Magnetic Responsive Hydrogels Research Articles

Multifunctional Self-Assembled Block Copolymer/Iron Oxide Nanocomposite Hydrogels Formed from Wormlike Micelles.

This article reports the preparation of multifunctional magnetic nanocomposite hydrogels formed from wormlike micelles. Specifically, iron oxide nanoparticles were incorporated into a temperature responsive block copolymer, poly(glycerol monomethacrylate)-b-poly(2-hydroxypropyl methacrylate) (PGMA-b-PHPMA), and graphene oxide (GO) dispersion at a low temperature (∼2 °C) through high-speed mixing and returning the mixture to room temperature, resulting in the formation of nanocomposite gels. The optimal concentrations of iron oxide and GO enhanced the gel strength of the nanocomposite gels, which exhibited a strong magnetic response when a magnetic field was applied. These materials retained the thermoresponsiveness of the PGMA-PHPMA wormlike micelles allowing for a solid-to-liquid transition to occur when the temperature was reduced. The mechanical and rheological properties and performance of the nanocomposite gels were demonstrated to be adjustable, making them suitable for a wide range of potential applications. These nanocomposite worm gels were demonstrated to be relatively adhesive and to act as strain and temperature sensors, with the measured electrical resistance of the nanocomposite gels changing with applied strain and temperature sweeps. The nanocomposite gels were found to recover efficiently after the application of high shear with approximately 100% healing efficiency within seconds. Additionally, these nanocomposite worm gels were injectable, and the addition of GO and iron oxide nanomaterials seemed to have no significant adverse impact on the biocompatibility of the copolymer gels, making them suitable not only for 3D printing in nanocomposite engineering but also for potential utilization in various biomedical applications as an injectable magnetic responsive hydrogel.

Synthesis and characterization of hydrogel-based magnetite nanocomposite adsorbents for the potential removal of Acid Orange 10 dye and Cr(VI) ions from aqueous solution

Magnetic responsive hydrogels (CMX-cl-P4VP/M-NPs) were successfully synthesized through in situ co-precipitation procedure and investigated using various techniques. The surface morphology analysis revealed that the M-NPs were uniformly distributed within the hydrogel matrix and had average sizes ranging from 4.98 to 15.02 nm. The graft copolymer containing nanoparticles exhibited a sensitive magnetic response, and their recovery could be facilitated by applying a magnetic field. The purpose of this research is to study the ability of the prepared magnetic hydrogel to remove AO-10 dye and hexavalent chromium ions (Cr(VI)) from the aqueous solution under various factors, namely contact time, pH, amount of adsorbent, coexisting ions and AO-10 and Cr(VI) concentrations. The outcomes of the batch adsorption demonstrated that the adsorbent hydrogel incorporated with a low percentage (10 %) of M-NPs had a strong affinity for the removal of AO-10 dye and Cr(VI) ions at an optimum pH = 3, and the removal percentage reached 99.3 and 97.4 % for 500 mg L−1 and 300 mg L−1 of AO-10 dye and Cr(VI) ions within 90, 50 min, respectively. The data were well-fitted by pseudo-first-order kinetics. The maximum adsorption capacities of AO-10 dye and Cr(VI) ions onto adsorbent were 2448 and 574.7 mg g−1 at 298 K, calculated from the Langmuir model.

Remotely Temporal Scheduled Macrophage Phenotypic Transition Enables Optimized Immunomodulatory Bone Regeneration.

