Field-Induced Agglomerations of Polyethylene-Glycol-Functionalized Nanoclusters: Rheological Behaviour and Optical Microscopy.

This research aims to investigate the agglomeration processes of magnetoresponsive functionalized nanocluster suspensions in a magnetic field, as well as how these structures impact the behaviour of these suspensions in biomedical applications. The synthesis, shape, colloidal stability, and magnetic characteristics of PEG-functionalized nanoclusters are described in this paper. Experiments using TEM, XPS, dynamic light scattering (DLS), VSM, and optical microscopy were performed to study chain-like agglomeration production and its influence on colloidal behaviour in physiologically relevant suspensions. The applied magnetic field aligns the magnetic moments of the nanoclusters. It provides an attraction between neighbouring particles, resulting in the formation of chains, linear aggregates, or agglomerates of clusters aligned along the applied field direction. Optical microscopy has been used to observe the creation of these aligned linear formations. The design of chain-like structures can cause considerable changes in the characteristics of ferrofluids, ranging from rheological differences to colloidal stability changes.

Ofloxacin Removal from Aqueous Media by Means of Magnetoactive Electrospun Fibrous Adsorbents.

Functionalized electrospun polymer microfibrous membranes were fabricated by electrospinning and further surface-functionalized with magnetic iron oxide (FexOy) nanoparticles to yield magnetoactive nanocomposite fibrous adsorbents. The latter were characterized in respect to their morphology, mechanical properties and magnetic properties while they were further evaluated as substrates for removing Ofloxacin (OFL) from synthetic aqueous media and secondary urban wastewater (UWW) under varying physicochemical parameters, including the concentration of the pharmaceutical pollutant, the solution pH and the membranes' magnetic content. The magnetic-functionalized fibrous adsorbents demonstrated significantly enhanced adsorption efficacy in comparison to their non-functionalized fibrous analogues while their magnetic properties enabled their magnetic recovery and regeneration.

Magnetoresponsive Functionalized Nanocomposite Aggregation Kinetics and Chain Formation at the Targeted Site during Magnetic Targeting.

Drug therapy for vascular disease has been promoted to inhibit angiogenesis in atherosclerotic plaques and prevent restenosis following surgical intervention. This paper investigates the arterial depositions and distribution of PEG-functionalized magnetic nanocomposite clusters (PEG_MNCs) following local delivery in a stented artery model in a uniform magnetic field produced by a regionally positioned external permanent magnet; also, the PEG_MNCs aggregation or chain formation in and around the implanted stent. The central concept is to employ one external permanent magnet system, which produces enough magnetic field to magnetize and guide the magnetic nanoclusters in the stented artery region. At room temperature (25 °C), optical microscopy of the suspension model's aggregation process was carried out in the external magnetic field. According to the optical microscopy pictures, the PEG_MNC particles form long linear aggregates due to dipolar magnetic interactions when there is an external magnetic field. During magnetic particle targeting, 20 mL of the model suspensions are injected (at a constant flow rate of 39.6 mL/min for the period of 30 s) by the syringe pump in the mean flow (flow velocity is Um = 0.25 m/s, corresponding to the Reynolds number of Re = 232) into the stented artery model. The PEG_MNC clusters are attracted by the magnetic forces (generated by the permanent external magnet) and captured around the stent struts and the bottom artery wall before and inside the implanted stent. The colloidal interaction among the MNC clusters was investigated by calculating the electrostatic repulsion, van der Waals and magnetic dipole-dipole energies. The current work offers essential details about PEG_MNCs aggregation and chain structure development in the presence of an external magnetic field and the process underlying this structure formation.

Biosynthesis of Iron Oxide Nanoparticles: Physico-Chemical Characterization and Their In Vitro Cytotoxicity on Healthy and Tumorigenic Cell Lines.

