FePSe3-Nanosheets-Integrated Cryogenic-3D-Printed Multifunctional Calcium Phosphate Scaffolds for Synergistic Therapy of Osteosarcoma

Clinical treatment of osteosarcoma encounters great challenges of postsurgical tumor recurrence and extensive bone defect. To develop an advanced artificial bone substitute that can achieve synergistic bone regeneration and tumor therapy for osteosarcoma treatment, a multifunctional calcium phosphate composite enabled by incorporation of bioactive FePSe₃-nanosheets within the cryogenic-3D-printed α-tricalcium phosphate scaffold (TCP-FePSe₃) is explored. The TCP-FePSe₃ scaffold exhibits remarkable tumor ablation ability due to the excellent NIR-II (1064 nm) photothermal property of FePSe₃-nanosheets. Moreover, the biodegradable TCP-FePSe₃ scaffold can release selenium element to suppress tumor recurrence by activating of the caspase-dependent apoptosis pathway. In a subcutaneous tumor model, it is demonstrated that tumors can be efficiently eradicated via the combination treatment with local photothermal ablation and the antitumor effect of selenium element. Meanwhile, in a rat calvarial bone defect model, the superior angiogenesis and osteogenesis induced by TCP-FePSe₃ scaffold have been observed in vivo. The TCP-FePSe₃ scaffold possesses improved capability to promote the repair of bone defects via vascularized bone regeneration, which is induced by the bioactive ions of Fe, Ca, and P released during the biodegradation of the implanted scaffolds. The TCP-FePSe₃ composite scaffolds fabricated by cryogenic-3D-printing illustrate a distinctive strategy to construct multifunctional platform for osteosarcoma treatment.     

Engineering 2D Mesoporous Silica@MXene‐Integrated 3D‐Printing Scaffolds for Combinatory Osteosarcoma Therapy and NO‐Augmented Bone Regeneration

The rising concerns of the recurrence and bone deficiency in surgical treatment of malignant bone tumors have raised an urgent need of the advance of multifunctional therapeutic platforms for efficient tumor therapy and bone regeneration. Herein, the construction of a multifunctional biomaterial system is reported by the integration of 2D Nb₂C MXene wrapped with S‐nitrosothiol (R? SNO)‐grafted mesoporous silica with 3D‐printing bioactive glass (BG) scaffolds (MBS). The near infrared (NIR)‐triggered photonic hyperthermia of MXene in the NIR‐II biowindow and precisely controlled nitric oxide (NO) release are coordinated for multitarget ablation of bone tumors to enhance localized osteosarcoma treatment. The in situ formed phosphorus and calcium components degraded from BG scaffold promote bone‐regeneration bioactivity, augmented by sufficient blood supply triggered by on‐demand NO release. The tunable NO generation plays a crucial role in sequential adjuvant tumor ablation, combinatory promotion of coupled vascularization, and bone regeneration. This study demonstrates a combinatory osteosarcoma ablation and a full osseous regeneration as enabled by the implantation of MBS. The design of multifunctional scaffolds with the specific features of controllable NO release, highly efficient photothermal conversion, and stimulatory bone regeneration provides an intriguing biomaterial platform for the diversified treatment of bone tumors.     

Hemoglobin Nanocrystals for Drugs Free,Synergistic Theranostics of Colon Tumor (Small 8/2023)

The conventional approach in cancer nanomedicine involves advanced drug nanocarriers delivering preloaded therapeutics to targeted tumor sites to maximize drug efficiency. However, both cancer drugs and nanocarriers inevitably produce side effects and systemic toxicity. Herein, hemoglobin nanocrystals (HbC) as drug-free theranostic nanoformulations with the tumor microenvironment (TME) activated diagnostic and therapeutic abilities towards colon tumors are introduced. HbC can release Fe²⁺ oxidized to Fe³⁺ in the Fenton reaction with tumor endogenous H₂O₂, concurrently with the generation of cytotoxic hydroxyl radicals (•OH) that allow for chemodynamic therapy (CDT). Furthermore, in situ-produced Fe³⁺ reacts with colon tumor-abundant H₂S, resulting in the production of Fe_1−xS, which provides magnetic resonance imaging (MRI) contrast and allows for NIR light-inducible photothermal therapy (PTT). In vitro and in vivo studies revealed that HbC produced CDT towards 4T1 tumors, and MRI-guided, synergistically enhanced combination of CDT and PTT against H₂S abundant colon tumors (CT26), with negligible toxicity towards normal tissues, enlightening HbC as highly efficient and biocompatible TME activated theranostic nanoplatform specific against colon cancer without any traditional drugs and drug carriers.     

RhRu Alloy-Anchored MXene Nanozyme for Synergistic Osteosarcoma Therapy

Noble metal nanozymes hold promise in cancer therapy due to adjustable enzyme-like activities, unique physicochemical properties, etc. But catalytic activities of monometallic nanozyme are confined. In this study, 2D titanium carbide (Ti₃C₂T_x)-supported RhRu alloy nanoclusters (RhRu/Ti₃C₂T_x) are prepared by a hydrothermal method and utilized for synergistic therapy of chemodynamic therapy (CDT), photodynamic therapy (PDT), and photothermal therapy (PTT) on osteosarcoma. The nanoclusters are small in size (3.6 nm), uniform in distribution, and have excellent catalase (CAT) and peroxidase (POD)-like activities. Density functional theory calculations show that there is a significant electron transfer interaction between RhRu and Ti₃C₂T_x, which has strong adsorption to H₂O₂ and is beneficial to enhance the enzyme-like activity. Furthermore, RhRu/Ti₃C₂T_x nanozyme acts as both PTT agent for converting light into heat, and photosensitizer for catalyzing O₂ to ¹O₂. With the NIR-reinforced POD- and CAT-like activity, excellent photothermal and photodynamic performance, the synergistic CDT/PDT/PTT effect of RhRu/Ti₃C₂T_x on osteosarcoma is verified by in vitro and in vivo experiments. This study is expected to provide a new research direction for the treatment of osteosarcoma and other tumors.     

