Magnetic Hybrid Nanomaterials Research Articles

Magnetic hybrid nanomaterial based on a natural polymer and an amino acid as pH/temperature dual-responsive nanoplatform for the delivery of tamoxifen

Magnetic hybrid nanomaterials offer promising properties for the advancement of nanoplatforms in cancer nanomedicine, particularly in drug delivery applications. These nanoplatforms can effectively respond to various stimuli present at the tumor site, such as pH and temperature fluctuations, allowing for controlled and triggered release of therapeutic payloads. In this study, we present a straightforward methodology for the synthesis of stable hybrid magnetic nanoplatforms (HMNP) based on Fe3O4 nanoparticles, L-cysteine (L-Cys), and hyaluronic acid (HA) as key constituents for the delivery of tamoxifen (TMX). The synthesized superparamagnetic HMNP, Fe3O4-L-Cys-HA, with a size of 11 nm, was successfully loaded with TMX. The incorporation of L-Cys showed superior interaction with the surface of Fe3O4 nanoparticles compared to other L-Cys derivatives explored as ligands. Consequently, L-Cys was selected for further functionalization with HA, providing the HMNP with active targeting properties toward CD44-overexpressed receptors. High loading efficiency of TMX (75%) was achieved via electrostatic interaction between the carboxylate groups exposed by the HMNP and the ammonium group of the TMX side chain. Efficient control in the TMX release towards different receptor media was observed. Notably, the release of TMX from HMNP-TMX was triggered under acidic pH and hyperthermia conditions, showcasing its responsiveness to both stimuli. Furthermore, enhanced anticancer activity of TMX against MDA-MB-231 breast cancer cells was observed when loaded into HMNP (IC50 almost 3-fold lower for HMNP-TMX compared to free TMX), indicating improved cell uptake of TMX-loaded HMNP in comparison to the free drug. Overall, pH/temperature dual-sensitive HMNP demonstrates promising potential as a nanoplatform for cancer nanomedicine, with prospects for magnetic hyperthermia therapy.

Rational design of stimuli‐responsive magnetic polymer hybrid (nano)materials

AbstractCombining organic and inorganic materials is a fascinating strategy to produce hybrid materials that combine the advantages of both polymeric and inorganic materials. Among the various types of organic–inorganic hybrids, stimuli‐responsive magnetic polymer hybrids (RMPHs) are particularly promising materials for a wide variety of applications. While the magnetic properties are generally provided by the presence of magnetic nanoparticles, such as iron oxide nanoparticles, the polymeric compound brings the stimuli‐responsiveness, e.g. responsiveness to pH, temperature, redox reaction or irradiation. Furthermore, as the chemical structure and architecture of the polymeric materials are diverse and easily tunable, stimuli‐RMPHs have found applications in various domains, including catalysis, biotechnology, (bio)imaging and cancer therapy. Given the importance of the hybrids' shape and morphology for the targeted application, this review presents the possible synthetic strategies to rationally design stimuli‐RMPHs of various morphologies ranging from nanometric core–shell structures to nanogels, microgels and membranes. © 2023 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Fabrication of monoBODIPY-functionalized Fe3O4@SiO2@TiO2 nanoparticles for the photocatalytic degradation of rhodamine B under UV irradiation and the detection and removal of Cu(II) ions in aqueous solutions

