Superparamagnetic Hyperbranched Polyglycerol‐Grafted Fe3O4 Nanoparticles as a Novel Magnetic Resonance Imaging Contrast Agent: An In Vitro Assessment

Hyperbranched polyglycerol‐grafted, magnetic Fe₃O₄ nanoparticles (HPG‐grafted MNPs) are successfully synthesized by surface‐initiated ring‐opening multibranching polymerization of glycidol. Reactive hydroxyl groups are immobilized on the surface of 6–9 nm Fe₃O₄ nanoparticles via effective ligand exchange of oleic acid with 6‐hydroxy caproic acid. The surface hydroxyl groups are treated with aluminum isopropoxide to form the nanosized macroinitiators. The successful grafting of HPG onto the nanoparticles is confirmed by infrared and X‐ray photoelectron spectroscopy. The HPG‐grafted MNPs have a uniform hydrodynamic diameter of (24.0 ± 3.0) nm, and are very stable in aqueous solution, as well as in cell culture medium, for months. These nanoparticles have great potential for application as a new magnetic resonance imaging contrast agent, as evidenced by their lack of cytotoxicity towards mammalian cells, low uptake by macrophages, excellent stability in aqueous medium and magnetic fields, and favorable magnetic properties. Furthermore, the possibility of functionalizing the hydroxyl end‐groups of the HPG with cell‐specific targeting ligands will expand the range of applications of these MNPs.     

Fe3O4磁性纳米颗粒的制备及性能表征

以Fe_2(SO_4)_3·6H_2O,FeSO_4·4H_2O和NH_3·H_2O为原料,采用化学共沉淀法制备Fe_3O_4磁性纳米颗粒,并通过XRD、FTIR、TEM和VSM手段,研究了反应温度对其结构、形貌和磁性能的影响。结果表明:制备的Fe_3O_4磁性纳米颗粒表面包裹了一层有机物质,呈球形,大小均匀,平均粒径在13nm左右,分散性好,饱和磁化强度Ms最大值可达53.38A·m~2·kg~(–1),且反应温度70℃时其磁性能最佳。     

Electrospinning Multilayered Scaffolds Loaded with Melatonin and Fe3O4 Magnetic Nanoparticles for Peripheral Nerve Regeneration

Peripheral nerve injury is a common clinical problem bringing heavy burden to patients, due to its high incidence and unsatisfactory treatment. Nerve guidance conduit (NGC) is a promising scaffold for peripheral nerve repair, and bioactive agents are applied for great functional recovery. Melatonin (MLT) and Fe₃O₄ magnetic nanoparticles (Fe₃O₄‐MNPs) are proven to inhibit oxidative stress, inflammation, and induce nerve regeneration. Herein, a multilayered composite NGC loaded with MLT and Fe₃O₄‐MNPs is designed for sequential and sustainable drug release, creating an appropriate microenvironment for nerve regeneration. The composite scaffold shows sufficient mechanical strength and biocompatibility in vitro, and evidently promotes morphological, functional, and electrophysiological recovery of regenerated sciatic nerves in vivo. This work proves that the multilayered conduits show great prospect in the long‐term nerve defects treatment due to easy manufacture and desired efficacy.     

Ultrasmall Water‐Soluble and Biocompatible Magnetic Iron Oxide Nanoparticles as Positive and Negative Dual Contrast Agents

Monodispersed water‐soluble and biocompatible ultrasmall magnetic iron oxide nanoparticles (UMIONs, D = 3.3 ± 0.5 nm) generated from a high‐temperature coprecipitation route are successfully used as efficient positive and negative dual contrast agents of magnetic resonance imaging (MRI). Their longitudinal relaxivity at 4.7 T (r₁ = 8.3 mM^?1 s^?1) is larger than that of clinically used T₁‐positive agent Gd‐DTPA (r₁ = 4.8 mM^?1 s^?1), and three times that of commercial contrast agent SHU‐555C (r₁ = 2.9 mM^?1 s^?1). The transversal relaxivity (r₂ = 35.1 mM^?1 s^?1) is six times that of Gd‐DTPA (r₂ = 5.3 mM^?1 s^?1), half of SHU‐555C (r₂ = 69 mM^?1 s^?1). The in vivo results show that the liver signal from T₁‐weighted MRI is positively enhanced 26%, and then negatively decreased 20% after injection of the iron oxide nanoparticles, which is stronger than those obtained from Gd‐DTPA (<10%) using the same dosage. The kidney signal is positively enhanced up to 35%, similar to that obtained from Gd‐DTPA. Under T₂‐weighted conditions, the liver signal is negatively enhanced ?70%, which is significantly higher than that from Gd‐DTPA (?6%). These results demonstrate the great potential of the UMIONs in dual contrast agents, especially as an alternative to Gd‐based positive contrast agents, which have risks of inducing side effects in patients.     

