pH‐Based Regulation of Hydrogel Mechanical Properties Through Mussel‐Inspired Chemistry and Processing

The mechanical holdfast of the mussel, the byssus, is processed at acidic pH yet functions at alkaline pH. Byssi are enriched in Fe³⁺ and catechol‐containing proteins, species with chemical interactions that vary widely over the pH range of byssal processing. Currently, the link between pH, Fe³⁺‐catechol reactions, and mechanical function is poorly understood. Herein, it is described how pH influences the mechanical performance of materials formed by reacting synthetic catechol polymers with Fe³⁺. Processing Fe³⁺‐catechol polymer materials through a mussel‐mimetic acidic‐to‐alkaline pH change leads to mechanically tough materials based on a covalent network fortified by sacrificial Fe³⁺‐catechol coordination bonds. These findings offer the first direct evidence of Fe³⁺‐induced covalent cross‐linking of catechol polymers, reveal additional insight into the pH dependence and mechanical role of Fe³⁺‐catechol interactions in mussel byssi, and illustrate the wide range of physical properties accessible in synthetic materials through mimicry of mussel‐protein chemistry and processing.     

Peptide Length and Dopa Determine Iron‐Mediated Cohesion of Mussel Foot Proteins

Mussel adhesion to mineral surfaces is widely attributed to 3,4‐dihydroxyphenylalanine (Dopa) functionalities in the mussel foot proteins (mfps). Several mfps, however, show a broad range (30%–100%) of tyrosine (Tyr) to Dopa conversion suggesting that Dopa is not the only desirable outcome for adhesion. Here, a partial recombinant construct of mussel foot protein‐1 (rmfp‐1) and short decapeptide dimers with and without Dopa are used and both their cohesive and adhesive properties on mica are assessed using a surface forces apparatus. Our results demonstrate that at low pH, both the unmodified and Dopa‐containing rmfp‐1s show similar energies for adhesion to mica and self–self‐interaction. Cohesion between two Dopa‐containing rmfp‐1 surfaces can be doubled by Fe³⁺ chelation, but remains unchanged with unmodified rmfp‐1. At the same low pH, the Dopa‐modified short decapeptide dimer did not show any change in cohesive interactions even with Fe³⁺. The results suggest that the most probable intermolecular interactions are those arising from electrostatic (i.e., cation–π) and hydrophobic interactions. It is also shown that Dopa in a peptide sequence does not by itself mediate Fe³⁺ bridging interactions between peptide films: peptide length is a crucial enabling factor.     

A Novel Double‐Crosslinking‐Double‐Network Design for Injectable Hydrogels with Enhanced Tissue Adhesion and Antibacterial Capability for Wound Treatment

Most photocrosslinkable hydrogels have inadequacy in either mechanical performance or biodegradability. This issue is addressed by adopting a novel hydrogel design by introducing two different chitosan chains (catechol‐modified methacryloyl chitosan, CMC; methacryloyl chitosan, MC) via the simultaneous crosslinking of carbon–carbon double bonds and catechol‐Fe³⁺ chelation. This leads to an interpenetrating network of two chitosan chains with high crosslinking‐network density, which enhances mechanical performance including high compressive modulus and high ductility. The chitosan polymers not only endow the hydrogels with good biodegradability and biocompatibility, they also offer intrinsic antibacterial capability. The quinone groups formed by Fe³⁺ oxidation and protonated amino groups of chitosan polymer further enhance antibacterial property of the hydrogels. Serving as one of the two types of crosslinking mechanisms, the catechol‐Fe³⁺ chelation can covalently link with amino, thiol, and imidazole groups, which substantially enhance the hydrogel's adhesion to biological tissues. The hydrogel's adhesion to porcine skin shows a lap shear strength of 18.1 kPa, which is 6‐time that of the clinically established Fibrin Glue's adhesion. The hydrogel also has a good hemostatic performance due to the superior tissue adhesion as demonstrated with a hemorrhaging liver model. Furthermore, the hydrogel can remarkably promote healing of bacteria‐infected wound.     

