Self-Tandem Bio-Heterojunctions Empower Orthopedic Implants with Amplified Chemo-Photodynamic Anti-Pathogenic Therapy and Boosted Diabetic Osseointegration

Hyperglycemic microenvironment in diabetes mellitus inevitably stalls the normal orchestrated course of bone regeneration and encourages pathogenic multiplication. Photodynamic therapy (PDT) and chemo-dynamic therapy (CDT) are extensively harnessed to combat pathogens, yet deep-seated diabetic bone defect has difficulty in supplying sufficient oxygen (O₂) and hydrogen peroxide (H₂O₂) stocks, resulting in inferior therapeutic efficiency. To address the tough plaguing, the self-tandem bio-heterojunctions (bio-HJs) consisting of molybdenum disulfide (MoS₂), graphene oxide (GO), and glucose oxidase (GOx) are constructed on orthopedic polyetheretherketone (PEEK) implants (SP-Mo/G@GOx) for amplified chemo-photodynamic anti-pathogenic therapy and boosted osseointegration in the deep-seated diabetic micromilieu. In this system, GOx exhausts glucose to generate H₂O₂, which provides an abundant stock for CDT. Besides, the bio-HJs produce hyperthermia upon near-infrared light (NIR) to accelerate the dynamic process, which amplifies the antibacterial potency of PDT by promoting the vast yield of singlet oxygen (¹O₂) in a self-tandem manner. More importantly, in vivo and in vitro assays demonstrate that the engineered implants exert a captivated bactericidal ability and significantly boost osseointegration in an infectious diabetic bone defect model. As envisaged, this study furnishes a novel tactic to arm orthopedic implants with self-tandem capability for the remedy of infectious diabetic bone defects.     

Magnetic Hyperthermia–Synergistic H2O2 Self‐Sufficient Catalytic Suppression of Osteosarcoma with Enhanced Bone‐Regeneration Bioactivity by 3D‐Printing Composite Scaffolds

Chemotherapy resistance and bone defects caused by surgical excision of osteosarcoma have been formidable challenges for clinical treatment. Although recently developed nanocatalysts based on Fenton‐like reactions for catalytic therapy demonstrate high potential to eliminate chemotherapeutic‐insensitive tumors, insufficient concentration of intrinsic hydrogen peroxide (H₂O₂) and low intratumoral penetrability hinder their applications and therapeutic efficiency. The synchronous enriching intratumor H₂O₂ amount or nanoagents and promoting osteogenesis are intriguing strategies to solve the dilemma in osteosarcoma therapy. Herein, a multifunctional “all‐in‐one” biomaterial platform is constructed by co‐loading calcium peroxide (CaO₂) and iron oxide (Fe₃O₄) nanoparticles into a three‐dimensional (3D) printing akermanite scaffold (AKT‐Fe₃O₄‐CaO₂). The loaded CaO₂ nanoparticles act as H₂O₂ sources to achieve H₂O₂ self‐sufficient nanocatalytic osteosarcoma therapy as catalyzed by coloaded Fe₃O₄ nanoagents, as well as provide calcium ion (Ca²⁺) pools to enhance bone regeneration. The synergistic osteosarcoma‐therapeutic effect is achieved from both magnetic hyperthermia as‐enabled by Fe₃O₄ nanoparticles under alternative magnetic fields and hyperthermia‐enhanced Fenton‐like nanocatalytic reaction for producing highly toxic hydroxyl radicals. Importantly, the constructed 3D AKT‐Fe₃O₄‐CaO₂ composite scaffolds are featured with favorable bone‐regeneration activity, providing a worthy base and positive enlightenment for future osteosarcoma treatment with bone defects by the multifunctional biomaterial platforms.     

