniques are classified according to the concept/group of the technique used, the information they can provide, or the materials that they are destined for. We describe the main characteristics of the techniques and their operation principles and we give various examples of their use, presenting them in a comparative mode, when possible, in relation to the property studied in each case

Development and Characterization of Curcumin-Silver Nanoparticles as a Promising Formulation to Test on Human Pterygium-Derived Keratinocytes

Pterygium is a progressive disease of the human eye arising from sub-conjunctival tissue and extending onto the cornea. Due to its invasive growth, pterygium can reach the pupil compromising visual function. Currently available medical treatments have limited success in suppressing efficiently the disease. Previous studies have demonstrated that curcumin, polyphenol isolated from the rhizome of Curcuma longa, induces apoptosis of human pterygium fibroblasts in a dose- and time-dependent manner showing promising activity in the treatment of this ophthalmic disease. However, this molecule is not very soluble in water in either neutral or acidic pH and is only slightly more soluble in alkaline conditions, while its dissolving in organic solvents drastically reduces its potential use for biomedical applications. A nanoformulation of curcumin stabilized silver nanoparticles (Cur-AgNPs) seems an effective strategy to increase the bioavailability of curcumin without inducing toxic effects. In fact, silver nitrates have been used safely for the treatment of many ophthalmic conditions and diseases for a long time and the concentration of AgNPs in this formulation is quite low. The synthesis of this new compound was achieved through a modified Bettini's method adapted to improve the quality of the product intended for human use. Indeed, the pH of the reaction was changed to 9, the temperature of the reaction was increased from 90 °C to 100 °C and after the synthesis the Cur-AgNPs were dispersed in Borax buffer using a dialysis step to improve the biocompatibility of the formulation. This new compound will be able to deliver both components (curcumin and silver) at the same time to the affected tissue, representing an alternative and a more sophisticated strategy for the treatment of human pterygium. Further in vitro and in vivo assays will be required to validate this formulation

Impact of Coated Zinc Oxide Nanoparticles on Photosystem II of Tomato Plants

Zinc oxide nanoparticles (ZnO NPs) have emerged as a prominent tool in agriculture. Since photosynthetic function is a significant measurement of phytotoxicity and an assessment tool prior to large-scale agricultural applications, the impact of engineered irregular-shaped ZnO NPs coated with oleylamine (ZnO@OAm NPs) were tested. The ZnO@OAm NPs (crystalline size 19 nm) were solvothermally prepared in the sole presence of oleylamine (OAm) and evaluated on tomato (Lycopersicon esculentum Mill.) photosystem II (PSII) photochemistry. Foliar-sprayed 15 mg L−1 ZnO@OAm NPs on tomato leaflets increased chlorophyll content that initiated a higher amount of light energy capture, which resulted in about a 20% increased electron transport rate (ETR) and a quantum yield of PSII photochemistry (ΦPSII) at the growth light (GL, 600 μmol photons m−2 s−1). However, the ZnO@OAm NPs caused a malfunction in the oxygen-evolving complex (OEC) of PSII, which resulted in photoinhibition and increased ROS accumulation. The ROS accumulation was due to the decreased photoprotective mechanism of non-photochemical quenching (NPQ) and to the donor-side photoinhibition. Despite ROS accumulation, ZnO@OAm NPs decreased the excess excitation energy of the PSII, indicating improved PSII efficiency. Therefore, synthesized ZnO@OAm NPs can potentially be used as photosynthetic biostimulants for enhancing crop yields after being tested on other plant species

Tailoring Ca-Based Nanoparticles by Polyol Process for Use as Nematicidals and pH Adjusters in Agriculture

The remarkable progress in nanotechnology has extended the application of inorganic nanoparticles (NPs) in the agriculture sector, as both economically sustainable and environmentally sound alternatives. Root knot nematodes are undoubtedly a foremost problem of agriculture, and research strives to develop effective materials to tackle this issue. Herein, the microwave-assisted selective polyol synthesis of different compositions of Ca-based NPs, Ca(OH)2, Ca(OH)2/CaCO3, and CaCO3 is reported and the products were evaluated as nematicides and pH adjusters. Two precursors (CaCl2 and Ca(NO3)2) and three polyols (1,2-propylene glycol (PG), tetraethylene glycol (TEG), polyethylene glycol (PEG 8000)) that differ in their redox potential have been utilized to provide selectivity over composition. On the basis of the utilized polyols, NPs are produced as inorganic/organic hybrid formulations with a biocompatible organic coating that provides increased colloidal stability and controlled release of active components. Characterization of NPs has been carried out by XRD, TGA, FTIR, TEM, and pH-metry. Each composition exhibited different pH changing ability, an essential feature for agrochemical applications. The in vitro nematicidal activity of Ca(OH)2, Ca(OH)2/CaCO3, and CaCO3NPs was evaluated on second stage juveniles (J2) of two Meloidogyne species (Meloidogyne incognita and Meloidogyne javanica) based on nematode paralysis experiments. Results unveiled nematicidal activity for all evaluated Ca-based NPs, while Ca(OH)2 and CaCO3 NPs appeared to be the most and the least effective ones, respectively. The nematicidal effect appears to be boosted by the release of [OH]- anions, as indicated by pH-metric measurements, displaying the crucial role of [OH]- anions in their nematicidal activity

