Superparamagnetic Nanoparticles Research Articles

A Short Appraisal of Magnetic Nanoparticles for Breast Cancer: In vitro and In vivo Research.

The increasing incidence of breast cancer and the associated morbidity due to higher metastasis created the urge to develop a nanocarrier that can be used as a potent therapeutic carrier with targeting efficacy. The use of superparamagnetic nanoparticles in breast cancer research and treatment has gained considerable attention in recent years. Magnetic nanoparticles (MNPs) can be used to construct nanocarriers since they possess superior properties such as superparamagnetism, easy surface functionalization to attach ligands, and non-immunogenic. MNPs are superior carriers that are used to target cancer cells without harming the normal cells in the body, which leads to therapeutic efficacy in the body. Along with their established anticancer potential and enhanced drug concentration at endosomal pH, the superparamagnetic property of MNPs was further exploited for their applications in reticuloendothelial uptake, drug delivery, medical imaging, and theranostics applications in breast cancer. Moreover, the clinical translational of MNPs, along with future prospects and key challenges in vivo, have been duly presented in the final review. The scientists preferred the ongoing research in MNPs due to their high biocompatibility and ease of targeting at molecular and cellular levels. The review highlighted the in vitro and in vivo research and patent supported data for potential use of MNPs for the treatment of breast cancer.

Sensitive, accurate, and high spatiotemporal resolution photonic thermometry

Real-time temperature monitoring with high accuracy and spatiotemporal resolution is critical for many biological applications, including disease diagnosis, drug delivery, and biomedical research. However, traditional methods for measuring temperature in biological systems present difficulties for a variety of reasons, such as slow response time, limited spatial resolution, low amplitude, and susceptibility to electromagnetic interference. Most importantly, in many cases, the thermal mass of temperature probes limits the accuracy and speed of measurement significantly. Here, we show that photonic microring resonators (MRRs) can be used for sensitive, precise, and high spatiotemporal resolution measurement of temperature in the biological milieu. The high refractive index of Si MRR and negligible thermal mass enable sensitive, ultrafast, and accurate temperature transients. By using a double resonator circuit, we demonstrate that MRR sensors can measure temperature with a 1 mm spatial resolution. We then show that MRR yields more accurate results than fiber optic probes for measuring temperature transients. Finally, we demonstrate the localized temperature measurement capability of MRRs in mouse brain tissue heated by superparamagnetic nanoparticles in an alternating magnetic field. This compact, lab-on-chip photonic temperature sensing platform holds great promise for continuous monitoring of temperature in critical biological and biomedical applications.

Controlling the Magnetic Responsiveness of Cellulose Nanofiber Particles Embedded with Iron Oxide Nanoparticles.

2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofiber (TOCN) particles, an innovative biobased material derived from wood biomass, have garnered significant interest, particularly in the biomedical field, for their distinctive properties as biocompatible particle adsorbents. However, their microscopic size complicates their separation in liquid media, thereby impeding their application in various domains. In this study, superparamagnetic magnetite nanoparticles (NPs), specifically iron oxide Fe3O4 NPs with an average size of 15 nm, were used to enhance the collection efficiency of TOCN-Fe3O4 composite particles synthesized through spray drying. These composite particles exhibited a remarkable ζ-potential (approximately -50 mV), indicating their high stability in water, as well as impressive magnetization properties (up to 47 emu/g), and rapid magnetic responsiveness within 60 s in water (3 wt % Fe3O4 to TOCN, 1 T magnet). Furthermore, the influence of Fe3O4 NP concentrations on the measurement of the speed of magnetic separation was quantitatively discussed. Additionally, the binding affinity of the synthesized particles for proteins was assessed on a streptavidin-biotin binding system, offering crucial insights into their binding capabilities with specific proteins and underscoring their significant potential as functionalized biomedical materials.