A Copper Single-Atom Cascade Bionanocatalyst for Treating Multidrug-Resistant Bacterial Diabetic Ulcer

Diabetic ulcers induced by multidrug-resistant (MDR) bacteria have severely endangered diabetic populations. These ulcers are very challenging to treat because the local high glucose concentration can both promote bacterial growth and limit the immune system's bactericidal action. Herein, a glucose oxidase-peroxidase (GOx-POD) dual-enzyme mimetic (DEM) bionanocatalyst, Au@CuBCats is synthesized to simultaneously control glucose concentration and bacteria in diabetic ulcers. Specifically, the AuNPs can serve as GOx mimics and catalyze the oxidation of glucose for the formation of H₂O₂; the H₂O₂ can then be further catalytically converted into OH via the POD-mimetic copper single atoms. Notably, the unique copper single atoms coordinated by one oxygen and two nitrogen atoms (CuN₂O₁) exhibit better POD catalytic performance than natural peroxidase. Further DFT calculations are conducted to study the catalytic mechanism and reveal the advantage of this CuN₂O₁ structure as compared to other copper single-atom sites. Both in vitro and in vivo experiments confirm the outstanding antibacterial therapeutic efficacy of the DEM bionanocatalyst. This new bionanocatalyst will provide essential insights for the next generation of antibiotic-free strategies for combating MDR bacterial diabetic ulcers, and also offer inspiration for designing bionanocatalytic cascading medicines.     

Ni3V2O8 Nanosheets Grafted on 3D Helical-shaped Carbon Nanocoils as A Binder-free Hierarchical Composite for Efficient Non-enzymatic Glucose Sensing

High fabrication cost, chemical instability, and complex immobilization of enzyme molecules are critical issues of enzyme-based glucose sensors. Designing state-of-the-art, binder-free, and non-enzymatic glucose sensing probes plays an imperative role to cope with the aforementioned issues. 3D carbonaceous nanomaterials coated with transition metal vanadates (TMVs) are a favorable biomimetic platform for glucose quantification. Peculiar hierarchical structure, enhanced conductivity, synergistic interaction, multiple oxidation states, and high catalytic activity would make such composite a potential contender for non-enzymatic glucose sensing. Herein, 3D helical-shaped carbon nanocoils (CNCs) are grown on nickel foam (NF) via chemical vapor deposition method to prepare a robust CNCs/NF scaffold. Then, a hydrothermal route is followed to grow interconnected free-standing Ni₃V₂O₈ nanosheets (NSs) on CNCs/NF scaffold. This novel and binder-free Ni₃V₂O₈ NSs/CNCs/NF hierarchical composite possesses superior electrochemical active area (ECSA) and exceptional electrochemical efficacy. Amperometric analysis exhibits extremely prompt detection time (0.1 s), elevated sensitivity (5214 µA mM⁻¹ cm⁻²), and low detection limit (0.04 µM). Developed sensor demonstrates appreciable recoveries (93.3 to 103.3%) regarding glucose concentration in human serum. The appealing analytical results show that deployment of a 3D helical-shaped hierarchical smart scaffold can be an effective strategy for developing efficient and advanced non-enzymatic glucose sensors.     

A Highly Efficient Electrochemical Biosensing Platform by Employing Conductive Nanocomposite Entrapping Magnetic Nanoparticles and Oxidase in Mesoporous Carbon Foam

