Tumor Microenvironment‐Triggered Aggregation of Antiphagocytosis 99mTc‐Labeled Fe3O4 Nanoprobes for Enhanced Tumor Imaging In Vivo

A tumor microenvironment responsive nanoprobe is developed for enhanced tumor imaging through in situ crosslinking of the Fe₃O₄ nanoparticles modified with a responsive peptide sequence in which a tumor‐specific Arg‐Gly‐Asp peptide for tumor targeting and a self‐peptide as a “mark of self” are linked through a disulfide bond. Positioning the self‐peptide at the outmost layer is aimed at delaying the clearance of the nanoparticles from the bloodstream. After the self‐peptide is cleaved by glutathione within tumor microenvironment, the exposed thiol groups react with the remaining maleimide moieties from adjacent particles to crosslink the particles in situ. Both in vitro and in vivo experiments demonstrate that the aggregation substantially improves the magnetic resonance imaging (MRI) contrast enhancement performance of Fe₃O₄ particles. By labeling the responsive particle probe with ^99mTc, single‐photon emission computed tomography is enabled not only for verifying the enhanced imaging capacity of the crosslinked Fe₃O₄ particles, but also for achieving sensitive dual modality imaging of tumors in vivo. The novelty of the current probe lies in the combination of tumor microenvironment‐triggered aggregation of Fe₃O₄ nanoparticles for boosting the T₂ MRI effect, with antiphagocytosis surface coating, active targeting, and dual‐modality imaging, which is never reported before.     

Rational Design of Multifunctional Fe@γ‐Fe2O3@H‐TiO2 Nanocomposites with Enhanced Magnetic and Photoconversion Effects for Wide Applications: From Photocatalysis to Imaging‐Guided Photothermal Cancer Therapy

Titanium dioxide (TiO₂) has been widely investigated and used in many areas due to its high refractive index and ultraviolet light absorption, but the lack of absorption in the visible–near infrared (Vis–NIR) region limits its application. Herein, multifunctional Fe@γ‐Fe₂O₃@H‐TiO₂ nanocomposites (NCs) with multilayer‐structure are synthesized by one‐step hydrogen reduction, which show remarkably improved magnetic and photoconversion effects as a promising generalists for photocatalysis, bioimaging, and photothermal therapy (PTT). Hydrogenation is used to turn white TiO₂ in to hydrogenated TiO₂ (H‐TiO₂), thus improving the absorption in the Vis–NIR region. Based on the excellent solar‐driven photocatalytic activities of the H‐TiO₂ shell, the Fe@γ‐Fe₂O₃ magnetic core is introduced to make it convenient for separating and recovering the catalytic agents. More importantly, Fe@γ‐Fe₂O₃@H‐TiO₂ NCs show enhanced photothermal conversion efficiency due to more circuit loops for electron transitions between H‐TiO₂ and γ‐Fe₂O₃, and the electronic structures of Fe@γ‐Fe₂O₃@H‐TiO₂ NCs are calculated using the Vienna ab initio simulation package based on the density functional theory to account for the results. The reported core–shell NCs can serve as an NIR‐responsive photothermal agent for magnetic‐targeted photothermal therapy and as a multimodal imaging probe for cancer including infrared photothermal imaging, magnetic resonance imaging, and photoacoustic imaging.     

Multifunctional Magnetic Gd3+‐Based Coordination Polymer Nanoparticles: Combination of Magnetic Resonance and Multispectral Optoacoustic Detections for Tumor‐Targeted Imaging in vivo