Structural,optical and electrical properties of Fe-doped SnO2 fabricated by sol–gel dip coating technique

Nanosized Fe³⁺-doped SnO₂ thin film was prepared by the sol–gel dip coating (SGDC) technique on quartz class substrate and sintered at 800 °C. The microstructures, surface morphology and optical properties of these films were then characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical absorption measurements, respectively. Electrical properties were analyzed, and resistivity, type and number of carrier concentration, Hall mobility measured as a function of Fe³⁺ doping and temperature. The XRD spectrum shows the decrease in peak heights as a result of Fe³⁺-doping while SEM images reveal reduction in crystallite size with increase in Fe³⁺ content. The optical studies showed a direct band gap reducing with increase in Fe³⁺-doping from 3.87 to 3.38 eV. From the electrical measurements, it was found that the resistivity initially increased with Fe³⁺-doping before reducing at higher doping level. Hall mobility measurements showed n-type conductivity at lower Fe³⁺-doping levels and p-type at higher levels. The increase in conductivity with temperature ascertained the semiconducting behavior of these films.     

Water‐Induced Phase Separation Forming Macrostructured Epitaxial Quartz Films on Silicon

Quartz has been widely used as a bulk material in optics, the microelectronic industry, and sensors. The nanostructuring and direct integration of oriented quartz crystals onto a semiconductor platform has proven to be challenging. However, here, a new approach is presented to integrate epitaxial quartz films with macroperforations within the range of 500 nm and 1 μm using chemical solution deposition. This method constitutes an appealing approach to develop piezoelectric mass sensors with enhanced resonance frequencies due to the thickness reduction. Perforated quartz films on (100)‐silicon are prepared from amorphous silica films deposited via dip‐coating and doped with metal cations that catalyze quartz crystallization. The metal cations are also active in the formation of the macroperforations, which arise due to a phase separation mechanism. Cationic surfactant–anion–metal cation assemblies stabilize droplets of water, creating an indentation in the hydrophilic silica matrix which remains after solvent evaporation. Many cations induce phase separation, including Li⁺, Na⁺, Sr²⁺, Mn²⁺, Fe²⁺/Fe³⁺, Ca²⁺, Ce³⁺ and La³⁺ but only the Sr²⁺ and Ca²⁺ cations in this series induce the epitaxial growth of α‐quartz films under the conditions studied. The combination of sol–gel chemistry and epitaxial growth opens new opportunities for the integration of patterned quartz on silicon.     

NIR Light-Triggered Shape Memory Polymers Based on Mussel-Inspired Iron–Catechol Complexes

Shape memory polymers (SMPs) with the permanent shape reconfiguration capability have received much research interest because they are capable of diversified tasks and the ability to work in conditions that required complex geometry. However, most of such SMPs are thermally triggered, which limits their applications. Inspired by reversible mussel adhesive protein chemistry, NIR light-triggered SMPs with the permanent shape reconfiguration capability are prepared. The polymer networks are constructed using biocompatible polyethylene glycol, which is crosslinked based on catechol–Fe³⁺ coordination. The polymer networks have a uniform network structure and exhibit a considerable one-way shape memory effect (1W-SME) as well as a good two-way shape memory effect (2W-SME) under stress conditions. Taking advantage of the dynamic nature of the catechol–Fe³⁺ coordination, the permanent shape of the polymers could be reconfigured. Moreover, the catechol–Fe³⁺ complexes have a broad absorption in the NIR window, which bestows the polymers with excellent NIR light-triggered SME. Further, the great potential of the obtained polymers in biomedical and electronic applications is presented. Owing to the NIR-triggered 1W-SME and the permanent shape reconfiguration capability, the polymer could be used as a personalizing vascular stent. Additionally, the polymer could be applied in light-driven switches based on the NIR light-triggered 2W-SME.     

Metal Ion‐Terpyridine‐Functionalized L‐Tyrosinamide Aptamers: Nucleoapzymes for Oxygen Insertion into C?H Bonds and the Transformation of L‐Tyrosinamide into Amidodopachrome