A conductive multi‐catalyst system consisting of Fe₃O₄ magnetic nanoparticles (MNPs) and oxidative enzymes co‐entrapped in the pores of mesoporous carbon is developed as an efficient and robust electrochemical biosensing platform. The construction of the nanocomposite begins with the incorporation of MNPs by impregnating Fe(NO₃)₃ on a wall of mesoporous carbon followed by heat treatment under an Ar/H₂ atmosphere, which results in the formation of magnetic mesoporous carbon (MMC). Glucose oxidase (GOx) is subsequently immobilized in the remaining pore spaces of the MMC by using glutaraldehyde crosslinking to prevent enzyme leaching from the matrix. H₂O₂ generated by the catalytic action of GOx in proportion to the amount of target glucose is subsequently reduced into H₂O by the peroxidase mimetic activity of MNPs generating cathodic current, which can be detected through the conductive carbon matrix. To develop a robust and easy‐to‐use electrocatalytic biosensing platform, a carbon paste electrode is prepared by mechanically mixing the nanocomposite or MMCs and mineral oil. Using this strategy, H₂O₂ and several phenolic compounds are amperometrically determined employing MMCs as peroxidase mimetics, and target glucose was successfully detected over a wide range of 0.5 × 10^?3 to 10 × 10^?3 M , which covers the actual range of glucose concentration in human blood, with excellent storage stability of over two months at room temperature. Sensitivities of the biosensor (19 to 36 nA mM ^?1) are about 7–14 times higher than that of the biosensor using immobilized GOx in mesoporous carbon without MNPs under optimized condition. The biosensor is of considerable interest because of its potential for expansion to any oxidases, which will be beneficial for use in practical applications by replacing unstable organic peroxidase with immobilized MNPs in a conductive carbon matrix.     

Biodegradable Calcium Phosphate Nanotheranostics with Tumor-Specific Activatable Cascade Catalytic Reactions-Augmented Photodynamic Therapy

Photodynamic therapy (PDT) is exploited as a promising strategy for cancer treatment. However, the hypoxic solid tumor and the lack of tumor-specific photosensitizer administration hinder the further application of oxygen (O₂)-dependent PDT. In this study, a biodegradable and O₂ self-supplying nanoplatform for tumor microenvironment (TME)-specific activatable cascade catalytic reactions-augmented PDT is reported. The nanoplatform (named GMCD) is constructed by coloading catalase (CAT) and sinoporphyrin sodium (DVDMS) in the manganese (Mn)-doped calcium phosphate mineralized glucose oxidase (GOx) nanoparticles. The GMCD can effectively accumulate in tumor sites to achieve an “off to on” fluorescence transduction and a TME-activatable magnetic resonance imaging. After internalization into cancer cells, the endogenous hydrogen peroxide (H₂O₂) can be catalyzed to generate O₂ by CAT, which not only promotes GOx catalytic reaction to consume more intratumoral glucose, but also alleviates tumor hypoxia and enhances the production of cytotoxic singlet oxygen from light-triggered DVDMS. Moreover, the H₂O₂ generated by GOx-catalysis can be converted into highly toxic hydroxyl radicals by Mn²⁺-mediated Fenton-like reaction, further amplifying the oxidative damage of cancer cells. As a result, GMCD displays superior therapeutic effects on 4T1-tumor bearing mice by a long term cascade catalytic reactions augmented PDT.     

Co–Ferrocene MOF/Glucose Oxidase as Cascade Nanozyme for Effective Tumor Therapy

Chemodynamic therapy (CDT), enabling selective therapeutic effects and low side effect, attracts increasing attention in recent years. However, limited intracellular content of H₂O₂ and acid at the tumor site restrains the lasting Fenton reaction and thus the anticancer efficacy of CDT. Herein, a nanoscale Co–ferrocene metal–organic framework (Co‐Fc NMOF) with high Fenton activity is synthesized and combined with glucose oxidase (GOx) to construct a cascade enzymatic/Fenton catalytic platform (Co‐Fc@GOx) for enhanced tumor treatment. In this system, Co‐Fc NMOF not only acts as a versatile and effective delivery cargo of GOx molecules to modulate the reaction conditions, but also possesses excellent Fenton effect for the generation of highly toxic ?OH. In the tumor microenvironment, GOx delivered by Co‐Fc NMOF catalyzes endogenous glucose to gluconic acid and H₂O₂. The intracellular acidity and the on‐site content of H₂O₂ are consequently promoted, which in turn favors the Fenton reaction of Co‐Fc NMOF and enhances the generation of reactive oxygen species (ROS). Both in vitro and in vivo results demonstrate that this cascade enzymatic/Fenton catalytic reaction triggered by Co‐Fc@GOx nanozyme enables remarkable anticancer properties.     