Precise timing of macrophage polarization plays a pivotal role in immunomodulation of tissue regeneration, yet most studies mainly focus on M2 macrophages for their anti-inflammatory and regenerative effects while the essential proinflammatory role of the M1 phenotype on the early inflammation stage is largely underestimated. Herein, a superparamagnetic hydrogel capable of timely controlling macrophage polarization is constructed by grafting superparamagnetic nanoparticles on collagen nanofibers. The magnetic responsive hydrogel network enables efficient polarization of encapsulated macrophage to the M2 phenotype through the podosome/Rho/ROCK mechanical pathway in response to static magnetic field (MF) as needed. Taking advantage of remote accessibility of magnetic field together with the superparamagnetic hydrogels, a temporal engineered M1 to M2 transition course preserving the essential role of M1 at the early stage of tissue healing, as well as enhancing the prohealing effect of M2 at the middle/late stages is established via delayed MF switch. Such precise timing of macrophage polarization matching the regenerative process of injured tissue eventually leads to optimized immunomodulatory bone healing in vivo. Overall, this study offers a remotely time-scheduled approach for macrophage polarization, which enables precise manipulation of inflammation progression during tissue healing.

Experimental study on the temporary plugging performance of magnetic responsive hydrogel in hydraulic fracturing of hydrocarbon reservoirs

In this study, we designed a magnetic responsive hydrogel, also known as magnetorheological gel (MRG), based on a carbonyl iron particle@polyacrylamide (CIP@PAM) composite and a water-soluble PAM matrix to use as a temporary plugging agent (TPA) in the hydraulic fracturing of unconventional hydrocarbon reservoirs. The CIP@PAM composite was synthesized and characterized by Fourier transform infrared spectrometry (FT-IR), scanning electron microscopy (SEM), laser particle size analysis (LPSA) and vibrating sample magnetometry (VSM). The results show that a thin and uniform PAM layer was successfully coated on the surface of the CIPs, which plays a key role in enhancing the antioxidant capacity of the CIPs. Meanwhile, the CIP@PAM composite possesses a high saturation magnetization (148.8 emu/g). MRG as a TPA has a high gel strength and magnetorheological effect under a magnetic field intensity of 1 T, providing a breakthrough pressure up to 38.13 MPa at room temperature. Compared with the conventional temporary plugging agent, MRG as the temporary plugging agent possesses high magnetic responsiveness to easily control, good degradability and recyclability, providing great potential application in hydraulic fracturing.

Tannin-bridged magnetic responsive multifunctional hydrogel for enhanced wound healing by mechanical stimulation-induced early vascularization.

Wound healing is a complex process. Wound-repair materials require multiple functionalities, such as anti-inflammatory, antibacterial, angiogenesis, pro-proliferation, and remodeling. To achieve rapid tissue regeneration, magnetic field-assisted therapy has become a promising means. In this study, a homogeneous magnetic responsive nanocomposite hydrogel with enhanced mechanical properties was obtained through a tannin (TA)-assisted bridge between magneto-deformable cobalt ferrite nanoparticles (CFO NPs) and polyvinyl alcohol (PVA) matrix. In the presence of an external static magnetic field (SMF), the TA bridge could efficiently transmit magnetically actuated deformation to the PVA, which originated from the CFO NPs, generating a larger topographic change on the surface. The change of topography provided a mechanical cue to increase cell adhesion and proliferation. Moreover, due to the synergistic effects of TA modification and CFO NPs, the obtained magnetic responsive hydrogel exhibited considerable antibacterial activity. Furthermore, the results of in vivo study confirmed the anti-inflammatory properties of the TA-CFO/PVA hydrogel. More importantly, the TA-CFO/PVA hydrogel accelerated wound healing under a SMF, which contributed to the early vascularization induced by mechanical stimuli generated from the TA-CFO/PVA nanocomposite hydrogel. As a proof-of-concept, we provided an optimizing strategy for magneto-controlled skin tissue regeneration, which may have important guiding significance for the clinical application of magnetic field-assisted therapy.