Antiepileptic drug-loaded and multifunctional iron oxide@silica@gelatin nanoparticles for acid-triggered drug delivery

The current study developed an innovative design for the production of smart multifunctional core-double shell superparamagnetic nanoparticles (NPs) with a focus on the development of a pH-responsive drug delivery system tailored for the controlled release of Phenytoin, accompanied by real-time monitoring capabilities. In this regard, the ultra-small superparamagnetic iron oxide@silica NPs (IO@Si MNPs) were synthesized and then coated with a layer of gelatin containing Phenytoin as an antiepileptic drug. The precise saturation magnetization value for the resultant NPs was established at 26 emu g-1. The polymeric shell showed a pH-sensitive behavior with the capacity to regulate the release of encapsulated drug under neutral pH conditions, simultaneously, releasing more amount of the drug in a simulated tumorous-epileptic acidic condition. The NPs showed an average size of 41.04 nm, which is in the desired size range facilitating entry through the blood–brain barrier. The values of drug loading and encapsulation efficiency were determined to be 2.01 and 10.05%, respectively. Moreover, kinetic studies revealed a Fickian diffusion process of Phenytoin release, and diffusional exponent values based on the Korsmeyer-Peppas equation were achieved at pH 7.4 and pH 6.3. The synthesized NPs did not show any cytotoxicity. Consequently, this new design offers a faster release of PHT at the site of a tumor in response to a change in pH, which is essential to prevent epileptic attacks.

Ultrasensitive and Rapid Circulating Tumor DNA Liquid Biopsy Using Surface-Confined Gene Amplification on Dispersible Magnetic Nano-Electrodes.

Circulating tumor DNA (ctDNA) detection has been acknowledged as a promising liquid biopsy approach for cancer diagnosis, with various ctDNA assays used for early detection and treatment monitoring. Dispersible magnetic nanoparticle-based electrochemical detection methods have been proposed as promising candidates for ctDNA detection based on the detection performance and features of the platform material. This study proposes a nanoparticle surface-localized genetic amplification approach by integrating Fe3O4-Au core-shell nanoparticles into polymerase chain reactions (PCR). These highly dispersible and magnetically responsive superparamagnetic nanoparticles act as nano-electrodes that amplify and accumulate target ctDNA in situ on the nanoparticle surface upon PCR amplification. These nanoparticles are subsequently captured and subjected to repetitive electrochemical measurements to induce reconfiguration-mediated signal amplification for ultrasensitive (∼3 aM) and rapid (∼7 min) metastatic breast cancer ctDNA detection in vitro. The detection platform can also detect metastatic biomarkers from in vivo samples, highlighting the potential for clinical applications and further expansion to rapid and ultrasensitive multiplex detection of various cancers.

The Influence of Blood and Serum Microenvironment on Spin-Labeled Magnetic Nanoparticles

The investigation and clarification of the properties of surface-functionalized superparamagnetic nanoparticles in a biological environment are key challenges prior to their medical applications. In the present work, electron paramagnetic resonance spectroscopy (EPR) combined with the spin labeling technique was utilized to better understand the behavior of nitroxides attached to magnetite nanoparticles dispersed in body fluid. EPR spectra of spin-labeled, silane-coated Fe3O4 nanoparticles in human serum and whole blood were recorded and analyzed for both room- and low-temperature values. In all cases, the obtained EPR signal consisted of a broad line from magnetite cores and a characteristic signal from the attached 4-Amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO). Even for liquid samples, the anisotropic components of magnetic tensors did not fully average out, which was reflected in the differences in the intensity of three narrow hyperfine lines from nitroxide. At 230 K the irregular slow-motion signal from the attached radical was also simulated using the EasySpin toolbox, which allowed to determine the parameters related to magnetic tensors and the dynamics of the spin label. The study showed that the anisotropy of the motion of the spin label 4-amino-TEMPO reflects its interactions with the surrounding medium and the manner of the attachment of the nitroxide to the surface of nanoparticles.