In this study, the potential of magnetic fluorescence hybrid nanoparticle (Fe3O4@SiO2@TiO2-APTMS-monoBODIPY) for simultaneous detection and removal of inorganic contaminant Cu(II) ions and photocatalytic degradation of organic contaminant Rhodamine B (RhB) dye in aqueous solutions under UV light was investigated. Samples were synthesized at each stage, and the magnetic fluorescence hybrid nanoparticle was characterized by SEM, TEM, EDX, FTIR, and XRD. When Cu(II) ions were added to the Fe3O4@SiO2@TiO2-APTMS-monoBODIPY suspension mixture, the fluorescence intensity at ~ 543 nm decreased. In addition, the addition of Cu(II) ions in the presence of different cation species caused dramatic fluorescent quenching that was very selective for Cu(II) ions. The detection limit values of Cu(II) ions using the Fe3O4@SiO2@TiO2-APTMS-monoBODIPY is 0.47 µM. The prepared magnetic fluorescent hybrid nanoparticle was used for Cu(II) adsorption from aqueous solutions. Four different adsorption isotherms were calculated, and it was found that the Langmuir isotherm fit better, and the maximum adsorption capacity was 50.505 mg/g. Kinetic research followed the pseudo-second-order kinetics model. Thermodynamic parameters were calculated, and the adsorption of Cu(II) ions turned out to be endothermic, favorable, and spontaneous. RhB dyes in the suspension mixture were adsorbed on magnetic fluorescent hybrid nanomaterial in the dark with stirring for 30 min. Then after 60 min of mixing under UV light, they showed an RhB degradation percentage of 29.49%.

Magnetic hybrid nanoparticles modified with morin for the removal of Sc(III) from aqueous solutions

In this research magnetic hybrid nanomaterials modified with morin for sorption of scandium ions have been synthesized and investigated. In general, sorption of scandium increases with increasing pH. However, Fe@COO-morin nanocomposite with covalently bonded morin showed superiority over physically coated Fe3O4@morin nanoparticles. Several models have been applied for investigation of different aspects of sorption onto Fe@COO-morin. Results show, that it follows Langmuir model and pseudo-second order kinetics. Developed hybrid Fe@COO-morin nanoparticles were successfully applied for separation and preconcentration of scandium using magnetic solid phase extraction from spiked water samples. Optimized procedure includes selective sorption of scandium at pH 5, elution with 1 mol L−1 HNO3 and ICP OES determination. A preconcentration factor of 20 was achieved and sorbent provides the possibility of multiple use.

Preparation of novel hybrid nanomaterials based on LaFeO3 and phosphotungstic acid as a highly efficient magnetic photocatalyst for the degradation of methylene blue dye solution

Novel magnetic hybrid nanomaterials 1 (LaFeO3.Fe3O4@SiO2‐NH2/PW12) were synthesized by supporting phosphotungstic acid (H3PW12O40; PW12) on LaFeO3.Fe3O4 nanomaterials through sono‐assisted method. The synthesized nanomaterials were fully characterized by using FT‐IR, XRD, UV–vis, BET‐BJH, VSM, SEM, and TEM analyses. FT‐IR, XRD, and UV–vis confirmed successful synthesis of nanomaterials. The SEM and TEM images revealed spherical morphology with core‐shell structure for hybrid nanomaterials 1. VSM results confirmed the magnetic property of hybrid nanomaterials 1 and suggested it as easily recyclable photocatalyst for removal of organic dyes from aqueous solution. The photocatalytic activity of hybrid nanomaterials 1 has been studied over the degradation of methylene blue (MB) and methyl orange (MO) solution under UV–vis light irradiation. Importantly the hybrid nanomaterials 1 showed outstanding degradation efficiency for MB solution in comparison with bare LaFeO3.Fe3O4 and PW12. The photocatalytic activity was enhanced mainly due to the high efficiency in separation of electron–hole pairs induced by the remarkable synergistic effects of LaFeO3.Fe3O4 and PW12 semiconductors. After the photocatalytic reaction, the nanocomposite can be easily separated from the reaction solution and reused several times without loss of its photocatalytic activity. Trapping experiments indicated that hole (hVB+) and •OH radicals were the main reactive species for dye degradation in the present photocatalytic system. On the basis of the experimental results and estimated band gaps, the mechanism for the enhanced photocatalytic activity was proposed.