Dexamethasone-Loaded Injectable In-situ Thermal Crosslinking Magnetic Responsive Hydrogel for the Physiochemical Stimulation of Acupoint to Suppress Pain in Sciatica Rats

The physicochemical stimulation of acupoints is a widespread treatment strategy for different diseases, such as sciatica. Its efficacy is mainly based on the temporal and spatial modulation of the physicochemical properties of the acupoints. The existing therapies based on the stimulation of acupoints have certain disadvantages. Therefore, in this study, injectable dexamethasone (DXM)- and magnetic Fe3O4 nanoparticles-loaded chitosan/β-glycerophosphate (CS/GP) thermal crosslinking hydrogels were prepared, thereby improving the performance of embedding materials. The sciatica rat models were established to compare the therapeutic effects of hydrogels and catgut. The DXM or Fe3O4-loaded CS/GP hydrogels were compared in terms of their gelation kinetics, release kinetics, magnetic responsiveness in-vitro, and biocompatibility as well as their analgesic effects on the chronic constriction injury of the sciatic nerve (CCI) rats in-vivo. The CS/GP/Fe3O4/DXM hydrogel showed comparable gelation kinetics and good magnetic responsiveness in-vitro. This hydrogel could relieve sciatica by reducing the expression levels of inflammatory factors in serum, inhibiting the p38MAPK (p38, mitogen-activated protein kinase) phosphorylation, and decreasing the expression level of the P2X4 receptor (P2X4R) in the spinal dorsal horn. In conclusion, the DXM or Fe3O4-loaded CS/GP hydrogels can be considered as a treatment option for the physiochemical stimulation therapy of acupoints to improve sciatica.

3D Printing Unique Nanoclay-Incorporated Double-Network Hydrogels for Construction of Complex Tissue Engineering Scaffolds.

The development of new biomaterial inks with good structural formability and mechanical strength is critical to the fabrication of 3D tissue engineering scaffolds. For extrusion-based 3D printing, the resulting 3D constructs are essentially a sequential assembly of 1D filaments into 3D constructs. Inspired by this process, this paper reports the recent study on 3D printing of nanoclay-incorporated double-network (NIDN) hydrogels for the fabrication of 1D filaments and 3D constructs without extra assistance of support bath. The frequently used "house-of-cards" architectures formed by nanoclay are disintegrated in the NIDN hydrogels. However, nanoclay can act as physical crosslinkers to interact with polymer chains of methacrylated hyaluronic acid (HAMA) and alginate (Alg), which endows the hydrogel precursors with good structural formability. Various straight filaments, spring-like loops, and complex 3D constructs with high shape-fidelity and good mechanical strength are fabricated successfully. In addition, the NIDN hydrogel system can easily be transformed into a new type of magnetic responsive hydrogel used for 3D printing. The NIDN hydrogels also supported the growth of bone marrow mesenchymal stem cells and displayed potential calvarial defect repair functions.

Stimuli-Responsive Hydrogels for Cancer Treatment: The Role of pH, Light, Ionic Strength and Magnetic Field.

Simple SummaryCancer remains as the world second leading cause of death. The severe side effects associated to high doses of chemotherapy and the development of drug resistance are major drawbacks for a successful cancer treatment. Therefore, new formulations that promote localized therapy at tumor sites are needed to improve the therapeutic outcomes and patient welfare. The use of hydrogels is a very promising alternative, since they can be composed by smart materials able to respond to external factors, changing their properties accordingly and promoting a localized drug delivery. As a result, a more specific, efficient, and less toxic local cancer treatment can be accomplished. In this context, the most important characteristics of hydrogels recent studies regarding the application of pH-, light-, ionic strength-, and magnetic-responsive hydrogels in cancer treatment are here presented.Cancer remains as the second leading cause of death, worldwide. Despite the enormous important advances observed in the last decades, advanced stages of the disease remain incurable. The severe side effects associated to systemic high doses of chemotherapy and the development of drug resistance impairs a safe and efficiency anticancer therapy. Therefore, new formulations are continuously under research and development to improve anticancer drugs therapeutic index through localized delivery at tumor sites. Among a wide range of possibilities, hydrogels have recently gained special attention due to their potential to allow in situ sustained and controlled anticancer drug release. In particular, stimuli-responsive hydrogels which are able to change their physical state from liquid to gel accordingly to external factors such as temperature, pH, light, ionic strength, and magnetic field, among others. Some of these formulations presented promising results for the localized control and treatment of cancer. The present work aims to discuss the main properties and application of stimuli-responsive hydrogels in cancer treatment and summarize the most important advances observed in the last decades focusing on the use of pH-, light-, ionic strength-, and magnetic-responsive hydrogels.