Abstract PO5-20-01: SENTINOT2- Use of superparamagnetic iron oxide tracer to avoid unnecessary sentinel lymph node biopsies

Abstract Background/Purpose: The use of superparamagnetic nanoparticles of iron oxide tracers (Magtrace) and electromagnetometers (SentiMag) for the detection of sentinel lymph nodes (SLN) during breast cancer surgery has been demonstrated to be noninferior to traditional radioisotope (RI) and blue dye detection, with additional safety benefits. Previous work has shown that transcutaneous detection of SLN with Magtrace/Sentimag is possible for over 30 days. Because of the safety, efficacy, and long detection window of Magtrace, we aim to investigate the use of Magtrace to prevent unnecessary SLN biopsies (SLNB) in breast cancer surgery. SLNB are commonly performed during breast conserving surgeries (BCS) or mastectomy for patients with a preoperative diagnosis of ductal carcinoma in-situ (DCIS). Because metastasis is not expected in patients diagnosed with DCIS, SLNB may be unnecessary and potentially harmful. However, in 15-25% of cases, unexpected invasive carcinoma is found during the post-surgical histopathological analysis of the resected breast tissue. For these cases, if SLNB are forgone during the initial surgery, SLNB during a second (delayed) procedure is the usual standard of care to evaluate SLN for metastasis. However, potential changes to lymphatic drainage following the initial resection may affect tracer localization to SLN. Consequently, we aim to compare SLN detection rates during delayed SLNB with Magtrace administered prior to initial BCS or mastectomy and subsequent RI tracer administered prior to delayed SLNB. Methods: SENTINOT2 is an ongoing international trial with BCM as the sole US site. For eligible patients with a preoperative diagnosis of DCIS, Magtrace will be administered prior to BCS or mastectomy. If invasive carcinoma is found from the post-surgical histopathological analysis, patients will receive delayed SLNB within 4 weeks of their initial surgery. Prior to delayed SLNB, patients will be randomized into two groups differing in the order of modality used for SLN detection (Magtrace or RI). Subjects with the following conditions will be excluded from the study: hypersensitivity to Magtrace, iron overload disease, pregnancy, and lactation. The total expected accrual for this study is 538 subjects globally and 50 subjects at BCM. Results: Currently, 19 patients have been enrolled in SENTINOT2. The subject population is 11% Asian, 26% Black/African American, and 47% Caucasian with non-Hispanic ethnicity. 5% of subjects identified as Hispanic Caucasian and 11% of subjects declined to report their race or ethnicity. 79% of patients had mastectomies, while 21% had BCS. After post-surgical histopathological analysis, 21% (4/19) patients were determined to have invasive carcinoma and received delayed SLNB. 50% (2/4) of these patients were randomized to have Magtrace as their first SLN detection modality (Mag-RI) while the other 50% (2/4) had RI as their first SLN detection modality (RI-Mag). Table 1 shows comparable SLN detection rates between Magtrace and RI for patients who received delayed SLNB. Only 1/4 patients showed SLN metastasis. For this patient, the positive SLN was successfully detected by both modalities. Conclusion: Magtrace has shown potential in delayed SLN detection and the use of Magtrace has prevented 79% (15/19) of enrolled patients from receiving unnecessary SLNB. Table 1. Number of Lymph Nodes (LN) Detected by Magtrace/Radioisotope, Biopsied and Positive for Metastasis Citation Format: Mary Bajomo, Ivan Marin, Jessica Montalvan, Margarita Riojas-Barrett, Logan Healy, Elizabeth Bonefas, Stacey Carter, Alastair Thompson. SENTINOT2- Use of superparamagnetic iron oxide tracer to avoid unnecessary sentinel lymph node biopsies [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PO5-20-01.