Iron oxide nanoparticles were synthesized starting from two aqueous extracts based on Artemisia absinthium L. leaf and stems, employing a simplest, eco-friendliness and low toxicity method-green synthesis. The nanoparticles were characterized by powder X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), X-ray fluorescence analysis (XRF), thermal analysis (TG/DSC), and scanning electron microscopy (SEM). Lack of magnetic properties and the reddish-brown color of all the samples confirms the presence of hematite as majority phase. The FTIR bands located at 435 cm-1 and 590 cm-1, are assigned to Fe-O stretching vibration from hematite, confirming the formation of α-Fe2O3 nanoparticles (NPs). The in vitro screening of the samples revealed that the healthy cell line (HaCaT) presents a good viability (above 80%) after exposure to iron oxide NPs and lack of apoptotic features, while the tumorigenic cell lines manifested a higher sensitivity, especially the melanoma cells (A375) when exposed to concentration of 500 µg/mL iron oxide NPs for 72 h. Moreover, A375 cells elicited significant apoptotic markers under these parameters (concentration of 500 µg/mL iron oxide NPs for a contact time of 72 h).

Double-Layer Fatty Acid Nanoparticles as a Multiplatform for Diagnostics and Therapy.

Today, public health is one of the most important challenges in society. Cancer is the leading cause of death, so early diagnosis and localized treatments that minimize side effects are a priority. Magnetic nanoparticles have shown great potential as magnetic resonance imaging contrast agents, detection tags for in vitro biosensing, and mediators of heating in magnetic hyperthermia. One of the critical characteristics of nanoparticles to adjust to the biomedical needs of each application is their polymeric coating. Fatty acid coatings are known to contribute to colloidal stability and good surface crystalline quality. While monolayer coatings make the particles hydrophobic, a fatty acid double-layer renders them hydrophilic, and therefore suitable for use in body fluids. In addition, they provide the particles with functional chemical groups that allow their bioconjugation. This work analyzes three types of self-assembled bilayer fatty acid coatings of superparamagnetic iron oxide nanoparticles: oleic, lauric, and myristic acids. We characterize the particles magnetically and structurally and study their potential for resonance imaging, magnetic hyperthermia, and labeling for biosensing in lateral flow immunoassays. We found that the myristic acid sample reported a large r2 relaxivity, superior to existing iron-based commercial agents. For magnetic hyperthermia, a significant specific absorption rate value was obtained for the oleic sample. Finally, the lauric acid sample showed promising results for nanolabeling.

Biologic Impact of Green Synthetized Magnetic Iron Oxide Nanoparticles on Two Different Lung Tumorigenic Monolayers and a 3D Normal Bronchial Model-EpiAirwayTM Microtissue.

The present study reports the successful synthesis of biocompatible magnetic iron oxide nanoparticles (MNPs) by an ecofriendly single step method, using two ethanolic extracts based on leaves of Camellia sinensis L. and Ocimum basilicum L. The effect of both green raw materials as reducing and capping agents was taken into account for the development of MNPs, as well as the reaction synthesis temperature (25 °C and 80 °C). The biological effect of the MNPs obtained from Camellia sinensis L. ethanolic extract (Cs 25, Cs 80) was compared with that of the MNPs obtained from Ocimum basilicum L. ethanolic extract (Ob 25, Ob 80), by using two morphologically different lung cancer cell lines (A549 and NCI-H460); the results showed that the higher cell viability impairment was manifested by A549 cells after exposure to MNPs obtained from Ocimum basilicum L. ethanolic extract (Ob 25, Ob 80). Regarding the biosafety profile of the MNPs, it was shown that the EpiAirwayTM models did not elicit important viability decrease or significant histopathological changes after treatment with none of the MNPs (Cs 25, Cs 80 and Ob 25, Ob 80), at concentrations up to 500 µg/mL.

Green Synthesis, Characterization, and Antibacterial Properties of Silver Nanoparticles Obtained by Using Diverse Varieties of Cannabis sativa Leaf Extracts.