Silica -magnetic inorganic hybrid nanomaterials as versatile sensing platform

Several hybrid sensing materials, which are organized by interaction of organic molecules onto inorganic supports, have been developed as a novel and hopeful class of hybrid sensing probes. The hybrid silica-magnetic based sensors provide perfect properties for production of various devices in sensing technology. The hybridization of silica and magnetic NPs as biocompatible, biodegradable and superparamagnetic structures provides the opportunity to produce capable sensing materials. The fluorescence, electrochemical and calorimetric sensors based on silica-magnetic materials can be applied in quantitative detection of various analytes. This review touches upon a subject of the design and synthesis of different sensors based on magnetic-silica hybrid nanomaterials and discusses their applications for improved detection of analytes in environmental and biological fields.

Magnetically recoverable Ni@CuI hybrid nanocatalysts affording spiropyrroline heterocycles from ketoximes and alkenes

AbstractThe design of magnetic hybrid nanomaterials for cooperative activation of diverse functional groups drives future nanocatalysis toward green and sustainable multi‐component organic synthesis. Here, we report the synthesis of unique Ni@CuI hybrid nanocatalysts by oxidation of the Cu0 surface in Ni@Cu core‐shell precursor using an ethanolic I2 solution. The morphological (scanning electron microscopy and energy‐dispersive X‐ray spectroscopy) and structural (powder X‐ray diffraction and X‐ray photoelectron spectroscopy) characterizations conform the formation of Ni0 and CuI hybrid nanocatalysts. These are efficient catalysts for the activation of oxime and olefin substrates to afford spiropyrrolines in a short time and excellent yields under green reaction conditions. The control experiments delineate the role of Cu sites as redox (I–III) triggered cleavage of N−O bond (oximes) and Ni0 sites adsorb the olefin (C=C) which is proximity to the Cu‐enamide intermediate to enhance the intermolecular cyclization lead to spiropyrrolines. The robustness of Ni@CuI hybrid nanocatalyst is demonstrated over five cycles without loss in its turnover and structural integrity, which follows ideal green chemistry metrics.

Synthesis and Characterization of Triamine modified coated Iron Sand Hybrid Nanomaterials originating from Kendal Coast

Nanomaterials have broad and unique applications in various fields. In this research, synthesis of Iron Sand Magnetic Hybrid nanomaterials coated with propyldiethylenetriammine modified silica (PB@SiO2@TA) originating from the coast of Muara Kencan, Kendal Regency. This study began with iron sand preparation, continued with activation, dispersing iron sand, then coating iron sand with propyldiethylenetriammine modified silica. The resulting product was characterized by X-Ray Fluorescence (XRF), Fourier Transform Infrared (FT-IR) Spectrophotometer, X-Ray Diffractometer (XRD), and Transmission Electron Microscope (TEM). The characterization results show that the iron sand of the coast of Muara Kencan Beach has a high iron oxide content (81.66%) with minerals in the form of magnetite. The characterization results also showed that the nanomaterial hybrid iron sand coated with propyldiethylenetriammine modified silica (PB@SiO2@TA) was successfully synthesized with a crystal size of 36.21 nm, with better particle dispersion than the prepared iron sand.

Synthesis of a novel β-cyclodextrin-functionalized Fe3O4/BaMoO4:Dy3+ magnetic luminescent hybrid nanomaterial and its application as a drug carrier.

Magnetic luminescent hybrid nanoparticles Fe3O4/BaMoO4:Dy3+ (MLHNPs) were successfully synthesized by the co-precipitation method using ethylene glycol. The MLHNPs are functionalized with β-cyclodextrin (CD) using 3-aminopropyl triethoxysilane (APTES). The surface functionalization of nanoparticles and their conjugation have been confirmed via powder XRD, FTIR, HRTEM, and PL analyses. The feasibility of functionalized MLHNPs as nanocarriers for hydrophobic drugs (triazole derivatives) was verified by studying the uptake and release profile using a triazole derivative as a hydrophobic drug. In addition, the photoluminescence spectroscopy results confirmed the optical imaging capability of MLHNPs. The outcomes of loading and release disclose that this system is likely to be a suitable tool as a hydrophobic drug carrier.