Nano-structuring of all-d-metal NiCoMnTi-based Heusler compounds

The emerging all-d-metal Ni(Co)MnTi-based Heusler compounds attract extensive attention because it can potentially be employed for solid-state refrigeration. However, in comparison to the abundant physical functionalities in bulk conditions, the hidden properties related to the NiCoMnTi-based Heusler nanoparticles (NPs) have not yet been investigated experimentally. Here, we present NiCoMnTi Heusler NPs that have been manufactured by spark ablation under Ar gas flow, and the related magnetic and microstructural properties have been studied. Compared with the bulk sample, it is found that the magneto-structurally coupled transition in the bulk sample has collapsed into a magnetic transition for the NPs sample. Superparamagnetic NPs with widely distributed dislocations have directly been observed by high-resolution transmission electron microscopy. For the NPs, the magnetocrystalline anisotropy constant is 3.54 × 104 J/m3, while the saturation magnetization after post-treatment has been estimated to be around 26 Am2 kg−1. Our current research reveals that Ni-Co-Mn-Ti-based quaternary NPs could show interesting properties for future nano-application, and the produced NPs will further expand the functionalities of this material family.

GMI-based biosensor for the detection and quantification of doxorubicin anticancer drugs labeled to Fe3O4 superparamagnetic nanoparticles

We present the results of research on a Co-based giant magnetoimpedance (GMI) biosensor for Fe3O4-labelled doxorubicin (DOX) anticancer drugs. Co62Fe5Ni4Si15B14 ribbons were used as biosensing material for test solutions containing different concentrations of DOX. The plain ribbon, ribbon+Fe3O4 and ribbon+DOX2 samples exhibited low coercivity (Hc), high saturation magnetization (Ms) and low anisotropy (Hk). The GMI ratio (ΔZ/Z) increased from 33% to 38% with the increase of doxorubicin content in the ribbon. It was found that the ΔZ/Z ratio first increased rapidly up to a frequency of ∼2 MHz, and then decreased slowly as the frequency increased. While the magnetic field dependent ΔZ/Z has a single peak at 1 MHz, it has a double peak at 5 MHz. It was found that the peak height of ΔZ/Z in the ribbons with test solution of 20 ng/ml and 50 ng/ml increased by ∼3% and ∼6%, respectively, compared to the ribbon without test solution. Then the ΔZ/Z ratio decreased very rapidly with the increase of the applied external magnetic fields. The frequency-dependent GMI sensitivity (η) increased with increasing frequency and reached a maximum value at a critical frequency (∼1.6 MHz), after which it decreased. The detection sensitivity of the GMI biosensor (ξ) increased rapidly with increasing doxorubicin concentration up to ∼80 ng/ml and then remained almost unchanged. The results show that doxorubicin (DOX+Fe3O4), used as an anticancer drug, can be effectively detected even at low concentrations using the GMI based sensors fabricated in this study.

Superparamagnetic iron oxide nanoparticles functionalized by biocompatible ligands with enhanced high specific absorption rate for magnetic hyperthermia

This study introduces a novel green nanocomposite system of iron oxide coated with secondary metabolites (Fe3O4@SM) and compares it with commonly used materials for hyperthermia cancer treatment. Fe3O4@SM magnetic nanoparticles were synthesized through a simple co-precipitation process using metal precursors, followed by heating in pressure reactor to obtain superparamagnetic nanoparticles (Hc = 36.5–54.1 Oe at 300 K). These nanoparticles were subsequently coated with plant-based phytochemicals. XRD analysis confirmed the presence of magnetite iron oxide nanoparticles. SEM images further confirmed the spherical shape of the synthesized nanoparticles, exhibiting a face-centered cubic (FCC) iron oxide structure with sizes ranging from 12±7–85±15 nm. Characterization through dynamic light scattering (DLS) and zeta potential (ζ) analysis demonstrated colloidal stability, with a polydispersity index (PDI) ranging from 0.226 to 0.436 and zeta potential values ranging from −29.761–1.85 mV. The surface of the nanoparticles was analyzed using GC-MS, which identified bioactive functional groups including ester (42.79 %), terpene (20.69 %), hydrocarbons (17.4 %), and carboxylic (12.37 %) compounds. Compared to Fe3O4 and Fe3O4@GO, Fe3O4@SM exhibited a higher rate of temperature increase within the therapeutic range, reaching Tmax = 45°C with a heating rate (dT/dt) of 0.273 °C/s and specific absorption rate (SAR) of 230.6 W/g at 304 kHz and 400 Oe. In vitro assays utilizing a triple negative breast cancer microenvironment confirmed the non-toxicity of these materials through a DNS assay. The developed nanoparticles offer dual mechanisms of action, combining thermal and chemo effects, making them promising candidates for hyperthermia cancer treatment.