To overcome traditional barriers in optical imaging and microscopy, optoacoustic‐imaging has been changed to combine the accuracy of spectroscopy with the depth resolution of ultrasound, achieving a novel modality with powerful in vivo imaging. However, magnetic resonance imaging provides better spatial and anatomical resolution. Thus, a single hybrid nanoprobe that allows for simultaneous multimodal imaging is significant not only for cutting edge research in imaging science, but also for accurate clinical diagnosis. A core‐shell‐structured coordination polymer composite microsphere has been designed for in vivo multimodality imaging. It consists of a Fe₃O₄ nanocluster core, a carbon sandwiched layer, and a carbocyanine‐Gd^III (Cy‐Gd^III) coordination polymer outer shell (Fe₃O₄@C@Cy‐Gd^III). Folic acid‐conjugated poly(ethylene glycol) chains are embedded within the coordination polymer shell to achieve extended circulation and targeted delivery of probe particles in vivo. Control of Fe₃O₄ core grain sizes results in optimal r₂ relaxivity (224.5 × 10^–3 m ⁻¹ s^‐1) for T₂‐weighted magnetic resonance imaging. Cy‐Gd^III coordination polymers are also regulated to obtain a maximum 25.1% of Cy ligands and 5.2% of Gd^III ions for near‐infrared fluorescence and T₁‐weighted magnetic resonance imaging, respectively. The results demonstrate their impressive abilities for targeted, multimodal, and reliable imaging.     

Dendrimer‐Assisted Formation of Fe3O4/Au Nanocomposite Particles for Targeted Dual Mode CT/MR Imaging of Tumors

A unique dendrimer‐assisted approach is reported to create Fe₃O₄/Au nanocomposite particles (NCPs) for targeted dual mode computed tomography/magnetic resonance (CT/MR) imaging of tumors. In this approach, preformed Fe₃O₄ nanoparticles (NPs) are assembled with multilayers of poly(γ‐glutamic acid) (PGA)/poly(l ‐lysine)/PGA/folic acid (FA)‐modified dendrimer‐entrapped gold nanoparticles via a layer‐by‐layer self‐assembly technique. The interlayers are crosslinked via 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide chemistry, the assembled Au core NPs are then used as seed particles for subsequent seed‐mediated growth of Au shells via iterative Au salt reduction process, and subsequent acetylation of the remaining amines of dendrimers leads to the formation of Fe₃O₄/Au_n.Ac‐FA NCPs with a tunable molar ratio of Au/Fe₃O₄. It is shown that the Fe₃O₄/Au_n.Ac‐FA NCPs at an optimized Au/Fe₃O₄ molar ratio of 2.02 display a relatively high R₂ relaxivity (92.67 × 10^?3 M^?1 s^?1) and good X‐ray attenuation property, and are cytocompatible and hemocompatible in the given concentration range. Importantly, with the FA‐mediated targeting, the Fe₃O₄/Au_n.Ac‐FA NCPs are able to be specifically uptaken by cancer cells overexpressing FA receptors, and be used as an efficient nanoprobe for targeted dual mode CT/MR imaging of a xenografted tumor model. With the versatile dendrimer chemistry, the developed Fe₃O₄/Au NCPs may be differently functionalized, thereby providing a unique platform for diagnosis and therapy of different biological systems.     

Multifunctional pDNA‐Conjugated Polycationic Au Nanorod‐Coated Fe3O4 Hierarchical Nanocomposites for Trimodal Imaging and Combined Photothermal/Gene Therapy

It is very desirable to design multifunctional nanocomposites for theranostic applications via flexible strategies. The synthesis of one new multifunctional polycationic Au nanorod (NR)‐coated Fe₃O₄ nanosphere (NS) hierarchical nanocomposite (Au@pDM/Fe₃O₄) based on the ternary assemblies of negatively charged Fe₃O₄ cores (Fe₃O₄‐PDA), polycation‐modified Au nanorods (Au NR‐pDM), and polycations is proposed. For such nanocomposites, the combined near‐infrared absorbance properties of Fe₃O₄‐PDA and Au NR‐pDM are applied to photoacoustic imaging and photothermal therapy. Besides, Fe₃O₄ and Au NR components allow the nanocomposites to serve as MRI and CT contrast agents. The prepared positively charged Au@pDM/Fe₃O₄ also can complex plasmid DNA into pDNA/Au@pDM/Fe₃O₄ and efficiently mediated gene therapy. The multifunctional applications of pDNA/Au@pDM/Fe₃O₄ nanocomposites in trimodal imaging and combined photothermal/gene therapy are demonstrated using a xenografted rat glioma nude mouse model. The present study demonstrates that the proper assembly of different inorganic nanoparticles and polycations is an effective strategy to construct new multifunctional theranostic systems.     