Fluorescence‐Amplifying Detection of Hydrogen Peroxide with Cationic Conjugated Polymers,and Its Application to Glucose Sensing

A highly sensitive hydrogen peroxide probe that takes advantage of the amplified fluorescence quenching of conjugated polymers has been developed. The cationic conjugated polymer, poly(9,9‐bis(6′‐N,N,N‐trimethylammonium‐hexyl) fluorene phenylene) (PFP‐NMe₃⁺) and peroxyfluor‐1 with boronate protecting groups (Fl‐BB) are used to detect H₂O₂ optically. Without the addition of H₂O₂, the absence of electrostatic interactions between the cationic PFP‐NMe₃⁺ and the neutral Fl‐BB keeps the Fl‐BB well separated from the PFP‐NMe₃⁺, and no fluorescence quenching of the PFP‐NMe₃⁺ occurs. In the presence of H₂O₂, the formation of the anionic quencher, fluorescein, by specific reaction of the Fl‐BB with H₂O₂ results in strong electrostatic interactions between the PFP‐NMe₃⁺ and the fluorescein, and therefore efficient fluorescence quenching of the PFP‐NMe₃⁺ occurs. The absorption of fluorescein overlaps the emission of PFP‐NMe₃⁺, which encourages fluorescence resonance energy transfer (FRET) from the PFP‐NMe₃⁺ to the fluorescein. The H₂O₂ probe has very good sensitivity, with a detection range of 15 to 600 nM. Since glucose oxidase (GOx) can specifically catalyze the oxidation of β‐D ‐(+)‐glucose to generate H₂O₂, glucose detection is also realized with the H₂O₂ probe as the signal transducer.     

A Multifunctional Pro‐Healing Zwitterionic Hydrogel for Simultaneous Optical Monitoring of pH and Glucose in Diabetic Wound Treatment

Diabetic ulcer is the most common kind of chronic wound worldwide. Though great efforts have been devoted, diabetic ulcer still remains as a challenge that requires constant monitoring and management. In this work, a multifunctional zwitterionic hydrogel is developed to simultaneously detect two fluctuant wound parameters, pH and glucose level, to monitor the diabetic wound status. A pH indicator dye (phenol red) and two glucose sensing enzymes, glucose oxidase (GOx) and horseradish peroxidase (HRP), are encapsulated in the anti‐biofouling and biocompatible zwitterionic poly‐carboxybetaine (PCB) hydrogel matrix. The visible images are collected by a smartphone and transformed into RGB signals to quantify the wound parameters. Results show that the activity and stability of both two enzymes are improved within PCB hydrogel, and the K_cat/K_m value of PCB‐HRP is ≈5.5 fold of free HRP in artificial wound exudate. This novel wound dressing can successfully monitor the pH range of 4–8 and glucose level of 0.1–10 × 10^?3 m . Meanwhile, it also provides a moist healing environment that can promote diabetic wound healing. This multifunctional wound dressing may open vistas in chronic wound management and guide the diabetes treatment in clinical applications.     

Liver‐Target and Glucose‐Responsive Polymersomes toward Mimicking Endogenous Insulin Secretion with Improved Hepatic Glucose Utilization

Oral insulin therapy that targets the liver and further mimics glucose‐responsive secretion holds promise for correcting defects in glucose metabolism caused by peripheral delivery. This work describes the construction of polymersomes (Pep‐PMS), which are composed of glucose‐responsive polymers decorated with peptides that readily bind to the ganglioside‐monosialic acid (GM1) receptor in the intestinal epithelium. Pep‐PMS are efficiently transported across the intestinal epithelium through GM1‐mediated transcytosis, leading to their abundant accumulation in the liver. Moreover, Pep‐PMS can efficiently encapsulate insulin in euglycemia and release them in hyperglycemia. Under hyperglycemic conditions, the Pep‐PMS dissociate to release the encapsulated insulin in response to glucose oxidase (GOx)‐induced H₂O₂. Surprisingly, the postprandial blood glucose levels of diabetic rats treated with Pep‐PMS can be maintained even after being challenged by glucose administration. Hepatic glucose uptake and glycogen production are also elevated after treating diabetic rats with Pep‐PMS, which is similar to glucose utilization in normal rats. Oral delivery systems that target the liver and serve as a reservoir for glucose‐responsive insulin secretion may improve the therapeutic effect in people with diabetes.     