MRI-traceable multifunctional magnetic mesoporous silica nanoparticles (MMSN) capped with graphene quantum dots (GQD) as a theragnostic system in colorectal cancer treatment

In the study, a multifunctional nanosystem composed of magnetic core-mesoporous silica nanoparticles (MMSN) capped with graphene quantum dots (GQD) was proposed as a theragnostic platform against colorectal cancer cells. The theragnostic carrier was well characterized and had an average particle size of 140 nm, with a specific surface of 475.82 m2 g−1. The superparamagnetic nanoparticles showed a hysteresis loop, with a maximum magnetization of 14.93 emu.g−1 and a remanence of 2.64 emu.g−1. The functionalization of MMSN was confirmed using the ninhydrin test. Regorafenib (REGO), an anticancer drug, was used with a loading capacity of 77.5 μg mg−1. The drug release profiles from the carrier and the sensitivity of the interaction between MMSN and GQD to pH were examined, revealing that more drug release was observed in acidic pH. The cytotoxicity of the MMSN-REGO/GQD system was evaluated on colorectal cancer cell line SW-480 using MTT assay, and the results indicated that no cytotoxicity was observed for the MMSN/GQD carrier. Furthermore, the IC50 of REGO was significantly reduced from 85 μg ml−1 to 6 μg ml−1 in the loaded form. The response of MMSN/GQD nanoparticles to the external magnetic field exhibited the capability of the theragnostic system as an MRI contrast agent. Generally, biocompatible, theragnostic, pH-responsive, multifunctional MMSN/GQD can be considered promising candidates for treatment, MRI imaging, and hyperthermia in colorectal cancer treatment.

Construction of GPC3-modified Lipopolymer SiRNA Delivery System.

Gene therapy has been widely concerned because of its unique therapeutic mechanism. However, due to the lack of safe and effective carries, it has not been widely used in clinical practice. Glypican 3 (GPC3) is a highly specific proteoglycan for hepatocellular carcinoma and is a potential diagnostic and therapeutic target for hepatocellular carcinoma. Herein, to monitor the effect of gene therapy and enhance the transfection efficiency of gene carriers, GPC3-modified lipid polyethyleneimine-modified superparamagnetic nanoparticle (GLPS), a type of visualized carrier for siRNA (small-interfering RNA) targeting the liver, was prepared. We performed in vitro gene silencing, cytotoxicity, and agarose gel electrophoresis to identify the optimal GLPS formulation. In vitro MRI and Prussian blue staining verified the liver-targeting function of GLPS. We also analyzed the biocompatibility of GLPS by co-culturing with rabbit red blood cells. Morphological changes were evaluated using HE staining. The GLPS optimal formulation consisted of LPS and siRNA at a mass ratio of 25:1 and LPS and DSPE-PEG-GPC3 at a molar ratio of 2:3. GLPS exhibited evident liver-targeting function. In vitro, we did not observe morphological changes in red blood cells or hemolysis after co-culture. In vivo, routine blood analysis revealed no abnormalities after GLPS injection. Moreover, the tissue morphology of the kidney, spleen, and liver was normal without injury or inflammation. GLPS could potentially serve as an effective carrier for liver-targeted MRI monitoring and siRNA delivery.