Sb‐Doped SnO2 Nanorods Underlayer Effect to the α‐Fe2O3 Nanorods Sheathed with TiO2 for Enhanced Photoelectrochemical Water Splitting

Here, a Sb‐doped SnO₂ (ATO) nanorod underneath an α‐Fe₂O₃ nanorod sheathed with TiO₂ for photoelectrochemical (PEC) water splitting is reported. The experimental results, corroborated with theoretical analysis, demonstrate that the ATO nanorod underlayer effect on the α‐Fe₂O₃ nanorod sheathed with TiO₂ enhances the PEC water splitting performance. The growth of the well‐defined ATO nanorods is reported as a conductive underlayer to improve α‐Fe₂O₃ PEC water oxidation performance. The α‐Fe₂O₃ nanorods grown on the ATO nanorods exhibit improved performance for PEC water oxidation compared to α‐Fe₂O₃ grown on flat fluorine‐doped tin oxide glass. Furthermore, a simple and facile TiCl₄ chemical treatment further introduces TiO₂ passivation layer formation on the α‐Fe₂O₃ to reduce surface recombination. As a result, these unique nanostructures show dramatically improved photocurrent density (139% higher than that of the pure hematite nanorods).     

Yolk–Shell Nanostructure: An Ideal Architecture to Achieve Harmonious Integration of Magnetic–Plasmonic Hybrid Theranostic Platform

Magnetic–plasmonic hybrid nanoparticles (MPHNs) have attracted great interest in cancer theranostics. However, the relaxivity of the magnetic component is typically reduced by the plasmonic component in conventional core–shell structured MPHNs, due to the presence of a water‐impenetrable coating which severely restricts the proximity of protons to the magnetic portion. To circumvent this issue, yolk–shell structured MPHNs comprising a Fe₃O₄ core within a hollow cavity encircled by a porous Au outer shell are designed. As expected, the introduction of hollow cavity between the magnetic and plasmonic portions significantly prevents the decline in relaxivity of the Fe₃O₄ core caused by the Au layer. Moreover, in addition to conferring high near‐infrared absorption to plasmonic component, the hollow cavity and the pores in the outer shell can also provide a large storage space and release channels for anticancer drugs. Furthermore, the multicomponent nanoparticles (NPs) still have a compact size of less than 100 nm to ensure efficient tumor accumulation. Taken together, the yolk–shell Fe₃O₄@Au NPs can be regarded as an ideal magnetic–plasmonic theranostic platform for magnetic resonance/photoacoustic/positron emission tomography multimodal imaging and light‐activated chemothermal synergistic therapy.     

Giant Magnetic Heat Induction of Magnesium‐Doped γ‐Fe2O3 Superparamagnetic Nanoparticles for Completely Killing Tumors

Magnetic fluid hyperthermia has been recently considered as a Renaissance of cancer treatment modality due to its remarkably low side effects and high treatment efficacy compared to conventional chemotheraphy or radiotheraphy. However, insufficient AC induction heating power at a biological safe range of AC magnetic field (H_appl·f_appl < 3.0–5.0 × 10⁹ A m^?1 s^?1), and highly required biocompatibility of superparamagnetic nanoparticle (SPNP) hyperthermia agents are still remained as critical challenges for successful clinical hyperthermia applications. Here, newly developed highly biocompatible magnesium shallow doped γ‐Fe₂O₃ (Mg_0.13‐γFe₂O₃) SPNPs with exceptionally high intrinsic loss power (ILP) in a range of 14 nH m² kg^?1, which is an ≈100 times higher than that of commercial Fe₃O₄ (Feridex, ILP = 0.15 nH m² kg^?1) at H_appl·f_appl = 1.23 × 10⁹ A m^?1 s^?1 are reported. The significantly enhanced heat induction characteristics of Mg_0.13‐γFe₂O₃ are primarily due to the dramatically enhanced out‐of‐phase magnetic susceptibility and magnetically tailored AC/DC magnetic softness resulted from the systematically controlled Mg²⁺ cations distribution and concentrations in octahedral site Fe vacancies of γ‐Fe₂O₃ instead of well‐known Fe₃O₄ SPNPs. In vitro and in vivo magnetic hyperthermia studies using Mg_0.13‐γFe₂O₃ nanofluids are conducted to estimate bioavailability and biofeasibility. Mg_0.13‐γFe₂O₃ nanofluids show promising hyperthermia effects to completely kill the tumors.     