Silica Removal Using Magnetic Iron-Aluminum Hybrid Nanomaterials: Measurements, Adsorption Mechanisms, and Implications for Silica Scaling in Reverse Osmosis.

Composite magnetic aluminum hydroxide at iron oxide nanomaterials, Al(OH)3@Fe3O4, with a well-defined core-shell structure, were used as pretreatment adsorbents for the removal of silica in brackish water. The Al(OH)3 outer shell confers silica adsorption capacity, and the superparamagnetic Fe3O4 core allows material separation and magnetic recovery. The as-prepared nanomaterials (2 g L-1) remove ∼95 and ∼80% silica from Si-rich solutions with 0.5 and 2 mM initial silica concentrations, respectively. Regeneration under basic conditions was evaluated, and post-adsorption treatment with 0.05 M NaOH yielded optimal material reusability. After four regeneration cycles, the Al(OH)3@Fe3O4 nanomaterials retain their magnetic property while still being able to remove ∼40% silica from solutions at an adsorbent concentration of 2 g L-1. The mechanism of silica adsorption onto the surface of the nanomaterials was probed using several spectroscopic techniques. ATR-FTIR (attenuated total reflection-Fourier transform infrared) integrated with two-dimensional correlation analysis shows that silica species vary from Q2 to Q4 with adsorption time corresponding to silica polymerization. 29Si solid-state NMR spectra show an upfield chemical shift displacement of the Q2 signal, which indicates the formation of Q4 units, suggesting silica polymerization onto the Al(OH)3 shell. In addition, a laboratory-scale reverse osmosis setup was used to evaluate Al(OH)3@Fe3O4 as pretreatment materials for silica removal. Results show that silica scaling was significantly alleviated, and water recovery was enhanced when feed waters were pretreated with the magnetic nanomaterials. Taken together, our study highlights the promise of magnetic Al(OH)3@Fe3O4 nanomaterials in treating brackish water and achieving higher water recovery for inland desalination.

Carbon decorated octahedral shaped Fe3O4 and α-Fe2O3 magnetic hybrid nanomaterials for next generation supercapacitor applications

Octahedral shaped Fe3O4 and α-Fe2O3 nanoparticles were prepared by simple chemical oxidation method. The prepared magnetic nanoparticles were surface modified with carbon using sugar solution as a carbon source. The crystallinity, structural and morphological studies through XRD, FESEM and TEM analysis confirmed the successful formation of the desired nanostructures. The obtained carbon modified octahedral shaped Fe3O4 nanoparticles exhibited a larger saturation magnetization of 87 emu/g. Further, the carbon modified magnetic hybrid nanoparticles were exploited as a negative electrode material for supercapacitor application and observed a high specific capacitance value of 274 F/g for the post annealed samples. The enhanced specific capacitance value is due to the fraction of carbon in hybrid material and it could be enhanced further by increasing the carbon fraction. The cycle stability performance was tested with 5 A/g and showed 83% retention even after 5000 cycles.

Synthesis and characterization of magnetic hybrid nanomaterials via RAFT polymerization: A pH sensitive drug delivery system.

Herein, a facile and versatile method for the synthesis of a novel magnetic nanocarrier via surface- initiated reversible addition-fragmentation chain transfer (RAFT) polymerization is introduced. At first, RAFT agent was successfully attached to the surface of Fe3O4 nanoparticles and, then, poly (glycidyl methacrylate) (PGMA) chains were grown and anchored onto the surface of Fe3O4 nanoparticles. At the end, hydrazine (Hy) groups were introduced to the PGMA chains via reaction between epoxy rings and hydrazine molecules. Doxorubicin (DOX) was covalently conjugated to the prepared nanocarrier (Fe3O4@PGMA@Hy) through a hydrazone linkage. The in vitro drug release of Fe3O4@PGMA@Hy@DOX examined in buffers with pH 7.4 and pH 5.4 exhibited a strong pH-sensitive behavior. The results showed that Fe3O4@PGMA@Hy@DOX successfully performed the delivery and controlled release of doxorubicin (DOX) anticancer drug.