Enhanced photocatalytic activity of graphene oxide/titania nanosheets composites for methylene blue degradation

In the present work, we report enhanced photocatalytic degradation of methylene blue dye in aqueous solution by using ultra-thin anatase TiO₂ nanosheets (NSs) combined with graphene oxide (GO) as a photocatalyst. The two-dimensional ultra-thin anatase TiO₂ NSs are fabricated via chemical exfoliation. By completely delaminating a lepidocrocite-type layered protonic titanate H_xTi_2−x/4□_x/4O₄·H₂O (x=0.7, □: vacancy) into individual layers through ion exchange with tetrabutylammonium (TBA⁺) cations, well-dispersed ultra-thin colloidal Ti_0.91O₂ NSs with a lateral size up to a few micrometers are obtained. Subsequent acid treatment induces colloidal Ti_0.91O₂ to reassemble and precipitate into a gelation form, followed by thermal annealing to convert the Ti_0.91O₂ gelation into anatase TiO₂ nanosheets as photocatalyst for methylene blue degradation. TiO₂ NSs show a high photocatalytic degradation efficiency of 53.2% due to the ultra-thin thickness for facile electron transfering and large surface area for methylene blue absorption. Moreover, photocatalytic effect can be further improved by simply adding GO suspension to achieve colloidal self-assembly of GO and TiO₂ NSs. An optimal GO content of 3 wt% further increases the photocatalytic degradation efficiency to 91.2% due to faster electron–hole seperation and improved surface area provided by GO. This work provides a simple but effective approach by combing graphene oxide with TiO₂ nanosheets synthesized via the exfoliation method for methylene blue degradation.     

3D Superelastic Scaffolds Constructed from Flexible Inorganic Nanofibers with Self‐Fitting Capability and Tailorable Gradient for Bone Regeneration

Repair of bone defects with irregular shapes or at soft tissue insertion sites faces a huge challenge. Scaffolds capable of adapting to bone cavities, generating stiffness gradients, and inducing osteogenesis are necessary. Herein, a superelastic 3D ceramic fibrous scaffold is developed by assembly of intrinsically rigid, structurally flexible electrospun SiO₂ nanofibers with chitosan as bonding sites (SiO₂ NF‐CS) via a lyophilization technique. SiO₂ NF‐CS scaffolds exhibit excellent elasticity (full recovery from 80% compression), fast recovery rate (>500 mm min^?1), and good fatigue resistance (>10 000 cycles of compression) in an aqueous medium. SiO₂ NF‐CS scaffolds induce human mesenchymal stem cell (hMSC) elongation and differentiation into osteoblasts. In vivo self‐fitting capability is demonstrated by implanting compressed SiO₂ NF‐CS scaffolds into different shaped mandibular defects in rabbits, with a spontaneous recovery and full filling of defects. Rat calvarial defect repair validates enhanced bone formation and vascularization by cell (hMSC) histomorphology analysis. Further, subchondral bone scaffolds with gradations in SiO₂ nanofibers are developed, leading to a stiffness gradient and spatially chondrogenic and osteogenic differentiation of hMSCs. This work presents a type of 3D ceramic fibrous scaffold, which can closely match bone defects with irregular shapes or at different implant sites, and is promising for clinical translation.     