Dotted Core–Shell Nanoparticles for T1‐Weighted MRI of Tumors

Gd‐based T ₁‐weighted contrast agents have dominated the magnetic resonance imaging (MRI) contrast agent market for decades. Nevertheless, they are reported to be nephrotoxic and the U.S. Food and Drug Administration has issued a general warning concerning their use. In order to reduce the risk of nephrotoxicity, the MRI performance of the Gd‐based T ₁‐weighted contrast agents needs to be improved to allow a much lower dosage. In this study, novel dotted core–shell nanoparticles (FeGd‐HN3‐RGD2) with superhigh r ₁ value (70.0 mM^?1 s^?1) and very low r ₂/r ₁ ratio (1.98) are developed for high‐contrast T ₁‐weighted MRI of tumors. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay and histological analyses show good biocompatibility of FeGd‐HN3‐RGD2. Laser scanning confocal microscopy images and flow cytometry demonstrate active targeting to integrin α_vβ₃ positive tumors. MRI of tumors shows high tumor ΔSNR for FeGd‐HN3‐RGD2 (477 ± 44%), which is about 6‐7‐fold higher than that of Magnevist (75 ± 11%). MRI and inductively coupled plasma results further confirm that the accumulation of FeGd‐HN3‐RGD2 in tumors is higher than liver and spleen due to the RGD2 targeting and small hydrodynamic particle size (8.5 nm), and FeGd‐HN3‐RGD2 is readily cleared from the body by renal excretion.     

Multistimuli Responsive Core–Shell Nanoplatform Constructed from Fe3O4@MOF Equipped with Pillar[6]arene Nanovalves

An intelligent theranostic nanoplatform based on nanovalve operated metal–organic framework (MOF) core–shell hybrids, incorporating tumorous microenvironment‐triggered drug release, magnetic resonance imaging (MRI) guidance, sustained release, and effective chemotherapy in one pot is reported. The core–shell hybrids are constructed by an in situ growth method, in which Fe₃O₄ particles with superior abilities of MRI and magnetic separation form the core and UiO‐66 MOF with high loading capacity compose the shell, and then are surface‐installed with pillararene‐based pseudorotaxanes as tightness‐adjustable nanovalves. This strategy endows the system with the ability of targeted, multistimuli responsive drug release in response to pH changes, temperature variations, and competitive agents. Water‐soluble carboxylatopillar[6]arene system achieved sustained drug release over 7 days due to stronger host–guest binding, suggesting that the nanovalve tightness further reinforces the desirable release of anticancer agent over a prolonged time at the lesion site.     

Fluorescent Magnetic Fe3O4/Rare Earth Colloidal Nanoparticles for Dual‐Modality Imaging

Fluorescent magnetic colloidal nanoparticles (FMCNPs) are produced by a two‐step, seed emulsifier‐free emulsion polymerization in the presence of oleic acid and sodium undecylenate‐modified Fe₃O₄ nanoparticles (NPs). The Fe₃O₄/poly(St‐co‐GMA) nanoparticles are first synthesized as the seed and Eu(AA)₃Phen is copolymerized with the remaining St and GMA to form the fluorescent polymer shell in the second step. The uniform core–shell structured FMCNPs with a mean diameter of 120 nm exhibit superparamagnetism with saturation magnetization of 1.92 emu/g. Red luminescence from the FMCNPs is confirmed by the salient fluorescence emission peaks of europium ions at 594 and 619 nm as well as 2‐photon confocal scanning laser microscopy. The in vitro cytotoxicity test conducted using the MTT assay shows good cytocompatibility and the T₂ relaxivity of the FMCNPs is 353.86 mM^?1S^?1 suggesting its potential in magnetic resonance imaging (MRI). In vivo MRI studies based on a rat model show significantly enhanced T₂‐weighted images of the liver after administration and prussian blue staining of the liver tissue slice reveals accumulation of FMCNPs in the organ. The cytocompatibility, superparamagnetism, and excellent fluorescent properties of FMCNPs make them suitable for biological imaging probes in MRI and optical imaging.     