Collagen–iron oxide nanoparticle based ferrogel: large reversible magnetostrains with potential for bioactuation

Smart materials such as stimuli responsive polymeric hydrogels offer unique possibilities for tissue engineering and regenerative medicine. As, however, most synthetic polymer systems and their degradation products lack complete biocompatibility and biodegradability, this study aims to synthesize a highly magnetic responsive hydrogel, based on the abundant natural biopolymer collagen. As the main component of vertebratal extracellular matrix, it reveals excellent biocompatibility. In combination with incorporated magnetic iron oxide nanoparticles, a novel smart nano-bio-ferrogel can be designed. While retaining its basic biophysical properties and interaction with living cells, this collagen-nanoparticle hydrogel can be compressed to 38% of its original size and recovers to 95% in suitable magnetic fields. Besides the phenomenology of this scenario, the underlying physical scenarios are also discussed within the framework of network models. The observed reversible peak strains as large as 150% open up possibilities for the fields of biomedical actuation, soft robotics and beyond.

A Novel pH, Thermo, and Magnetic Responsive Hydrogel Nanocomposite Containing Nanogel for Anticancer Drug Delivery

Hydrogels, nanogels, and nanocomposites have attracted much attention as drug delivery systems during the past decades. In this work, a novel drug delivery system was synthesized by incorporation of nanogel into multi responsive hydrogel nanocomposite. At first, nanogel was prepared by copolymerization of N‑isopropylacrylamide (NIPAM) and (2-dimethylamino)ethyl methacrylate (DMA). Then it was embedded it into pH, thermo, and magnetic responsive hydrogel nanocomposite including graft copolymerization of poly(2-dimethylamino)ethyl methacrylate (PDMA) onto salep (PDMA-g-salep) and Fe3O4 nanoparticles (NPs). The synthesized samples were characterized by Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and atomic force micrographs (AFM). The sensitivity of the synthesized sample to temperature, pH, and magnetic field was studied using the swelling experiments. The drug release ability of the sample was also investigated at different pH, temperatures, and magnetic field. Finally, different kinetic models were used to discuss about the mechanism of drug release from the prepared sample. Our results represented the high efficiency of this kind of hydrogel nanocomposite for applications in cancer therapy.

Injectable and Magnetic Responsive Hydrogels with Bioinspired Ordered Structures.

Injectable hydrogels are particularly interesting for applications in minimally invasive tissue engineering and regenerative medicine strategies. However, the typical isotropic microstructure of these biomaterials limits their potential for the regeneration of ordered tissues. In the present work, we decorated rod-shaped cellulose nanocrystals with magnetic nanoparticles and coated these with polydopamine and polyethylene glycol polymer brushes to obtain chemical and colloidal stable nanoparticles. Then, these nanoparticles (0.1-0.5 wt %) were incorporated within gelatin hydrogels, creating injectable and magnetically responsive materials with potential for various biomedical applications. Nanoparticle alignment within the hydrogel matrix was achieved under exposure to uniform low magnetic fields (108 mT), resulting in biomaterials with directional microstructure and anisotropic mechanical properties. The biological performance of these nanocomposite hydrogels was studied using adipose tissue derived human stem cells. Cells encapsulated in the nanocomposite hydrogels showed high rates of viability demonstrating that the nanocomposite biomaterials are not cytotoxic. Remarkably, the microstructural patterns stemming from nanoparticle alignment induced the directional growth of seeded and, to a lower extent, encapsulated cells in the hydrogels, suggesting that this injectable system might find application in both cellular and acellular strategies targeting the regeneration of anisotropic tissues.