Cannabis sativa L. (hemp) is a plant used in the textile industry and green building material industry, as well as for the phytoremediation of soil, medical treatments, and supplementary food products. The synergistic effect of terpenes, flavonoids, and cannabinoids in hemp extracts may mediate the biogenic synthesis of metal nanoparticles. In this study, the chemical composition of aqueous leaf extracts of three varieties of Romanian hemp (two monoecious, and one dioecious) have been determined by Fourier-Transformed Infrared spectroscopy (FT-IR), high-performance liquid chromatography, and mass spectrometry (UHPLC-DAD-MS). Then, their capability to mediate the green synthesis of silver nanoparticles (AgNPs) and their pottential antibacterial applications were evaluated. The average antioxidant capacity of the extracts had 18.4 ± 3.9% inhibition determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH•) and 78.2 ± 4.1% determined by 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS™) assays. The total polyphenolic content of the extracts was 1642 ± 32 mg gallic acid equivalent (GAE) L-1. After this, these extracts were reacted with an aqueous solution of AgNO3 resulting in AgNPs, which were characterized by UV-VIS spectroscopy, FT-IR, scanning electron microscopy (SEM-EDX), and dynamic light scattering (DLS). The results demonstrated obtaining spherical, stable AgNPs with a diameter of less than 69 nm and an absorbance peak at 435 nm. The mixture of extracts and AgNPs showed a superior antioxidant capacity of 2.3 ± 0.4% inhibition determined by the DPPH• assay, 88.5 ± 0.9% inhibition as determined by the ABTS•+ assay, and a good antibacterial activity against several human pathogens: Escherichia coli, Klebsiella pneumoniae, Pseudomonas fluorescens, and Staphylococcus aureus.

Affordable Magnetic Hydrogels Prepared from Biocompatible and Biodegradable Sources.

Magnetic hydrogels composed of poly(vinyl alcohol) (PVA)/water-soluble tricarboxy cellulose (CO)/magnetic fluids (MFs) have been prepared by a freeze-thaw cycle technique. The system designed here combines the renewability and biocompatibility aspects of PVA and CO, as well as the magnetic properties of MFs, thereby offering special properties to the final product with potential applications in medicine. In the first step, the water-soluble CO is synthesized using a one-shot oxidation procedure and then the aqueous solutions of CO are mixed with PVA solutions and magnetic fluids in the absence of any additional cross-linking agent. The magnetic hydrogels were thoroughly investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), magnetometry (VSM), and thermogravimetric analysis. The morphological results show an excellent distribution of magnetic particles and CO inside the PVA matrix. The VSM results show that the magnetic hydrogels possess superparamagnetic properties.

Biocompatible Magnetic Colloidal Suspension Used as a Tool for Localized Hyperthermia in Human Breast Adenocarcinoma Cells: Physicochemical Analysis and Complex In Vitro Biological Profile.

Magnetic iron oxide nanoparticles are the most desired nanomaterials for biomedical applications due to their unique physiochemical properties. A facile single-step process for the preparation of a highly stable and biocompatible magnetic colloidal suspension based on citric-acid-coated magnetic iron oxide nanoparticles used as an effective heating source for the hyperthermia treatment of cancer cells is presented. The physicochemical analysis revealed that the magnetic colloidal suspension had a z-average diameter of 72.7 nm at 25 °C with a polydispersity index of 0.179 and a zeta potential of -45.0 mV, superparamagnetic features, and a heating capacity that was quantified by an intrinsic loss power analysis. Raman spectroscopy showed the presence of magnetite and confirmed the presence of citric acid on the surfaces of the magnetic iron oxide nanoparticles. The biological results showed that breast adenocarcinoma cells (MDA-MB-231) were significantly affected after exposure to the magnetic colloidal suspension with a concentration of 30 µg/mL 24 h post-treatment under hyperthermic conditions, while the nontumorigenic (MCF-10A) cells exhibited a viability above 90% under the same thermal setup. Thus, the biological data obtained in the present study clearly endorse the need for further investigations to establish the clinical biological potential of synthesized magnetic colloidal suspension for magnetically triggered hyperthermia.

From Single-Core Nanoparticles in Ferrofluids to Multi-Core Magnetic Nanocomposites: Assembly Strategies, Structure, and Magnetic Behavior.