Furin‐Controlled Fe3O4 Nanoparticle Aggregation and 19F Signal “Turn‐On” for Precise MR Imaging of Tumors

For cancer diagnosis, ¹H magnetic resonance imaging (MRI) is advantageous in sensitivity but lacks selectivity. Endogenous ¹⁹F MRI signal in humans is barely detectable and thus ¹⁹F MRI has very high selectivity. A combination of ¹H and ¹⁹F MRI is ideal for precise tumor imaging but a protease‐controlled strategy of simultaneous T₂ ¹H MRI enhancement and ¹⁹F MRI “Turn‐On” has not been reported. Here, used is a click condensation reaction to rationally project a dual‐functional fluorine probe 4‐(trifluoromethyl)benzoic acid (TFMB)‐Arg‐Val‐Arg‐Arg‐Cys(StBu)‐Lys‐CBT ( 1 ), which is further utilized to functionalize Fe₃O₄ nanoparticle ( IONP ) to achieve IONP@1 . As such, the IONP aggregation can be activated by furin addition, thereby enhancing the T₂ ¹H MRI signal and switching the ¹⁹F NMR/MRI signal “On”. Using this strategy, IONP@1 is successfully applied to detect the activity of the furin enzyme with “Turn‐On” ¹⁹F NMR/MRI and T₂ ¹H MRI signals are enhanced. Moreover, IONP@1 is also applied for precise dual‐mode (¹H and ¹⁹F) MR imaging of tumors in zebrafish under 14.1 T. The current approach, therefore, provides a feasible and robust means to reconcile the dilemma between selectivity and sensitivity of conventional MRI probes. More importantly, it is envisioned that, by substituting the TFMB moiety in 1 with a perfluorinated compound, this “smart” method could be of potential use for precise ¹H MR and ¹⁹F MR imaging of tumor in mouse or in bigger rodents in near future.     

Adsorbing and Activating N2 on Heterogeneous Au–Fe3O4 Nanoparticles for N2 Fixation

Electrochemical nitrogen reduction reaction (NRR) is a promising approach to convert earth‐adundant N₂ into highly value‐added NH₃. Herein, it is demonstrated that the heterogeneous Au–Fe₃O₄ nanoparticles (NPs) can be adopted as highly efficient catalysts for NRR. Due to the synergistic effect of the strong N₂ fixation ability of Fe₃O₄ and the charge transfer capability of Au, the Au–Fe₃O₄ NPs show excellent performance with a high yield (NH₃: 21.42 µg mg_cat^?1 h^?1) and a favorable faradaic efficiency (NH₃: 10.54%) at ?0.2 V (vs reversible hydrogen electrode), both of which are much better than those of the Au NPs, Fe₃O₄ NPs, as well as core@shell Au@Fe₃O₄ NPs. It also exhibits good stability with largely maintained performance after six cycles. The N₂ temperature‐programmed desorption, surface valance band spectra, and X‐ray photoelectron spectroscopy collectively confirm that Au–Fe₃O₄ NPs have a strong adsorption capacity for the reaction species and suitable surface structure for electronic transfer. The theoretical calculations reveal that Fe provides the active site to fix N₂ into *N₂H while introducing Au optimizes the adsorption of NRR intermediates, making the NRR pathway on Au–Fe₃O₄ along an energetic‐favorable process and enhancing the NRR.     