Facile preparation of a hydrophilic magnetic hybrid nanomaterial with solid-phase extraction capability for highly efficient enrichment of phthalates in environmental water

Phthalic acid esters (PAEs) are involved in endocrine disrupting effects and have become a potential threat to human health.

Cover Image, Volume 10, Issue 1

The cover image, by Xin Tian et al., is based on the Focus Article Functional magnetic hybrid nanomaterials for biomedical diagnosis and treatment, DOI: 10.1002/wnan.1476. image

Functional magnetic hybrid nanomaterials for biomedical diagnosis and treatment.

Magnetic nanomaterials integrating supplemental functional materials are called magnetic hybrid nanomaterials (MHNs). Such MHNs have drawn increasing attention due to their biocompatibility and the potential applications either as alternative contrast enhancing agents or effective heat nanomediators in hyperthermia therapy. The joint function comes from the hybrid nanostructures. Hybrid nanostructures of different modification can be easily achieved owing to the large surface-area-to-volume ratio and sophisticated surface characteristic. In this focus article, we mainly discussed the design and synthesis of MHNs and their applications as multimodal imaging probes and therapy agents in biomedicine. These MHNs consisting magnetic nanomaterials with functional nanocomponents such as noble metal or isotopes could perform not only superparamagnetism but also features that can be adapted in, for example, enhancing computed tomography contrast modalities, positron emission tomography, and single-photon emission computed tomography. The combination of several techniques provides more comprehensive information by both synergizing the advantages, such as quantitative evaluation, higher sensitivity and spatial resolution, and mitigating the disadvantages. Such hybrid nanostructures could also provide a unique nanoplatform for enhanced medical tracing, magnetic field, and light-triggered hyperthermia. Moreover, potential advantages and opportunities will be achieved via a combination of diagnostic and therapeutic agents within a single platform, which is so-called 'theranostics.' We expect the combination of unique structural characteristics and integrated functions of multicomponent magnetic hybrid nanomaterials will attract increasing research interest and could lead to new opportunities in nanomedicine and nanobiotechnology. WIREs Nanomed Nanobiotechnol 2018, 10:e1476. doi: 10.1002/wnan.1476 This article is categorized under: Diagnostic Tools > Diagnostic Nanodevices.

Generation of Multishell Magnetic Hybrid Nanoparticles by Encapsulation of Genetically Engineered and Fluorescent Bacterial Magnetosomes with ZnO and SiO2.

Magnetic nanoparticles (MNPs) have great potential in biomedical applications, but the chemical synthesis of size-controlled and functionalized core-shell MNPs remain challenging. Magnetosomes produced by the magnetotactic bacterium Magnetospirillum gryphiswaldense are naturally uniform and chemically pure magnetite MNPs with superior magnetic characteristics. Here, additional functionalities are made possible by the incorporation of biomolecules on the magnetosome surface; the magnetosome system is then chemically encapsulated with an inorganic coating. The novel multishell nanoparticles consist of the magnetosome core-which includes the magnetite crystal, the magnetosome membrane, and additional moieties, such as the enhanced green fluorescent protein (EGFP) and peptides-and an outer shell, comprising either silica or zinc oxide. Coating the functionalized magnetosomes with silica improves their colloidal stability and preserves the EGFP fluorescence in the presence of proteases and detergents. In addition, the surface charge of magnetosomes can be adjusted by varying the coating. This method will be useful for the versatile generation of new, multifunctional, multishell, and magnetic hybrid nanomaterials with potential applications in various biotechnological fields.