Nature-inspired fungal fusarinine C-powered dual-mode fluorometric/colorimetric biosensing of fecal Helicobacter pylori with high-reliability

Conventional diagnostic approaches for Helicobacter pylori lack sufficient sensitivity, accuracy, and flexibility, especially for low-density H. pylori infection. To overcome this limitation, we developed a highly reliable fluorometric/colorimetric dual-mode biosensing technique to detect minute quantities of H. pylori in human stool samples. Inspired by natural porphyrins, we discovered that the water-soluble fungal siderophore fusarinine C (FsC) emitted intense green fluorescence owing to intramolecular through-bond and intermolecular through-space conjugation, and turned reddish upon coordination with Fe3+. With FsC as an intrinsic fluorometric/colorimetric probe, a dual-mode biosensor was developed. It included an enrichment module of truncated H. pylori-specific-aptamer-modified superparamagnetic nanoparticles to capture H. pylori from samples, and a transduction module of alginate conjugated with FsC[Fe3+] and an optimized amount of FsC without Fe3+ to amplify the captured H. pylori to fluorescent and/or color signals. Remarkably, significantly increased sensitivity was achieved for this biosensor, with an actual limit of detection of 5 CFU/mL and single-cell-level detection resolution, as validated using laser-tweezer-sorted single H. pylori cells. Moreover, highly reliable dual-mode detection of low-density H. pylori (between 5 and 10 CFU/mL) was demonstrated. Using the colorimetric mode, a smartphone-biosensor platform for sensitive point-of-care testing of fecal H. pylori within 20 min was demonstrated, outperforming the clinical fecal antigen test strips; meanwhile, the fluorometric mode of the biosensor, owing to its greater sensitivity, can verify the colorimetric detection of minute H. pylori. This study first showcased a FsC-powered dual-mode biosensor for ultra-sensitive and accurate point-of-care detection of H. pylori with high reliability.

Induction heating of magnetic nanoparticles: role of thermo-physical properties of the coating moieties

Superparamagnetic nanoparticles (MNPs) are utilized for magnetic fluid hyperthermia (MFH)-based cancer therapeutics, where the MNPs are surface functionalized to impart desired stability and biological properties. In this study, the MFH properties of palmitic (PA) and stearic (SA) acid-coated superparamagnetic Fe3O4 MNPs, with similar sizes (∼ 10 ± 0.8 nm, and ∼ 11 ± 0.7 nm, respectively), and saturation magnetizations (∼ 40.8 emu/g, and ∼ 41 emu/g, respectively), are systematically probed to understand the role of the thermo-physical properties of the coating moieties on the MFH efficiency. PA and SA-coated MNPs are prepared using a one-step microwave-assisted co-precipitation technique, and the presence of the surface coatings is confirmed using Fourier transform infrared spectroscopy and thermogravimetric analyses. Magneto-calorimetric studies show a high induction heating efficiency, surpassing the threshold of MFH for a biologically relevant field-frequency range. The maximum heating efficiencies are found to be ∼ 164.5 ± 5.4 W/gFe and ∼ 223.9 ± 6.4 W/gFe for the PA and SA-coated MNPs, respectively. This indicates ∼ 36.1 % higher specific absorption rate (SAR) for the SA-coated MNPs under similar experimental conditions, even though the magneto-structural properties are identical for the PA and SA-coated MNPs. Further, finite element modelling is utilized to investigate the thermal transport from the magnetic core to the surrounding medium, where the thermo-physical properties of the coating moieties are considered. Finite element simulations indicate ∼ 32.6 % higher SAR for the SA-coated MNPs, which is consistent with the experimental findings. The higher SAR for the SA-coated MNPs is attributed to the ∼ 1.7 times higher thermal diffusivity of SA. The proposed model is experimentally validated using a third system consisting of lauric acid-coated Fe3O4 MNPs with comparable magneto-structural properties. Further, significant temperature rise in a tissue-equivalent agar medium and good bio-compatibility, as indicated by the in vitro cyto-toxicity studies, make the prepared MNPs potential candidates for MFH applications. The obtained results provide deeper insight into the role of the thermo-physical properties of the coating moieties on the induction heating efficiency of superparamagnetic MNPs.

Integrated micro/nano drug delivery system based on magnetically responsive phase-change droplets for ultrasound theranostics.