Time‐Dependent T1–T2 Switchable Magnetic Resonance Imaging Realized by c(RGDyK) Modified Ultrasmall Fe3O4 Nanoprobes

To achieve the accurate diagnosis of tumor with the magnetic resonance imaging (MRI), nanomaterials‐based contrast agents are developed rapidly. Here, a tumor targeting nanoprobe of c(RGDyK) modified ultrasmall sized iron oxide is reported with high saturation magnetization and high T₁‐weighted imaging capability, attributed to a large number of paramagnetic centers on the surface of nanoprobes and rapid water proton exchange rate (inner sphere model), as well as strong superparamagnetism (outer sphere model). These nanoprobes could actively target and gradually accumulate at the tumor site with a time‐dependent T₁–T₂ contrast enhancement imaging effect. In in vivo MRI experiments, the nanoprobes exhibit the best T₁ contrast enhancement at 30 min after intravenous administration, followed by gradually vanishing and generating T₂ contrast enhancement with increasing time at tumor site. This is likely due to time‐dependent nanoprobes aggregation in tumor, in good agreement with in vitro experiment where aggregated nanoprobes display larger r₂/r₁ value (19.1) than that of the dispersed nanoprobes (2.8). This dynamic property is completely different from other T₁‐T₂ dual‐modal nanoprobes which commonly exhibit the T₁‐ and T₂‐weighted enhancement effect at the same time. To sum up, these c(RGDyK) modified ultrasmall Fe₃O₄ nanoprobes have significant potential to improve the diagnostic accuracy and sensitivity in MRI.     

Fe3O4‐Decorated Co9S8 Nanoparticles In Situ Grown on Reduced Graphene Oxide: A New and Efficient Electrocatalyst for Oxygen Evolution Reaction

Cobalt sulfide materials have attracted enormous interest as low‐cost alternatives to noble‐metal catalysts capable of catalyzing both oxygen reduction and oxygen evolution reactions. Although recent advances have been achieved in the development of various cobalt sulfide composites to expedite their oxygen reduction reaction properties, to improve their poor oxygen evolution reaction (OER) activity is still challenging, which significantly limits their utilization. Here, the synthesis of Fe₃O₄‐decorated Co₉S₈ nanoparticles in situ grown on a reduced graphene oxide surface (Fe₃O₄@Co₉S₈/rGO) and the use of it as a remarkably active and stable OER catalyst are first reported. Loading of Fe₃O₄ on cobalt sulfide induces the formation of pure phase Co₉S₈ and highly improves the catalytic activity for OER. The composite exhibits superior OER performance with a small overpotential of 0.34 V at the current density of 10 mA cm^?2 and high stability. It is believed that the electron transfer trend from Fe species to Co₉S₈ promotes the breaking of the Co–O bond in the stable configuration (Co–O–O superoxo group), attributing to the excellent catalytic activity. This development offers a new and effective cobalt sulfide‐based oxygen evolution electrocatalysts to replace the expensive commercial catalysts such as RuO₂ or IrO₂.     

Three Birds,One‐Stone Strategy for Hybrid Microwave Synthesis of Ta and Sn Codoped Fe2O3@FeTaO4 Nanorods for Photo‐Electrochemical Water Oxidation

A “three birds, one stone” strategy is proposed to enhance the performance of hematite photoanode for photoelectrochemical water splitting. One‐pot hybrid microwave synthesis of Ta and Sn codoped Fe₂O₃@FeTaO₄ core–shell nanorods on F:SnO₂ substrate achieves three synergetic effects simultaneously: i) core–shell heterojunction formation to alleviate the significant electron–hole recombination; ii) preserved morphology of small‐diameter nanorods to provide a short hole diffusion distance; and iii) Ta and Sn codoping to enhance the electrical conductivity. These effects are not possible with conventional high temperature thermal synthesis in a furnace. As a result, core–shell Fe₂O₃@FeTaO₄ electrode with FeOOH cocatalyst achieves a photocurrent density of 2.86 mA cm^?2 at 1.23 V_RHE under AM 1.5 G simulated sunlight (100 mW cm^?2), which is ≈2.4 times higher than that of bare hematite (1.17 mA cm^?2). In addition, the FeOOH/Fe₂O₃@FeTaO₄ electrode exhibits a high surface charge separation efficiency of ≈85% and a modest bulk charge separation efficiency of ≈24%.