Iron oxide nanoparticles are the basic components of the most promising magnetoresponsive nanoparticle systems for medical (diagnosis and therapy) and bio-related applications. Multi-core iron oxide nanoparticles with a high magnetic moment and well-defined size, shape, and functional coating are designed to fulfill the specific requirements of various biomedical applications, such as contrast agents, heating mediators, drug targeting, or magnetic bioseparation. This review article summarizes recent results in manufacturing multi-core magnetic nanoparticle (MNP) systems emphasizing the synthesis procedures, starting from ferrofluids (with single-core MNPs) as primary materials in various assembly methods to obtain multi-core magnetic particles. The synthesis and functionalization will be followed by the results of advanced physicochemical, structural, and magnetic characterization of multi-core particles, as well as single- and multi-core particle size distribution, morphology, internal structure, agglomerate formation processes, and constant and variable field magnetic properties. The review provides a comprehensive insight into the controlled synthesis and advanced structural and magnetic characterization of multi-core magnetic composites envisaged for nanomedicine and biotechnology.

Thermosensitive Betulinic Acid-Loaded Magnetoliposomes: A Promising Antitumor Potential for Highly Aggressive Human Breast Adenocarcinoma Cells Under Hyperthermic Conditions.

PURPOSE: Breast cancer presents one of the highest rates of prevalence around the world. Despite this, the current breast cancer therapy is characterized by significant side effects and high risk of recurrence. The present work aimed to develop a new therapeutic strategy that may improve the current breast cancer therapy by developing a heat-sensitive liposomal nano-platform suitable to incorporate both anti-tumor betulinic acid (BA) compound and magnetic iron nanoparticles (MIONPs), in order to address both remote drug release and hyperthermia-inducing features. To address the above-mentioned biomedical purposes, the nanocarrier must possess specific features such as specific phase transition temperature, diameter below 200 nm, superparamagnetic properties and heating capacity. Moreover, the anti-tumor activity of the developed nanocarrier should significantly affect human breast adenocarcinoma cells. METHODS: BA-loaded magnetoliposomes and corresponding controls (BA-free liposomes and liposomes containing no magnetic payload) were obtained through the thin-layer hydration method. The quality and stability of the multifunctional platforms were physico-chemically analysed by the means of RAMAN, scanning electron microscopy-EDAX, dynamic light scattering, zeta potential and DSC analysis. Besides this, the magnetic characterization of magnetoliposomes was performed in terms of superparamagnetic behaviour and heating capacity. The biological profile of the platforms and controls was screened through multiple in vitro methods, such as MTT, LDH and scratch assays, together with immunofluorescence staining. In addition, CAM assay was performed in order to assess a possible anti-angiogenic activity induced by the test samples. RESULTS: The physico-chemical analysis revealed that BA-loaded magnetoliposomes present suitable characteristics for the purpose of this study, showing biocompatible phase transition temperature, a diameter of 198 nm, superparamagnetic features and heating capacity. In vitro results showed that hyperthermia induces enhanced anti-tumor activity when breast adenocarcinoma MDA-MB-231 cells were exposed to BA-loaded magnetoliposomes, while a low cytotoxic rate was exhibited by the non-tumorigenic breast epithelial MCF 10A cells. Moreover, the in ovo angiogenesis assay endorsed the efficacy of this multifunctional platform as a good strategy for breast cancer therapy, under hyperthermal conditions. Regarding the possible mechanism of action of this multifunctional nano-platform, the immunocytochemistry of the MCF7 and MDA-MB-231 breast carcinoma cells revealed a microtubule assembly modulatory activity, under hyperthermal conditions. CONCLUSION: Collectively, these findings indicate that BA-loaded magnetoliposomes, under hyperthermal conditions, might serve as a promising strategy for breast adenocarcinoma treatment.

Engineered magnetoactive collagen hydrogels with tunable and predictable mechanical response.