Magnetic hydrogels for levodopa release and cell stimulation triggered by external magnetic field.

Magnetic responsive hydrogels composed of alginate (Alg) and xanthan gum (XG), crosslinked with Ca2+ ions, were modified by in situ magnetic nanoparticles (MNP) formation. In comparison to magnetic Alg hydrogels, magnetic Alg-XG hydrogels presented superior mechanical and swelling properties, due to the high charge density and molecular weight of XG. The loading efficiency of levodopa (LD), an important antiparkinson drug, in the Alg-XG/MNP hydrogels was the highest (64%), followed by Alg/MNP (56%), Alg-XG (53%) and Alg (28%). A static external magnetic field (EMF) of 0.4 T stimulated the release of LD from Alg-XG/MNP hydrogels achieving 64 ± 6% of the initial loading after 30 h. The viability, proliferation and expression of dopaminergic markers of human neuroblastoma SH-SY5Y cell on the LD loaded magnetic hydrogels were successful, particularly under EMF, which stimulated the release of LD. Overall, the results of this study provided the rational design of magnetic hydrogels for the delivery of drugs, which combined with external magnetic stimulus, might improve cell proliferation and specific differentiation.

Multifunctional magnetic-responsive hydrogels to engineer tendon-to-bone interface

Photocrosslinkable magnetic hydrogels are attracting great interest for tissue engineering strategies due to their versatility and multifunctionality, including their remote controllability ex vivo, thus enabling engineering complex tissue interfaces. This study reports the development of a photocrosslinkable magnetic responsive hydrogel made of methacrylated chondroitin sulfate (MA-CS) enriched with platelet lysate (PL) with tunable features, envisioning their application in tendon-to-bone interface. MA-CS coated iron-based magnetic nanoparticles were incorporated to provide magnetic responsiveness to the hydrogel. Osteogenically differentiated adipose-derived stem cells and/or tendon-derived cells were encapsulated within the hydrogel, proliferating and expressing bone- and tendon-related markers. External magnetic field (EMF) application modulated the swelling, degradation and release of PL-derived growth factors, and impacted both cell morphology and the expression and synthesis of tendon- and bone-like matrix with a more evident effect in co-cultures. Overall, the developed magnetic responsive hydrogel represents a potential cell carrier system for interfacial tissue engineering with EMF-controlled properties.

Enhancement of membrane stability on magnetic responsive hydrogel microcapsules for potential on-demand cell separation

It is of high interest to obtain hydrogel membranes with optimum mechanical stability, which is a prerequisite to the successful fabrication of hydrogel microcapsules for cell separation. In this work, we developed magnetic responsive alginate/chitosan (MAC) hydrogel microcapsules by co-encapsulation of microbial cells and superparamagnetic iron oxide nanoparticles (SPIONs) reacting under a high voltage electrostatic field. We investigated the influence of the molecular weight of chitosan, microcapsules size, and membrane crosslinking time on the swelling behavior of microcapsules as an indicator of stability of the membranes. The results demonstrated that the suitable membrane stability conditions were obtained by a crosslinking of the microspheres with a chitosan presenting a molecular weight of 70kDa for 15–30min resulting in a membrane thickness of approximately 30mm. Considering the need of maintaining the cells inside the microcapsules, fermentation at 37°C and at neutral pH was favorable. Moreover, the MAC microcapsules sizing between 300 and 380μm were suitable for immobilizing Bacillus licheniformis in a 286h multiple fed-bath operation with no leakage of the SPIONs and cells. Overall, the results of this study provided strategies for the rational design of magnetic microcapsules exhibiting suitable mechanical stable membranes.

Bioinspired pH and magnetic responsive catechol-functionalized chitosan hydrogels with tunable elastic properties.