A series of metal ion‐terpyridine‐modified L‐tyrosinamide aptamers (M^{n +} = Cu²⁺ or Fe³⁺) act as enzyme‐mimicking catalysts (nucleoapzymes) for oxygen‐insertion into C? H bonds and the transformation of L‐tyrosinamide into amidodopachrome. The reaction proceeds in the presence of H₂O₂ and coadded L‐ascorbic acid. In one series of experiments, the catalyzed oxidation of L‐tyrosinamide to amidodopachrome by a set of nucleoapzymes consisting of Fe³⁺‐ or Cu²⁺‐terpyridine complexes tethered directly or through a 4 × thymidine (4 × T) bridge, to the 5′‐ or 3′‐end of the 49‐mer L‐tyrosinamide aptamer or to a shorter 23‐mer L‐tyrosinamide aptamer is examined. All nucleoapzymes reveal catalytic Michaelis–Menten enzyme‐like activities and the separated Fe³⁺‐ or Cu²⁺‐terpyridine and L‐tyrosinamide aptamer units show only minute catalytic properties. The catalytic activities of the nucleoapzymes are attributed to the concentration of the L‐tyrosinamide substrate by the aptamer units in proximity to the catalytic sites (K_d = (14 ± 0.1) × 10^?6 m for all 49‐mer catalysts and K_d = (2.5 ± 0.1) × 10^?6 m and K_d = (0.8 ± 0.04) × 10^?6 m for the 23‐mer catalysts). Electron spin resonance experiments reveal that ?OH radicals and ascorbate radicals participate in the transformation of tyrosine derivatives to catechol products. An autocatalytic feedback mechanism for the amplified generation of the two radicals is suggested.     

CoFe2O4 and CoFe2O4‐SiO2 Nanoparticle Thin Films with Perpendicular Magnetic Anisotropy for Magnetic and Magneto‐Optical Applications

This paper presents an efficient colloidal approach to process CoFe₂O₄ and SiO₂ nanoparticles into thin films for magnetic and magneto‐optical applications. Thin films of varying CoFe₂O₄‐to‐SiO₂ ratios (from 0 to 90 wt%) are obtained by sequential spin coating‐calcination cycles from the corresponding nanoparticle dispersions. Scanning electron microscopy analysis reveals a crack free and nanoparticulate structure of the sintered films with thicknesses of 480–1200 nm. Results from the optical characterization indicate a direct band gap ranging from 2.6 to 3.9 eV depending on the SiO₂ content. Similarly, the refractive indices and absorption coefficients are tunable upon SiO₂ incorporation. In‐plane measurements of the magnetic properties of the CoFe₂O₄ films reveal a superparamagnetic behavior with both Co²⁺ and Fe³⁺ contributing to the magnetism. Polar Kerr measurements show the presence of a spontaneous magnetization in the CoFe₂O₄ and CoFe₂O₄‐SiO₂ (with SiO₂ < 50 wt%) films, pointing to magnetic anisotropy perpendicular to the substrate. The origin of this effect is attributed to the constrained sintering conditions of the nano­particulate film and the negative magnetostriction of CoFe₂O₄.     

3D Printing of Mechanically Stable Calcium‐Free Alginate‐Based Scaffolds with Tunable Surface Charge to Enable Cell Adhesion and Facile Biofunctionalization

For the 3D printing of bioscaffolds, the importance of a suitable bioink cannot be overemphasized. With excellent printability and biocompatibility, alginate (Alg) is one of the most used bioinks. However, its bioinert nature and insufficient mechanical stability, due to only crosslinking via cation interactions, hinder the practical application of Alg‐based bioinks in the individualized therapy of tissue defects. To overcome these drawbacks, for the first time, an ε‐polylysine (ε‐PL)‐modified Alg‐based bioink (Alg/ε‐PL) is produced. The introduction of ε‐PL improves the printability of the Alg‐based bioink due to increasing electrostatic interactions, which enhances the self‐supporting stability of the as‐printed scaffolds. The presence of the functional crosslinking –COOH and –NH₂ groups in Alg and ε‐PL under mild conditions further enhances the mechanical stability of the scaffolds, far exceeding that of Alg/Ca²⁺ scaffolds. The surface charge of the prepared scaffolds is finely tuned by the feed ratio of Alg to ε‐PL and postimmobilization of different quantities of additional ε‐PL, with a view to enhancing cell adhesion and further biofunctionalization. The results indicate that chondroitin sulfate, an extracellular matrix component, and vascular endothelial growth factor can be successfully applied to biofunctionalize the scaffolds via electrostatic adsorption for enhanced biological activity.     