In the present study, the synthesis of superparamagnetic collagen-based nanocomposite hydrogels with tunable swelling, mechanical and magnetic properties is reported. The fabrication strategy involved the preparation of pristine collagen type-I hydrogels followed by their immersion in highly stable aqueous solutions containing pre-formed double-layer oleic acid-coated hydrophilic magnetite nanoparticles (OA.OA.Fe3O4) at different concentrations, to interrogate nanoparticles' deposition within the 3D fibrous collagen matrix. Besides the investigation of the morphology, composition and magnetic properties of the produced materials, their mechanical properties were experimentally evaluated under confined compressive loading conditions while an exponential constitutive equation was employed to describe their mechanical response. Moreover, the deposition of the nanoparticles in the collagenous matrix was modeled mathematically with respect to the swelling of the gel and the effective stiffness of the matrix. The model recapitulated nanoparticle diffusion and deposition as well as hydrogel swelling, in terms of nanoparticles' size and concentration of OA.OA.Fe3O4 aqueous solution.

Dental Adhesive Interfaces Reinforced with Magnetic Nanoparticles: Evaluation and Modeling with Micro-CT versus Optical Microscopy.

Dental adhesives are used in a wide range of applications, including to place direct composite restorations in frontal or posterior teeth. One of the most frequent causes for the failure of composite resin restorations is microleakages. The first aim of this work is to introduce a new type of self-etched dental adhesive doped with magnetic nanoparticles (MPs) synthetized in the laboratory. The scope is to produce adhesives with a minimized width/thickness to decrease the risk of microleakages. The second aim is to assess the width/thickness of the adhesive layer in all the characteristic areas of the teeth using both the less precise but most common optical microscopy and the more accurate and volumetric micro-Computed Tomography (CT) investigations. Twenty extracted teeth have been divided into four groups: Group 1 includes 'blank' samples with adhesives that are not doped with MPs; Group 2 includes samples with adhesives doped with MPs; Groups 3 and 4 include samples with adhesives doped with MPs that are subjected to an active magnetic field for 5 and 10 min, respectively. Microscopy investigations followed by micro-CT and EDAX are performed on the adhesive. While a rather good agreement is obtained between the microscopy and micro-CT results, the capability of the latter to offer a full volumetric reconstruction of the layer is exploited to analyze the adhesion of the four considered dental materials. Thus, from micro-CT results the graphs of the surface areas as functions of the adhesive layer width are modeled mathematically, as well as the volume of sealants, for each of the four groups. To our knowledge, it is the first time that such a methodology is used. Characteristic parameters are extracted and the ascertainment of the optimal parameter that should be utilized for such assessments is discussed. The study demonstrates the adhesion improvement produced for Groups 3 and 4, where MPs are used. It also concludes that the magnetic field should be applied to the adhesive material for the longest possible exposure time (with a trade-off with the clinical duration of the treatment).

Influence of Experimental Parameters of a Continuous Flow Process on the Properties of Very Small Iron Oxide Nanoparticles (VSION) Designed for T1-Weighted Magnetic Resonance Imaging (MRI).

This study reports the development of a continuous flow process enabling the synthesis of very small iron oxide nanoparticles (VSION) intended for T1-weighted magnetic resonance imaging (MRI). The influence of parameters, such as the concentration/nature of surfactants, temperature, pressure and the residence time on the thermal decomposition of iron(III) acetylacetonate in organic media was evaluated. As observed by transmission electron microscopy (TEM), the diameter of the resulting nanoparticle remains constant when modifying the residence time. However, significant differences were observed in the magnetic and relaxometric studies. This continuous flow experimental setup allowed the production of VSION with high flow rates (up to 2 mL·min-1), demonstrating the efficacy of such process compared to conventional batch procedure for the scale-up production of VSION.

Magnetic immunochromatographic test for histamine detection in wine.