Development of poly(vinyl acetate-methylacrylic acid)/chitosan/Fe3O4 nanoparticles for the diagnosis of non-alcoholic steatohepatitis with magnetic resonance imaging

Non-alcoholic steatohepatitis is a burgeoning health problem. To diagnose NASH with magnetic resonance imaging (MRI), an effective contrast agent, a stable suspension of superparamagnetic Fe₃O₄ nanoparticles, were newly developed. The negatively charged Fe₃O₄ nanoparticles were coated with positive chitosan (CS) firstly, and then assembled with poly(vinyl acetate-methylacrylic acid) (P(VAc-MAA)). Transmission electron microscope and dynamic light scattering confirmed that the obtained P(VAc-MAA)/CS/Fe₃O₄ nanoparticles had a spherical or ellipsoidal morphology with an average diameter in the range of 14–20 nm. The superparamagnetic property and spinel structure of the Fe₃O₄ nanoparticles were well preserved due to the protection of the P(VAc-MAA)/CS layers on the surface of the Fe₃O₄ nanoparticles. The in vivo rat experiments confirmed that the P(VAc-MAA)/CS/Fe₃O₄ nanoparticles were an effective contrast agent for MRI to diagnose NASH.     

Yolk–Shelled C@Fe3O4 Nanoboxes as Efficient Sulfur Hosts for High‐Performance Lithium–Sulfur Batteries

Owing to the high theoretical specific capacity (1675 mA h g^?1) and low cost, lithium–sulfur (Li–S) batteries offer advantages for next‐generation energy storage. However, the polysulfide dissolution and low electronic conductivity of sulfur cathodes limit the practical application of Li–S batteries. To address such issues, well‐designed yolk–shelled carbon@Fe₃O₄ (YSC@Fe₃O₄) nanoboxes as highly efficient sulfur hosts for Li–S batteries are reported here. With both physical entrapment by carbon shells and strong chemical interaction with Fe₃O₄ cores, this unique architecture immobilizes the active material and inhibits diffusion of the polysulfide intermediates. Moreover, due to their high conductivity, the carbon shells and the polar Fe₃O₄ cores facilitate fast electron/ion transport and promote continuous reactivation of the active material during the charge/discharge process, resulting in improved electrochemical utilization and reversibility. With these merits, the S/YSC@Fe₃O₄ cathodes support high sulfur content (80 wt%) and loading (5.5 mg cm^?2) and deliver high specific capacity, excellent rate capacity, and long cycling stability. This work provides a new perspective to design a carbon/metal‐oxide‐based yolk–shelled framework as a high sulfur‐loading host for advanced Li–S batteries with superior electrochemical properties.     

Personalized Cancer Immunotherapy via Transporting Endogenous Tumor Antigens to Lymph Nodes Mediated by Nano Fe3O4

While immunotherapy has a tremendous clinical potential to combat cancer, immune responses generated by conventional cancer immunotherapy remain not enough to completely eliminate tumors, mainly due to the tumor's immunosuppressive microenvironment and heterogeneity of tumor immunogenicity. To improve antitumor immune responses and realize personalized immunotherapy, in this report, endogenous tumor antigens (ETAs) that dynamically present on tumor cells are transported to lymph nodes (LNs). Based on the hypothesis that nano Fe₃O₄ (≈10 nm) could serve as the nanocarrier for transporting ETAs from the tumor to LNs, we wondrously find that Fe₃O₄ has a tremendous potential to improve cancer immunotherapy, because of its excellent protein‐captured efficiency and LNs‐targeted ability. To ensure the optimal ETAs‐bound efficiency of Fe₃O₄, a core–shell formulation (denoted as Ce6/Fe₃O₄‐L) is developed and specific release of Fe₃O₄ in tumor is enabled. These findings provide a simple and general strategy for boosting cytotoxic T‐cell response and realizing personalized cancer immunotherapy simultaneously.     