Z‐Scheme Heterojunction Functionalized Pyrite Nanosheets for Modulating Tumor Microenvironment and Strengthening Photo/Chemodynamic Therapeutic Effects

A Z‐scheme heterojunction with high electron–hole pairs separation efficacy and enhanced redox potentials exhibits tremendous potential in photonic theranostics, but still remains unexplored and challenging. Herein, novel 2D thermally oxidized pyrite nanosheets (TOPY NSs) with FeS₂ core and Fe₂O₃ shell are fabricated combining ball grinding and two‐step probe sonication assisted liquid exfoliation under different solution and air environments. The Fe₂O₃ shell and Fe³⁺/Fe²⁺ inside TOPY NSs can both damage the tumor microenvironment through glutathione consumption and O₂ production, and produce ·OH by Fenton reaction. More interestingly, a direct Z‐scheme heterojunction based on FeS₂ core and Fe₂O₃ shell is constructed, in which the electrons in the conduction band (CB) of Fe₂O₃ are recombined with the holes in the valence band (VB) of FeS₂, leaving stronger reduction/oxidation potentials in the CB of FeS₂ and the VB of Fe₂O₃. Under irradiation of a 650 nm laser, the generation of ·O₂^? from O₂ and ·OH from OH^? on the CB of FeS₂ and VB of Fe₂O₃, respectively, is largely enhanced. Furthermore, the NSs can be triggered by an 808 nm laser to generate local hyperthermia for photothermal therapy. Moreover, the fluorescent, photoacoustic, and photothermal imaging capabilities of the NSs allow multimodal imaging‐guided cancer treatment.     

Sulfite-Inserted MgAl Layered Double Hydroxides Loaded with Glucose Oxidase to Enable SO2-Mediated Synergistic Tumor Therapy

As a type of unique gaseous molecules, SO₂ presents capabilities in the feasible cellular influx and the induction of apoptosis by generating intracellular toxic radicals. Developing therapeutic platforms to enable effective SO₂ gas release at the tumor site is highly demanded in the exploration of more “green” and effective treatment protocols for cancer therapy but remains challenging. Here for the first time, fine nanosheets composing of Mg-Al layered double hydroxides (MgAl LDH) are synthesized and inserted with sulfite in its layered structures (MgAl-SO₃ LDH). After the loading of glucose oxidase (GOx/MgAl-SO₃ LDH), the composite nanosheets present the controllable SO₂ gas release in an acidic responsive manner. Owing to the glycolysis effect of GOx, the gluconic acid generated agitates the intracellular SO₂ release from nanosheets, and excessive H₂O₂ reacts with SO₂ effectively and facilitates the production of toxic radicals, inducing remarkable oxidative damages to tumor cells. Meanwhile, the consumption of intracellular glucose by GOx/MgAl-SO₃ LDH depletes the energy supply of tumor cells, favoring the tumor inhibition both in vitro and in vivo in a synergistic fashion. Therefore, this study has provided distinctive perspectives in the exploration of therapeutic platforms with green functionalities and biodegradability for effective tumor treatment.     

Stepwise Degradable Nanocarriers Enabled Cascade Delivery for Synergistic Cancer Therapy

Hypoxia‐activated prodrugs have brought new opportunities for safe and effective tumor ablation, but their therapeutic efficacy is limited by insufficient activation in tumor microenvironments. Herein, a novel cascade delivery system with tandem functions by integrating a hypoxia‐activated prodrug (AQ4N) and glucose oxidase (GOx) is designed to improve its efficacy. Innovative yolk–shell organosilica nanoparticles with a tetrasulfide bridged composition, a small‐pore yolk, and a large‐pore shell featuring a shell‐to‐yolk stepwise degradability are constructed as a carrier for AQ4N and GOx, one enzyme that catalyzes the oxidation of glucose to produce hydrogen peroxide. The glutathione (GSH) is depleted by tetrasulfide bond in the framework and induces shell degradation for fast release of GOx, which in turn induces starvation (glucose removal), oxidative cytotoxicity (H₂O₂ production and GSH depletion), and hypoxia (oxygen consumption). Finally, the hypoxia activates the liberated prodrug AQ4N for chemotherapy. The cascading and synergistic functions including GSH depletion, starvation, oxidative cytotoxicity, and chemotherapy lead to improved performance in tumor inhibition and antimetastasis.     