We have developed pH- and magnetic-responsive hydrogels that are stabilized by both covalent bonding and catechol/Fe(3+) ligands. The viscoelastic properties of the gels are regulated by the complexation valence and can be used to tune drug release profiles. The stable incorporation of magnetic nanoparticles further expands control over the mechanical response and drug release, in addition to providing magnetic stimuli-responsivity to the gels.

Temperature responsive hydrogel magnetic nanocomposites for hyperthermia and metal extraction applications

The present work deals with the development of temperature and magnetic responsive hydrogel networks based on poly (N-isopropylacrylamide)/acrylamido propane sulfonic acid. The hydrogel matrices are synthesized by polymerizing N-isopropylacrylamide (NIPAM) monomer in the presence of acrylamido propane sulphonicacid (AMPS) using a cross-linker (N,N-methylenebisacrylamide, MBA) and redox initiating system [ammonium persulphate (APS)/tetramethylethylenediamine (TMEDA)]. The magnetic nanoparticles are generated throughout the hydrogel networks using in situ method by incorporating iron ions and subsequent treatment with ammonia. A series of hydrogel-magnetic nanocomposites (HGMNC) are developed by varying AMPS composition. The synthesized hydrogel magnetic nanocomposites (HGMNC) are characterized by using Fourier Transform Infrared (FTIR) Spectroscopy, X-ray diffraction (XRD), Thermal Analyses and Electron Microscopy analysis (Scanning and Transmission Electron Microscope). The metal extraction capacities of the prepared hydrogel (HG) and hydrogel magnetic nanocomposites (HGMNC) were studied at different temperatures. The results suggest that HGMNCs have higher extraction capacity compared to HG and HG loaded iron ions. This data also reveals that the extraction of metals by hydrogel magnetic nanocomposites (HGMNCs) is higher at higher temperatures than room temperature. The prepared HGMNCs are also subjected to hyperthermia (cancer therapy) studies.

Adsorption of copper(II), lead(II), and cadmium(II) ions from aqueous solution by using hydrogel with magnetic properties

Hydrogels based on acrylamide and 2-acrylamido-2-methyl-1-propanesulfonic acid were synthesized via a gamma irradiation technique and used for preparation of magnetic responsive hydrogels. The hydrogels obtained were investigated by means of X-ray diffraction, Fourier-transform infrared (FT-IR), magnetic properties, thermogravimetric analysis, and energy-dispersive X-ray analysis. The extent of adsorption was investigated as a function of pH of medium, initial metal ion concentration, and contact time. The adsorption process was well described by pseudo-second-order kinetics, and the best interpretation of the equilibrium data was given by the Freundlich isotherm. The results from sequential adsorption–desorption cycles showed that the hydrogel exhibited good desorption and reusability. It was revealed that such hydrogel networks with magnetic properties can be effectively utilized for removal of pollutants and adsorbed heavy-metal ions. The maximum adsorption capacities were 321, 436, and 470 mg g−1 for Pb(II), Cd(II), and Cu(II) ions, respectively.

Synthesis and temperature response analysis of magnetic‐hydrogel nanocomposites

Magnetically responsive hydrogel networks based on composites of magnetic nanoparticles and temperature responsive hydrogels were developed. These systems show great promise as active components of microscale and nanoscale devices and are expected to have a wide applicability in various biomedical applications. Specifically, nanocomposite hydrogel systems based on the temperature sensitive N-isopropylacrylamide hydrogels crosslinked with ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and poly(ethylene glycol) 400 dimethacrylate (PEG400DMA) were synthesized and characterized. The composite systems were synthesized by UV free-radical polymerization. Iron oxide magnetic nanoparticles were incorporated into the hydrogel systems by polymerizing mixtures of the nanoparticles and monomer solutions. The swelling response of these composite systems to different crosslinking molecular weights, temperature, and the effect of the presence of the magnetic nanoparticles were examined.