Fabrication of Fe3O4 Dots Embedded in 3D Honeycomb‐Like Carbon Based on Metallo–Organic Molecule with Superior Lithium Storage Performance

A novel metallo–organic molecule, ferrocene, is selected as building block to construct Fe₃O₄ dots embedded in 3D honeycomb‐like carbon (Fe₃O₄ dots/3DHC) by using SiO₂ nanospheres as template. Unlike previously used inorganic Fe₃O₄ sources, ferrocene simultaneously contains organic cyclopentadienyl groups and inorganic Fe atoms, which can be converted to carbon and Fe₃O₄, respectively. Atomic‐scale Fe distribution in started building block leads to the formation of ultrasmall Fe₃O₄ dots (≈3 nm). In addition, by well controlling the feed amount of ferrocene, Fe₃O₄ dots/3DHC with well‐defined honeycomb‐like meso/macropore structure and ultrathin carbon wall can be obtained. Owing to unique structural features, Fe₃O₄ dots/3DHC presents impressive lithium storage performance. The initial discharge and reversible capacities can reach 2047 and 1280 mAh g^?1 at 0.05 A g^?1. With increasing the current density to 1 and 3 A g^?1, remarkable capacities of 963 and 731 mAh g^?1 remain. Moreover, Fe₃O₄ dots/3DHC also has superior cycling stability, after a long‐term charge/discharge for 200 times, a high capacity of 1082 mAh g^?1 can be maintained (80% against the capacity of the 2nd cycle).     

A Magnetic‐Field Guided Interface Coassembly Approach to Magnetic Mesoporous Silica Nanochains for Osteoclast‐Targeted Inhibition and Heterogeneous Nanocatalysis

1D core–shell magnetic materials with mesopores in shell are highly desired for biocatalysis, magnetic bioseparation, and bioenrichment and biosensing because of their unique microstructure and morphology. In this study, 1D magnetic mesoporous silica nanochains (Fe₃O₄@nSiO₂@mSiO₂ nanochain, Magn‐MSNCs named as FDUcs‐17C) are facilely synthesized via a novel magnetic‐field‐guided interface coassembly approach in two steps. Fe₃O₄ particles are coated with nonporous silica in a magnetic field to form 1D Fe₃O₄@nSiO₂ nanochains. A further interface coassembly of cetyltrimethylammonium bromide and silica source in water/n‐hexane biliquid system leads to 1D Magn‐MSNCs with core–shell–shell structure, uniform diameter (≈310 nm), large and perpendicular mesopores (7.3 nm), high surface area (317 m² g^?1), and high magnetization (34.9 emu g^?1). Under a rotating magnetic field, the nanochains with loaded zoledronate (a medication for treating bone diseases) in the mesopores, show an interesting suppression effect of osteoclasts differentiation, due to their 1D nanostructure that provides a shearing force in dynamic magnetic field to induce sufficient and effective reactions in cells. Moreover, by loading Au nanoparticles in the mesopores, the 1D Fe₃O₄@nSiO₂@mSiO₂‐Au nanochains can service as a catalytically active magnetic nanostirrer for hydrogenation of 4‐nitrophenol with high catalytic performance and good magnetic recyclability.     

Modulation of Inverse Spinel Fe3O4 by Phosphorus Doping as an Industrially Promising Electrocatalyst for Hydrogen Evolution

Fe‐based oxides have been seldom reported as electrocatalysts for the hydrogen evolution reaction (HER), limited by their weak intrinsic activity and conductivity. Herein, phosphorus doping modulation is used to construct inverse spinel P‐Fe₃O₄ with dual active sites supported on iron foam (P‐Fe₃O₄/IF) for alkaline HER with an extremely low overpotential of 138 mV at 100 mA cm^?2. The obtained inverse spinel Fe–O–P derived from controllable phosphorization can provide an octahedral Fe site and O atom, which bring about the unusual dissociation mechanisms of two water molecules to greatly accelerate the proton supply in alkaline media. Meanwhile, the ΔG_H of the P atom in Fe–O–P as an active site is theoretically calculated to be 0.01 eV. Notably, the NiFe LDH/IF⁽⁺⁾||P‐Fe₃O₄/IF^(?) couple achieves an onset potential of 1.47 V (vs RHE) for overall water splitting, with excellent stability for more than 1000 h at a current density of 1000 mA cm^?2, and even for 25 000 s at 10 000 mA cm^?2 in 6.0 m KOH at 60 °C. The excellent catalyst stability and low‐cost merits of P‐Fe₃O₄/IF may hold promise for industrial hydrogen production. This work may reveal a new design strategy of earth‐abundant materials for large‐scale water splitting.     