3D Neighborhood Nanostructure Reinforces Biosensing Membrane

The electron signals in the cell can be rapidly and accurately transmitted by the spatially confined and adjacently distributed enzyme pairs anchored in the cytomembrane. As inspiration, by leverage of tannic acid-3-aminopropyltriethoxysilane-Fe (TA-APTES-Fe) ternary coating, for the first time, a mesoporous biosensing membrane is developed by orderly assembly and targeted confinement of Prussian blue (PB) and glucose oxidase (GOx) with neighborhood nanostructure in the 3D mesoporous carbon nanotubes (CNTs) membrane electrode. The mesoporous biosensing membrane extends the triple-phase boundary from conventional 2D contact to 3D contact, promotes the transfer rates of the cascade reactants, enhances the proximity of PB, GOx, and the electrode, and achieves in–situ removal of interferents, thereby elevating the utilization of PB, enhancing the cascade reaction efficiency, increasing the availability of the electroactive hydrogen peroxide (H₂O₂), and improving its stability. It exhibits superior sensitivity (31.2 µA mM⁻¹) and long-term stability in continuous glucose monitoring with a negligible response drift for up to 8 h. In addition, the multienzyme mimic functions of PB are employed to imitate the “loosening-degradation” membrane cleaning process via bubble scrubbing and Fenton oxidation, thereby fully regenerating the fouled biosensing membrane. This work provides a novel design strategy for biosensors toward efficient, reliable, and stable sensing.     

Magnesium Gradient-Based Hierarchical Scaffold for Dual-Lineage Regeneration of Osteochondral Defect

Osteochondral regeneration remains a great challenge due to the limited self-healing ability and the complexity of its hierarchical structure and composition. Mg²⁺ and hypoxia are two effective modulators in boosting chondrogenesis. To this end, a double-layered scaffold (D) consisting of a hydrogel layer on a porous cryogel is fabricated to mimic the hierarchical structure of osteochondral tissue. An Mg²⁺ gradient is incorporated into the double-layered scaffold with hypoxia-mimicking deferoxamine (DFO) embedded in the hydrogel (D-Mg-DFO), which remarkably augments the dual-lineage regeneration of both cartilage and subchondral bone. The higher Mg²⁺ supplementation from the upper hydrogel, associated with its hypoxia-mimicking situation and small pore size, exhibits promotive effects on chondrogenic differentiation. The lower Mg²⁺ supplementation from the bottom cryogel, associated with its interconnected macroporous structure, achieves multiple contributions in stem cell migration from bone marrow cavity, matrix mineralization, and osteogenesis. Furthermore, rabbits’ trochlea osteochondral defects are established to evaluate the regenerative outcome. Compared to control scaffolds containing only Mg²⁺ or DFO, the D-Mg-DFO scaffold presents the best regenerative effect under the synergistic contribution of multiple factors. Overall, this work provides a new design of scaffold toward an effective repair of cartilage defect.     

A Bifunctional Biomaterial with Photothermal Effect for Tumor Therapy and Bone Regeneration