Atmosphere‐Induced Reversible Resistivity Changes in Ca/Y‐Doped Bismuth Iron Garnet Thin Films

Bismuth iron garnet Bi₃Fe₅O₁₂ (BIG) is a multifunctional insulating oxide exhibiting remarkably the largest known Faraday rotation and linear magnetoelectric coupling. Enhancing the electrical conductivity in BIG while preserving its magnetic properties would further widen its range of potential applications in oxitronic devices. Here, a site‐selective codoping strategy in which Ca²⁺ and Y³⁺ substitute for Bi³⁺ is applied. The resulting p‐ and n‐type doped BIG films combine state‐of‐the‐art magneto‐optical properties and semiconducting behaviors above room temperature with rather low resistivity: 40 Ω cm at 450 K is achieved in an n‐type Y‐doped BIG; this is ten orders of magnitude lower than that of Y₃Fe₅O₁₂. High‐resolution electron spectromicroscopy unveils the complete dopant solubility and the charge compensation mechanisms at the local scale in p‐ and n‐type systems. Oxygen vacancies as intrinsic donors play a key role in the conduction mechanisms of these doped BIG films. On the other hand, a self‐compensation of Ca²⁺ with oxygen vacancies tends to limit the conduction in p‐type Ca/Y‐doped BIG. These results highlight the possibility of integrating n‐type and p‐type doped BIG films in spintronic structures as well as their potential use in gas sensing applications.     

Multivalent‐Ion‐Mediated Stabilization of Hydrogen‐Bonded Multilayers

Hydrogen‐bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)‐co‐(maleic acid)] (PSSMA) and poly(N‐isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce⁴⁺ or Fe³⁺) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce⁴⁺‐ and Fe³⁺‐stabilized films, respectively), film loss is negligible. This provides a stark contrast with non‐stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen‐bonded structures non‐covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe³⁺‐treated films to iodide solutions.     

Combined First‐Principle Calculations and Experimental Study on Multi‐Component Olivine Cathode for Lithium Rechargeable Batteries

The electrochemical properties and phase stability of the multi‐component olivine compound LiMn_1/3Fe_1/3Co_1/3PO₄ are studied experimentally and with first‐principles calculation. The formation of a solid solution between LiMnPO₄, LiFePO₄, and LiCoPO₄ at this composition is confirmed by XRD patterns and the calculated energy. The experimental and first‐principle results indicate that there are three distinct regions in the electrochemical profile at quasi‐open‐circuit potentials of ～3.5 V, ～4.1 V, and ～4.7 V, which are attributed to Fe³⁺/Fe²⁺, Mn³⁺/Mn²⁺, and Co³⁺/Co²⁺ redox couples, respectively. However, exceptionally large polarization is observed only for the region near 4.1 V of Mn³⁺/Mn²⁺ redox couples, implying an intrinsic charge transfer problem. An ex situ XRD study reveals that the reversible one‐phase reaction of Li extraction/insertion mechanism prevails, unexpectedly, for all lithium compositions of Li_xMn_1/3Fe_1/3Co_1/3PO₄ (0 ≤ x ≤ 1) at room temperature. This is the first demonstration that the well‐ordered, non‐nanocrystalline (less than 1% Li–M disorder and a few hundred nanometer size particle) olivine electrode can be operated solely in a one‐phase mode.     

Ultracompliant Hydrogel‐Based Neural Interfaces Fabricated by Aqueous‐Phase Microtransfer Printing

Hydrogel‐based electronics are ideally suited for neural interfaces because they exhibit ultracompliant mechanical properties that match that of excitable tissue in the brain and peripheral nerve. Hydrogel‐based multielectrode arrays (MEAs) can conformably interface with tissues to minimize inflammation and improve the reliability to enhance signal transduction. However, MEA substrates composed of swollen hydrogels exhibit low toughness and poor adhesion when laminated on the tissue surface and also present incompatibilities with processes commonly used in MEA fabrication. Here, a strategy to fabricate an ultracompliant MEA is described based on aqueous‐phase transfer printing. This technique employs redox active adhesive motifs in hygroscopic polymer precursors that simultaneously form hydrogels through sol–gel phase transitions and bond to materials in the underlying microelectronic structures. Specifically, in situ gelation of four‐arm‐polyethylene glycol‐grafted catechol [PEG‐Dopa]₄ hydrogels induced by oxidation using Fe³⁺ produces conformal adhesive contact with the underlying MEA, robust adhesion to electronic sub‐structures, and rapid dissolution of water‐soluble sacrificial release layers. MEAs are integrated on hydrogel‐based substrates to produce free‐standing ultracompliant neural probes, which are then laminated to the surface of the dorsal root ganglia in feline subjects to record single‐unit neural activity.     