Boosted Interfacial Polarization from Multishell TiO2@Fe3O4@PPy Heterojunction for Enhanced Microwave Absorption

Core@shell structures have been attracting extensive attention to boost microwave absorption (MA) performance due to the unique interfacial polarization. However, it still remains a challenge to synthesize sophisticated 1D semiconductor‐based materials with excellent MA competence. Herein, a hierarchical cable‐like TiO₂@Fe₃O₄@PPy is fabricated by a sequential process of solvothermal treatment and polymerization. The complex permittivity of ternary composites can be optimized by tunable PPy coating thickness to improve the loss ability. The maximum reflection loss can reach ?61.8 dB with a thickness of 3.2 mm while the efficient absorption bandwidth can achieve over 6.0 GHz, which involves the X and Ku band at only a 2.2 mm thickness. Importantly, the heterojunction contacts constructed by PPy–Fe₃O₄ and Fe₃O₄–TiO₂ contribute to the enhanced polarization loss. Besides, the configuration of magnetic Fe₃O₄ sandwiched between dielectric TiO₂ and PPy facilitates the magnetic stray field to radiate into the TiO₂ core and out of the PPy shell, which significantly promotes magnetic–dielectric synergy. Electron holography validates the distinct charge distribution and magnetic coupling. The new findings might shed light on novel structures for functional core@shell composites and the design of semiconductor‐based materials for microwave absorption.     

Magnetic Metal–Organic Frameworks: γ‐Fe2O3@MOFs via Confined In Situ Pyrolysis Method for Drug Delivery

A general one‐step in situ pyrolysis route for the construction of metal–organic frameworks encapsulating superparamagnetic γ‐Fe₂O₃ NPs dispersed in the confined cavities of MOFs homogeneously is described. The integration of γ‐Fe₂O₃ NPs or clusters into MOFs can endow these porous materials with superparamagnetic element. By the combination of the thermal stability of MOFs and pyrolysis of metal triacetylacetonate complex at matched conditions, the porous structure of MOFs are well maintained while the size‐induced superparamagnetic property of nano γ‐Fe₂O₃ is obtained. As a proof of concept, both the γ‐ Fe₂O₃@ZIF‐8 and γ‐Fe₂O₃@MIL‐53(Al) were successfully prepared, and the latter was chosen to demonstrate its potential drug delivery as a magnetic MOF.     

Tumor‐Targeting Multifunctional Rattle‐Type Theranostic Nanoparticles for MRI/NIRF Bimodal Imaging and Delivery of Hydrophobic Drugs

The development of theranostic systems capable of diagnosis, therapy, and target specificity is considerably significant for accomplishing personalized medicine. Here, a multifunctional rattle‐type nanoparticle (MRTN) as an effective biological bimodal imaging and tumor‐targeting delivery system is fabricated, and an enhanced loading ability of hydrophobic anticancer drug (paclitaxel) is also realized. The rattle structure with hydrophobic Fe₃O₄ as the inner core and mesoporous silica as the shell is obtained by one‐step templates removal process, and the size of interstitial hollow space can be easily adjusted. The Fe₃O₄ core with hydrophobic poly(tert‐butyl acrylate) (PTBA) chains on the surface is not only used as a magnetic resonance imaging (MRI) agent, but contributes to improving hydrophobic drug loading amount. Transferrin (Tf) and a near‐infrared fluorescent dye (Cy 7) are successfully modified on the surface of the nanorattle to increase the ability of near‐infrared fluorescence (NIRF) imaging and tumor‐targeting specificity. In vivo studies show the selective accumulation of MRTN in tumor tissues by Tf‐receptor‐mediated endocytosis. More importantly, paclitaxel‐loaded MRTN shows sustained release character and higher cytotoxicity than the free paclitaxel. This theranostic nanoparticle as an effective MRI/NIRF bimodal imaging probe and drug delivery system shows great potential in cancer diagnosis and therapy.