Phase-change droplets (PCDs) are intelligent responsive micro and nanomaterials developed based on micro/nano bubbles. Subject to external energy inputs such as temperature and ultrasound, the core substance, perfluorocarbon (PFC), undergoes a phase transition from liquid to gas. This transformation precipitates alterations in the PCDs' structure, size, ultrasound imaging capabilities, drug delivery efficiency, and other pertinent characteristics. This gives them the ability to exhibit "intelligent responses". This study utilized lipids as the membrane shell material and perfluorohexane (PFH) as the core to prepare lipid phase-change droplets. Superparamagnetic nanoparticles (PEG-functionalized Fe3O4 nanoparticles) and the anti-tumor drug curcumin (Cur) were loaded into the membrane shell, forming magnetic drug-loaded phase-change droplets (Fe-Cur-NDs). These nanoscale phase-change droplets exhibited excellent magnetic resonance/ultrasound imaging capabilities and thermal/ultrasound-mediated drug release. The Fe-Cur-NDs showed excellent anti-tumor efficacy for the MCF-7 cells under low-intensity focused ultrasound (LIFU) guidance in vitro. Therefore, Fe-Cur-NDs represent a promising smart responsive theranostic integrated micro/nano drug delivery system.

Tuning Surface, Phase, and Magnetization of Superparamagnetic Magnetite by Ionic Liquids: Single-Step Microwave-Assisted Synthesis.

Achieving colloidal and chemical stability in ferrofluids by surface modification requires multiple steps, including purification, ex situ modification steps, and operation at high temperatures. In this study, a single-step microwave-assisted methodology is developed for iron oxide nanoparticle (IONP) synthesis utilizing a series of imidazolium-based ionic liquids (ILs) with chloride, bis(trifluoromethylsulfonyl)imide, and pyrrolide anions as the reaction media, thus eliminating the use of volatile organics while enabling rapid synthesis at 80 °C as well as in situ surface functionalization. The characterized surface functionality, hydrodynamic particle size, magnetization, and colloidal stability of the IONPs demonstrate a strong dependence on the IL structure, ion coordination strength, reactivity, and hydrophilicity. The IONPs present primarily a magnetite (Fe3O4) phase with superparamagnetism with the highest saturation magnetization at 81 and 73 emu/g at 10 and 300 K, respectively. Depending on the IL coating, magnetization and exchange anisotropy decrease by 20 and 2-3 emu/g (at 35 wt % IL), respectively, but still represent the highest magnetization achieved for coated IONPs by a coprecipitation method. Further, the surface-functionalized superparamagnetic magnetite nanoparticles show good dispersibility and colloidal stability in water and dimethyl sulfoxide at 0.1 mg/mL concentration over the examined 3 month period. This study reports on the intermolecular and chemical interactions between the particle surface and the ILs under synthetic conditions as they relate to the magnetic and thermal properties of the resulting IONPs that are well suited for a variety of applications, including separation and catalysis.

Increased endocytosis rate and enhanced lysosomal pathway of silica-coated superparamagnetic nanoparticles into M-HeLa cells compared with cultured primary motor neurons.

The unique properties of superparamagnetic iron oxide nanoparticles (SPIONs) enable their use as magnetic biosensors, targeted drug delivery, magnetothermia, magnetic resonance imaging, etc. Today, SPIONs are the only type of metal oxide nanoparticles approved for biomedical application. In this work, we analyzed the cellular response to the previously reported luminescent silica coated SPIONs of the two cell types: M-HeLa cells and primary motor neuron culture. Both internalization pathways and intracellular fate of SPIONs have been compared for these cell lines using fluorescence and transmission electron microscopy. We also applied a pharmacological approach to analyze the endocytosis pathways of SPIONs into the investigated cell lines. The penetration of SPIONs into M-HeLa cells is already noticeable within 30s of incubation through both caveolin-dependent endocytosis and micropinocytosis. However, incubation for a longer time (1h at least) is required for the internalization of SPIONs into motor neuron culture cells provided by dynamin-dependent endocytosis and macropinocytosis. The intracellular colocalization assay reveals that the lysosomal internalization pathway of SPIONs is also dependent on the cell type. The lysosomal pathway is much more pronounced for M-HeLa cells compared with motor neurons. The emphasized differences in cellular responses of the two cell lines open up new opportunities in the application of SPIONs in the diagnostics and therapy of cancer cells.