Stable Iron Oxide Nanoflowers with Exceptional Magnetic Heating Efficiency: Simple and Fast Polyol Synthesis

Magnetically induced hyperthermia has reached a milestone in medical nanoscience and in phase III clinical trials for cancer treatment. As it relies on the heat generated by magnetic nanoparticles (NPs) when exposed to an external alternating magnetic field, the heating ability of these NPs is of paramount importance, so is their synthesis. We present a simple and fast method to produce iron oxide nanostructures with excellent heating ability that are colloidally stable in water. A polyol process yielded biocompatible single core nanoparticles and nanoflowers. The effect of parameters such as the precursor concentration, polyol molecular weight as well as reaction time was studied, aiming to produce NPs with the highest possible heating rates. Polyacrylic acid facilitated the formation of excellent nanoheating agents iron oxide nanoflowers (IONFs) within 30 min. The progressive increase of the size of the NFs through applying a seeded growth approach resulted in outstanding enhancement of their heating efficiency with intrinsic loss parameter up to 8.49 nH m2 kgFe-1. The colloidal stability of the NFs was maintained when transferring to an aqueous solution via a simple ligand exchange protocol, replacing polyol ligands with biocompatible sodium tripolyphosphate to secure the IONPs long-term colloidal stabilization

Structure Differentiation of Hydrophilic Brass Nanoparticles Using a Polyol Toolbox

Nano-brasses are emerging as a new class of composition-dependent applicable materials. It remains a challenge to synthesize hydrophilic brass nanoparticles (NPs) and further exploit them for promising bio-applications. Based on red/ox potential of polyol and nitrate salts precursors, a series of hydrophilic brass formulations of different nanoarchitectures was prepared and characterized. Self-assembly synthesis was performed in the presence of triethylene glycol (TrEG) and nitrate precursors Cu(NO3)2·3H2O and Zn(NO3)2·6H2O in an autoclave system, at different temperatures, conventional or microwave-assisted heating, while a range of precursor ratios was investigated. NPs were thoroughly characterized via X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmition electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS), and ζ-potential to determine the crystal structure, composition, morphology, size, state of polyol coating, and aqueous colloidal stability. Distinct bimetallic α-brasses and γ-brasses, α-Cu40Zn25/γ-Cu11Zn24, α-Cu63Zn37, α-Cu47Zn10/γ-Cu19Zn24, and hierarchical core/shell structures, α-Cu59Zn30@(ZnO)11, Cu35Zn16@(ZnO)49, α-Cu37Zn18@(ZnO)45, Cu@Zinc oxalate, were produced by each synthetic protocol as stoichiometric, copper-rich, and/or zinc-rich nanomaterials. TEM sizes were estimated at 20–40 nm for pure bimetallic particles and at 45–70 nm for hierarchical core/shell structures. Crystallite sizes for the bimetallic nanocrystals were found ca. 30–45 nm, while in the case of the core-shell structures, smaller values around 15–20 nm were calculated for the ZnO shells. Oxidation and/or fragmentation of TrEG was unveiled and attributed to the different fabrication routes and formation mechanisms. All NPs were hydrophilic with 20–30% w/w of polyol coating, non-ionic colloidal stabilization (−5 mV < ζ-potential < −13 mV) and relatively small hydrodynamic sizes (<250 nm). The polyol toolbox proved effective in tailoring the structure and composition of hydrophilic brass NPs while keeping the crystallite and hydrodynamic sizes fixed

Conditions determining the morphology and nanoscale magnetism of Co nanoparticles: Experimental and numerical studies

Co-based nanostructures ranging from core-shell to hollow nanoparticles were produced by varying the reaction time and the chemical environment during the thermal decomposition of Co2(CO)8. Both structural characterization and kinetic model simulation illustrate that the diffusivities of Co and oxygen determine the growth ratio and the final morphology of the nanoparticles. Exchange coupling between Co and Co-oxide in core/shell nanoparticles induced a shift of field-cooled hysteresis loops that is proportional to the shell thickness, as verified by numerical studies. The increased nanocomplexity when going from core/shell to hollow particles, also leads to the appearance of hysteresis above 300 K due to an enhancement of the surface anisotropy resulting from the additional spin-disordered surfaces.Comment: 29 pages including 11 figures embedded. Submitted to Phys. Rev.