Physical Double‐Network Hydrogel Adhesives with Rapid Shape Adaptability,Fast Self‐Healing,Antioxidant and NIR/pH Stimulus‐Responsiveness for Multidrug‐Resistant Bacterial Infection and Removable Wound Dressing

Developing physical double‐network (DN) removable hydrogel adhesives with both high healing efficiency and photothermal antibacterial activities to cope with multidrug‐resistant bacterial infection, wound closure, and wound healing remains an ongoing challenge. An injectable physical DN self‐healing hydrogel adhesive under physiological conditions is designed to treat multidrug‐resistant bacteria infection and full‐thickness skin incision/defect repair. The hydrogel adhesive consists of catechol–Fe³⁺ coordination cross‐linked poly(glycerol sebacate)‐co‐poly(ethylene glycol)‐g‐catechol and quadruple hydrogen bonding cross‐linked ureido‐pyrimidinone modified gelatin. It possesses excellent anti‐oxidation, NIR/pH responsiveness, and shape adaptation. Additionally, the hydrogel presents rapid self‐healing, good tissue adhesion, degradability, photothermal antibacterial activity, and NIR irradiation and/or acidic solution washing‐assisted removability. In vivo experiments prove that the hydrogels have good hemostasis of skin trauma and high killing ratio for methicillin‐resistant staphylococcus aureus (MRSA) and achieve better wound closure and healing of skin incision than medical glue and surgical suture. In particular, they can significantly promote full‐thickness skin defect wound healing by regulating inflammation, accelerating collagen deposition, promoting granulation tissue formation, and vascularization. These on‐demand dissolvable and antioxidant physical double‐network hydrogel adhesives are excellent multifunctional dressings for treating in vivo MRSA infection, wound closure, and wound healing.     

Unusual Strain Accommodation and Conductivity Enhancement by Structure Modulation Variations in Sr4Fe6O12+δ Epitaxial Films

Mixed ionic and electronic conducting (MIEC) films can be applied in solid state electrochemical devices such as oxygen separation membranes for producing pure oxygen, gas sensors or as cathode in solid oxide fuel cells. The current interest in layered perovskite‐related phases, like Sr₄Fe₆O₁₃ (SFO), arises from their significant oxygen permeability as predicted from theoretical studies. Nevertheless, before any practical application further fundamental study on this fairly unknown oxide is required mainly to assess the mechanisms affecting the transport properties. Epitaxial Sr₄Fe₆O_12+δ (SFO) films of b‐axis orientation with different thicknesses have been prepared by the pulsed laser deposition technique onto different perovskite substrates: SrTiO₃, NdGaO₃ and LaAlO₃. The strain accommodation has been found to vary as a function of film thickness as well as the substrate material causing different type of defects in the film microstructure, as well as variations in the oxygen anion content and ordering. Correspondingly, the total electrical conductivity of the films has been also found to vary significantly as a function of thickness and substrate type showing an unexpected enhancement for strained thin films. The variations in the transport properties are discussed in terms of the different strain accommodation mechanisms and the variation of the modulated structure observed for this compound.     

A Stiff Injectable Biodegradable Elastomer

Injectable materials often have shortcomings in mechanical and drug‐eluting properties that are attributable to their high water contents. A water‐free, liquid four‐armed PEG modified with dopamine end groups is described which changes from liquid to elastic solid by reaction with a small volume of Fe³⁺ solution. The elastic modulus and degradation times increase with increasing Fe³⁺ concentrations. Both the free base and the water‐soluble form of lidocaine can be dissolved in the PEG₄‐dopamine and released in a sustained manner from the cross‐linked matrix. PEG₄‐dopamine is retained in the subcutaneous space in vivo for up to 3 weeks with minimal inflammation. This material's tailorable mechanical properties, biocompatibility, ability to incorporate hydrophilic and hydrophobic drugs and release them slowly are desirable traits for drug delivery and other biomedical applications.     

Ferroelectric and Magnetic Properties in Room‐Temperature Multiferroic GaxFe2−xO3 Epitaxial Thin Films