A comprehensive approach to characterize navigation instruments for magnetic guidance in biological systems

Achieving non-invasive spatiotemporal control over cellular functions, tissue organization, and behavior is a desirable aim for advanced therapies. Magnetic fields, due to their negligible interaction with biological matter, are promising for in vitro and in vivo applications, even in deep tissues. Particularly, the remote manipulation of paramagnetic (including superparamagnetic and ferromagnetic, all with a positive magnetic susceptibility) entities through magnetic instruments has emerged as a promising approach across various biological contexts. However, variations in the properties and descriptions of these instruments have led to a lack of reproducibility and comparability among studies. This article addresses the need for standardizing the characterization of magnetic instruments, with a specific focus on their ability to control the movement of paramagnetic objects within organisms. While it is well known that the force exerted on magnetic particles depends on the spatial variation (gradient) of the magnetic field, the magnitude of the field is often overlooked in the literature. Therefore, we comprehensively analyze and discuss both actors and propose a novel descriptor, termed ‘effective gradient’, which combines both dependencies. To illustrate the importance of both factors, we characterize different magnet systems and relate them to experiments involving superparamagnetic nanoparticles. This standardization effort aims to enhance the reproducibility and comparability of studies utilizing magnetic instruments for biological applications.

Removal of Metal Ions from Wastewater Using Co‐integrated Superparamagnetic Nanoparticles

AbstractThe column performance of silica‐coated, amino‐functionalized, superparamagnetic nanoparticles co‐integrated with Cynodon dactylon and Murraya koenigii plant extracts for the removal of CuII ions was evaluated. The co‐integrated nanoparticles were used as sorbent materials in fixed‐bed column studies, and the effects of inlet concentration, adsorbent bed depth, and flow rate were analyzed. Breakthrough time was calculated for various CuII inlet concentrations, depths of the adsorbent bed, and volumetric flow rates. Models such as Thomas, Yoon‐Nelson, and the bed depth model were evaluated to determine the experimental fit. The maximum breakthrough time for CuII ions of 1200 min was attained for a CuII inlet concentration of 100 mg L–1, sorbent bed depth of 3 cm, and volumetric flow rate of 1 mL min–1.

Exploring induced microstructural changes in magnetically modified crude oils through nonlinear rheology and magnetometry

Adsorptive phenomena involving dispersed iron oxide superparamagnetic nanoparticles and asphaltenes in crude oil have been profiled as promising technological alternatives, particularly since these interactions can induce significant structural changes within the oil matrices, effectively inhibiting the formation of complex long-range viscoelastic structures. Furthermore, the effect of adsorbed asphaltenes on magnetic dipolar interactions among particles has been proven, showing the formation of multiple asphaltene layers that stimulate a steric repulsive barrier. Despite the discussed hindering phenomena, this research demonstrated the effectiveness of the sequence of physical processes framework to provide intra-cycle structure-rheological interpretations in large amplitude oscillatory shear of a ferrofluid-modified heavy oil, upon the application of an external magnetic field. The analysis proved that disordered nanoparticle/asphaltene aggregates are highly extended and naturally formed in the absence of magnetic forces. In contrast, in the presence of a perpendicular field applied by a controlled rate magneto-rheometer, the formation of interacting structural aggregates of several hundred nanometers was observed, analogous to magnetorheological fluids. These results were validated by adjusting a phenomenological model that effectively represented the intricate processes involved in the formation and reorientation of aggregates, based on the experimental data acquired from zero-field-cooled and field-cooled magnetization curves. This revealed a distinct blocking temperature distribution at around 274 K, which was linked to Brownian relaxation phenomena exhibited by nanoparticle aggregates. In this regard, this research provided a precise extended description of the effect of magnetic fields on the microstructural organization of complex fluids using nonlinear rheology and magnetometry.