Malignant bone tumor is one of the major bone diseases. The treatment of such a bone disease typically requires the removal of bone tumor and regeneration of tumor‐initiated bone defects simultaneously. To address this issue, it is required that implanted biomaterials should combine the bifunctions of both therapy and regeneration. In this work, a bifunctional graphene oxide (GO)‐modified β‐tricalcium phosphate (GO‐TCP) composite scaffold combining a high photothermal effect with significantly improved bone‐forming ability is prepared by 3D‐printing and surface‐modification strategies. The prepared GO‐TCP scaffolds exhibit excellent photothermal effects under the irradiation of 808 nm near infrared laser (NIR) even at an ultralow power density of 0.36 W cm^?2, while no photothermal effects are observed for pure β‐TCP scaffolds. The photothermal temperature of GO‐TCP scaffolds can be effectively modulated in the range of 40–90 °C by controlling the used GO concentrations, surface‐modification times, and power densities of NIR. The distinct photothermal effect of GO‐TCP scaffolds induces more than 90% of cell death for osteosarcoma cells (MG‐63) in vitro, and further effectively inhibits tumor growth in mice. Meanwhile, the prepared GO‐TCP scaffolds possess the improved capability to stimulate the osteogenic differentiation of rabbit bone mesenchymal stem cells (rBMSCs) by upregulating bone‐related gene expression, and significantly promote new bone formation in the bone defects of rabbits as compared to pure β‐TCP scaffolds. These results successfully demonstrate that the prepared GO‐TCP scaffolds have bifunctional properties of photothermal therapy and bone regeneration, which is believed to pave the way to design and fabricate novel implanting biomaterials in combination of therapy and regeneration functions.     

Biomimetic Ultralight,Highly Porous,Shape‐Adjustable,and Biocompatible 3D Graphene Minerals via Incorporation of Self‐Assembled Peptide Nanosheets

Hybrid nanomaterials with tailored functions, consisting of self‐assembled peptides, are intensively applied in nanotechnology, tissue engineering, and biomedical applications due to their unique structures and properties. Herein, a peptide‐mediated biomimetic strategy is adopted to create the multifunctional 3D graphene foam (GF)‐based hybrid minerals. First, 2D peptide nanosheets (PNSs), obtained by self‐assembling a motif‐specific peptide molecule (LLVFGAKMLPHHGA), are expected to exhibit biofunctionality, such as the biomimetic mineralization of hydroxyapatite (HA) minerals. Subsequently, the noncovalent conjugation of PNSs onto GF support is utilized to form 3D GF‐PNSs hybrid scaffolds, which are suitable for the growth of HA minerals. The fabricated biomimetic 3D GF‐PNSs‐HA minerals exhibit adjustable shape, superlow weight (0.017 g cm^?3), high porosity (5.17 m² g^?1), and excellent biocompatibility, proving potential applications in both bone tissue engineering and biomedical engineering. To the best of the authors' knowledge, it is the first time to combine 2D PNSs and GF to fabricate 3D organic–inorganic hybrid scaffold. Further development of these hybrid GF‐PNSs scaffolds can potentially lead to materials used as matrices for drug delivery or bone tissue engineering as proven via successful 3D scaffold formation exhibiting interconnected pore‐size structures suitable for vascularization and medium transport.     

Rear‐Passivated Ultrathin Cu(In,Ga)Se2 Films by Al2O3 Nanostructures Using Glancing Angle Deposition Toward Photovoltaic Devices with Enhanced Efficiency

In this work, for the first time, the addition of aluminum oxide nanostructures (Al₂O₃ NSs) grown by glancing angle deposition (GLAD) is investigated on an ultrathin Cu(In,Ga)Se₂ device (400 nm) fabricated using a sequential process, i.e., post‐selenization of the metallic precursor layer. The most striking observation to emerge from this study is the alleviation of phase separation after adding the Al₂O₃ NSs with improved Se diffusion into the non‐uniformed metallic precursor due to the surface roughness resulting from the Al₂O₃ NSs. In addition, the raised Na concentration at the rear surface can be attributed to the increased diffusion of Na ion facilitated by Al₂O₃ NSs. The coverage and thickness of the Al₂O₃ NSs significantly affects the cell performance because of an increase in shunt resistance associated with the formation of Na₂Se_X and phase separation. The passivation effect attributed to the Al₂O₃ NSs is well studied using the bias‐EQE measurement and J–V characteristics under dark and illuminated conditions. With the optimization of the Al₂O₃ NSs, the remarkable enhancement in the cell performance occurs, exhibiting a power conversion efficiency increase from 2.83% to 5.33%, demonstrating a promising method for improving ultrathin Cu(In,Ga)Se₂ devices, and providing significant opportunities for further applications.