Histamine, a biogenic amine, is abundant in fermented foods and beverages, notably wine. A high intake of this monoamine may produce adverse reactions in humans, which may be severe in individuals with a reduced capacity to catabolise extrinsic histamine. Thus, control of histamine concentration during wine production and before distribution is advisable. Simple, rapid, point-of-use bioanalytical platforms are needed because traditional methods for the detection and quantification of histamine are expensive and time-consuming. This work applies the lateral flow immunoassay technique to histamine detection. Superparamagnetic particle labels, and an inductive sensor designed to read the test line in the immunoassay, enable magnetic quantification of the molecule. The system is calibrated with histamine standards in the interval of interest for wine production. A commercial optical strip reader is used for comparison measurements. The lateral flow system has a limit of detection of 1.2 and 1.5 mg/L for the inductive and optical readers, respectively. The capability of the inductive system for histamine quantification is demonstrated for wine samples at different processing points (at the end of alcoholic fermentation, at the end of malolactic fermentation, in freshly bottled wine, and in reserve wine). The results are validated by ultra-high-performance liquid chromatography. Graphical abstract.

Superparamagnetic Composites Based on Ionic Resin Beads/CaCO3 /Magnetite.

The preparation of superparamagnetic composites obtained by CaCO3 mineralization from supersaturate aqueous solutions is presented. The preparation was conducted in the presence of oleic acid stabilized magnetite nanoparticles as a water-based magnetic fluid and insoluble templates as gel-like cross-linked polymeric beads. The presence of the magnetic particles in the composites provides a facile way for external manipulation using a permanent magnet, thus allowing the separation and extraction of magnetically modified materials. Two ion exchangers based on divinylbenzene/ethyl acrylate/acrylonitrile cross-linked copolymer-a cation ion exchanger (CIE) and an amphoteric ion exchanger (AIE)-were used, as well as different addition orders of magnetite and CaCO3 crystals growth precursors. The morphology of the composites was investigated by SEM, the polymorphs content by X-ray diffraction, and the thermal stability by thermogravimetric analysis. Polymer, CaCO3 , and magnetite in the composite particles were shown to be present by energy dispersive X-ray (EDX), XPS, and TEM. The sorption capacity for CuII ions was tested, as compared to samples prepared without magnetite.

Magnetic iron oxide nanoparticles: Recent trends in design and synthesis of magnetoresponsive nanosystems.

Recent developments in nanotechnology and application of magnetic nanoparticles, in particular in magnetic iron oxide nanosystems, offer exciting possibilities for nanomedicine. Facile and precise synthesis procedures, high magnetic response, tunable morphologies and multiple bio-functionalities of single- and multi-core magnetic particles designed for nanomedicine applications are thoroughly appraised. This review focuses on the structural and magnetic characterization of the cores, the synthesis of single- and multicore iron oxide NPs, especially the design of the latter, as well as their protection, stabilization and functionalization by desired coating in order to protect against the corrosion of core, to prevent non-specific protein adsorption and particle aggregation in biological media, and to provide binding sites for targeting and therapeutic agents.

Magnetic microgels, a promising candidate for enhanced magnetic adsorbent particles in bioseparation: synthesis, physicochemical characterization, and separation performance.

For specific applications in the field of high gradient magnetic separation of biomaterials, magnetic nanoparticle clusters of controlled size and high magnetic moment in an external magnetic field are of particular interest. We report the synthesis and characterization of magnetic microgels designed for magnetic separation purposes, as well as the separation efficiency of the obtained microgel particles. High magnetization magnetic microgels with superparamagnetic behaviour were obtained in a two-step synthesis procedure by a miniemulsion technique using highly stable ferrofluid on a volatile nonpolar carrier. Spherical clusters of closely packed hydrophobic oleic acid-coated magnetite nanoparticles were coated with cross linked polymer shells of polyacrylic acid, poly-N-isopropylacrylamide, and poly-3-acrylamidopropyl trimethylammonium chloride. The morphology, size distribution, chemical surface composition, and magnetic properties of the magnetic microgels were determined using transmission electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. Magnetically induced phase condensation in aqueous suspensions of magnetic microgels was investigated by optical microscopy and static light scattering. The condensed phase consists of elongated oblong structures oriented in the direction of the external magnetic field and may grow up to several microns in thickness and tens or even hundreds of microns in length. The dependence of phase condensation magnetic supersaturation on the magnetic field intensity was determined. The experiments using high gradient magnetic separation show high values of separation efficiency (99.9-99.97%) for the magnetic microgels.