A novel Schiff base of Mn(III) complex supported on magnetic cobalt nanoparticles as a highly efficient retrievable heterogeneous catalyst in oxidation of alcohols and sulfides compounds

A novel Schiff base Mn(III) complex was successfully synthesized and covalently immobilized on silica-coated magnetic cobalt nanoparticles as a support. The prepared heterogeneous catalyst showed a high catalytic activity in the oxidation of alcohols with high yield and in a milder conditions. The synthesized hybrid nanomaterials were fully characterized by FT-IR spectra, XRD and EDAX analysis. Morphology of the nanomaterials was determined by SEM and TEM. Also, the metallic magnetic cobalt and silica in the core–shell structure were determined by XPS analyses. The synthesized catalyst shows a high catalytic activity in the oxidation of alcohols and sulfides to the corresponding aldehydes and sulfoxides. Also the magnetic properties of the magnetic support and hybrid nanomaterials were measured by AGFM analysis.

A novel magnetic hybrid nanomaterial as a highly efficient and selective catalyst for alcohol oxidation based on new Schiff base complexes of transition metal ions

In this study, novel heterogeneous catalysts of Schiff base complexes of transition metal ions supported on silica coated magnetic metallic cobalt nanoparticles were successfully synthesized. Firstly, silica coated cobalt nanoparticles were synthesized through a one-pot reaction. Secondly, Schiff base complexes of different transition metal ions were immobilized on a magnetic support. The catalytic activity of catalysts was studied in oxidation of various aromatic alcohols with environmentally friendly oxidant under different solvents and solvent free conditions. Also, the effects of parameters such as solvent, amount of oxidant and catalysts, reaction temperature and utilization efficiency of hydrogen peroxide were investigated. The synthesized catalysts acted selectively and converted the alcohols to corresponding aldehydes with high yield. The synthesized catalysts were fully characterized by a verity of techniques such as X-ray diffraction (XRD), EDAX analysis, scanning electron microscopy and FT-IR analysis. Also, the magnetic properties of these catalysts were investigated by AGFM. The catalysts could be reused several times without significant loss in their activities.

Preparation and characterization of magnetic chlorochromate hybrid nanomaterials with triphenylphosphine surface-modified iron oxide nanoparticles

In this paper, a new magnetic hybrid nanomaterial (Fe3O4@SiO2@PPh3@[CrO3Cl]) was reported for the first time. The magnetic Fe3O4 nanoparticles were prepared by hydrothermal process and coated with a silica shell. Then, the core–shell nanoparticles (Fe3O4@SiO2) were functionalized by 3-chloropropyl trimethoxysilane plus triphenylphosphine for forming the cationic part of support. Finally, anionic part of the Cr(VI) catalyst ([CrO3Cl]−) was immobilized on the magnetic support (Fe3O4@SiO2@PPh3). The structural characteristics of the product were determined using elemental analysis, X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and solid state UV–Vis. The particle size and morphology were identified by scanning electron microscope (SEM), transmission electron microscopy (TEM) and XRD. A vibrant sample was employed to determine the magnetic properties of the prepared samples.

Functionalized magnetic nanomaterials as solid-phase extraction adsorbents for organic pollutants in environmental analysis

Functionalized magnetic nanomaterials, composed of both organic and inorganic components, have recently been identified as promising solid-phase extraction adsorbents for various applications. Due to their superparamagnetic property, large specific surface area, as well as selective adsorption capacity, this unique class of nanomaterials exhibits an excellent performance in extracting and enriching numerous targeted analytes. This review mainly focuses on the recent advances in the synthesis and application of functionalized magnetic nanomaterials for the preconcentration of organic pollutants in environmental analysis. The development of three kinds of magnetic solid-phase adsorbents, including magnetic polymer nanomaterials, magnetic hybrid nanomaterials and magnetic mesoporous nanomaterials, are elaborated in this review.