GaFeO₃‐type iron oxide is a promising room‐temperature multiferroic material due to its large magnetization. To expand its usability, controlling the ferroelectric and magnetic properties is crucial. In this study, high‐quality Ga_xFe_2–xO₃ (x = 0–1) epitaxial films are fabricated and their properties are systematically investigated. All films exhibit room‐temperature out‐of‐plane ferroelectricity, showing that the coercive electric field (E_c) decreases monotonically with x. Additionally, the films show in‐plane ferrimagnetism with a Curie temperature (T_C) >350 K at x = 0–0.6. The coercive magnetic field (H_c) decreases with x at x ≤ 0.6, but shows a constant value at x > 0.6, whereas the saturated magnetization (M_s) increases with x at x ≤ 0.6, but decreases with x at x > 0.6. X‐ray magnetic circular dichroism reveals that the large magnetization at x = 0.6 is derived from Fe³⁺ (3d⁵) at octahedral sites. The controllable range of the E_c, H_c, and M_s values at room temperature (400–800 kV cm^?1, 1–8 kOe, and 0.2–0.6 µ_B/f.u.) is very wide and differs from those of well‐known multiferroic BiFeO₃. Furthermore, the Ga_xFe_2?xO₃ films exhibit room‐temperature magnetocapacitance effects, indicating that adjusting T_C near room temperature is useful to achieve large room‐temperature magnetocapacitance behavior.     

Biopolymer Networks for the Solid‐State Production of Porous Magnetic Beads and Wires

Aqueous solutions of sodium carboxymethyl cellulose are used for the morphosynthesis of spherical and wire‐shaped biopolymer networks, in which Fe³⁺ cations serve as a crosslinking and hardening agent. Their morphology remains intact upon drying, resulting in monolithic beads (1 mm) and wires (ca. 80 μm), which are exploited as reaction vessels to pre‐encapsulate poly(ethylene glycol) 400 (PEG 400) and cobalt cations. A solid‐state reaction in an inert atmosphere at 600 °C affords porous carbonaceous xerogels, macroscopically shaped as beads or wires and decorated with nanocrystalline magnetic iron oxide, metallic iron, or iron–cobalt alloy particles, thus imparting magnetic properties to the products. As such the reduction of Fe³⁺ species to α‐Fe nanoparticles can be achieved without H₂ treatment, since poly(ethylene glycol) serves as a reducing agent and the encapsulated Co²⁺ aids in the subsequent growth of the metallic iron particles. Particularly interesting are the magnetic properties of the carbon–α‐Fe composite, in which the size of the magnetic particles, estimated near the boundaries of the single magnetic domain, gives rise to increased coercivity compared with that of bulk iron.     

Nanoshells with Targeted Simultaneous Enhancement of Magnetic and Optical Imaging and Photothermal Therapeutic Response

Integrating multiple functionalities into individual nanoscale complexes is of tremendous importance in biomedicine, expanding the capabilities of nanoscale structures to perform multiple parallel tasks. Here, the ability to enhance two different imaging technologies simultaneously—fluorescence optical imaging and magnetic resonance imaging—with antibody targeting and photothermal therapeutic actuation is combined all within the same nanoshell‐based complex. The nanocomplexes are constructed by coating a gold nanoshell with a silica epilayer doped with Fe₃O₄ and the fluorophore ICG, which results in a high T₂ relaxivity (390 mM ^?1 s^?1) and 45× fluorescence enhancement of ICG. Bioconjugate nanocomplexes target HER2+ cells and induce photothermal cell death upon near‐IR illumination.     

A Marine‐Inspired Hybrid Sponge for Highly Efficient Uranium Extraction from Seawater

Marine sponges are used as biomonitors of heavy metals contamination in coastal environment as they process large amounts of water and have a high capacity for accumulating heavy metals. Here, inspired by the unique physical and physiological features of marine sponges, a surface engineered synthetic sponge for the highly efficient harvesting of uranium from natural seawater is developed. An ultrathin poly(imide dioxime) (PIDO)/alginate (Alg) interpenetrating polymer network hydrogel layer is uniformly wrapped around the skeleton of a melamine sponge (MS) substrate through a simple dipping–drying–crosslinking process, providing the hybrid MS@PIDO/Alg sponge with excellent uranium adsorption performance and sufficient mechanical strength to withstand the harsh conditions of practical applications. The maximum adsorption capacity reaches 910.98 mg‐U g‐gel^‐1 for the PIDO/Alg hydrogel layer and 291.51 mg‐U g‐sponge^‐1 for the whole hybrid MS@PIDO/Alg sponge in uranium‐spiked natural seawater. The adsorption capacity measured after 56 d of exposure in 5 tons of natural seawater is evaluated to be 5.84 mg‐U g‐gel^‐1 (1.87 mg‐U g‐sponge^‐1). This novel approach shows great promise for the mass production of high‐performance sponge adsorbent for uranium recovery from natural seawater and nuclear waste.