掺钕介孔硼硅酸盐生物活性玻璃陶瓷骨水泥的制备与性能表征

骨肉瘤是一种常见的恶性骨肿瘤, 常通过手术切除进行治疗。但术后造成的骨缺损难以自愈, 残余肿瘤细胞还会增加复发可能性。本研究开发了一种用于修复骨缺损和协同治疗骨肉瘤的掺钕介孔硼硅酸盐生物活性玻璃陶瓷骨水泥。首先通过溶胶-凝胶法结合固态反应制备了可作为光热剂和药物载体的掺钕介孔硼硅酸盐生物活性玻璃陶瓷微球(MBGC-xNd), 然后将微球与海藻酸钠(SA)溶液混合制备了可同时进行光热治疗和化学治疗的可注射骨水泥(MBGC-xNd/SA)。结果表明掺Nd³⁺赋予微球可控的光热性能, 负载阿霉素(DOX)的微球显示出持续的药物释放行为。此外, 载药骨水泥的药物释放量随着温度的升高而显著增加, 说明光热疗法产生的热量可促进DOX释放。体外细胞实验结果表明, MBGC-xNd/SA具有良好的促成骨活性, 并且光热-化学联合疗法对MG-63骨肉瘤细胞起到了更显著的杀伤作用, 表现出协同效应。因此,MBGC-xNd/SA作为一种新颖的多功能骨修复材料, 在骨肉瘤的术后治疗方面具有良好的应用前景。     

Synthesis of Uniquely Structured Yolk–Shell Metal Oxide Microspheres Filled with Nitrogen‐Doped Graphitic Carbon with Excellent Li–Ion Storage Performance

Novel structured composite microspheres of metal oxide and nitrogen‐doped graphitic carbon (NGC) have been developed as efficient anode materials for lithium‐ion batteries. A new strategy is first applied to a one‐pot preparation of composite (FeO_x‐NGC/Y) microspheres via spray pyrolysis. The FeO_x‐NGC/Y composite microspheres have a yolk–shell structure based on the iron oxide material. The void space of the yolk–shell microsphere is filled with NGC. Dicyandiamide additive plays a key role in the formation of the FeO_x‐NGC/Y composite microspheres by inducing Ostwald ripening to form a yolk–shell structure based on the iron oxide material. The FeO_x‐NGC/Y composite microspheres with the mixed crystal structure of rock salt FeO and spinel Fe₃O₄ phases show highly superior lithium‐ion storage performances compared to the dense‐structured FeO_x microspheres with and without carbon material. The discharge capacities of the FeO_x‐NGC/Y microspheres for the 1st and 1000th cycle at 1 A g^?1 are 1423 and 1071 mAh g^?1, respectively. The microspheres have a reversible discharge capacity of 598 mAh g^?1 at an extremely high current density of 10 A g^?1. Furthermore, the strategy described in this study is generally applied to multicomponent metal oxide–carbon composite microspheres with yolk–shell structures based on metal oxide materials.     

Synthesis and magnetic properties of nanocrystalline Y1 ? xCdxFeO3 ? δ (0 ≤ x ≤ 0.2)

We report the synthesis of Y_{1 − x} Cd _x FeO_{3 − δ} nanocrystals in the range x = 0–0.2. The Y_{1 − x} Cd _x FeO_{3 − δ} materials were shown to be single-phase by X-ray diffraction, with an average crystallite size from 23 to 34 nm, depending on composition. With increasing cadmium oxide content, the size of the Y_{1 − x} Cd _x FeO_{3 − δ} nanocrystals decreases and their magnetization rises.     

Hierarchically multifunctional bioactive nanoglass for integrated tumor/infection therapy and impaired wound repair

The complex wound repair induced by tumor surgery and infection is still the clinical challenge due to the subsequent tumor recurrence and serious inflammation. Herein, we develop a bioactive Si-Ca-Sr glass-based therapy-regeneration-enabled nanohybrids (BSr@PPE) with hierarchical versatility for overcoming the challenges of tumor and infection-impaired wound repair. BSr@PPE showed a representative concentration-dependent photothermal effect, strong free radical scavenging and antibacterial ability, as well as good UV-shielding properties and high biocompatibility. BSr@PPE could efficiently kill tumor cells through the photothermal effect, show the robust antibacterial activity against normal and multi-drug resistant bacteria and enhance the fibroblasts migration in vitro. In vivo animal experiments suggested that BSr@PPE could effectively promote epithelial reconstruction, collagen deposition and angiogenesis in normal wounds, reduce inflammation and enhance repair in multi-drug bacterial infected wounds, accelerate the tumor-impaired wound through inhibit the tumor cells. This work may provide a new strategy and multifunctional bioactive material for treating the tissue repair and regeneration under the multi-pathological environments.     

Biomimetic Nanobomb for Synergistic Therapy with Inhibition of Cancer Stem Cells

Cancer stem cells (CSCs), a type of cell with self-renewal, unlimited proliferation, and insensitivity to common physical and chemical factors, are the key to cancer metastasis, recurrence, and chemo-resistance. Available CSCs inhibition strategies are mainly based on small molecule drugs, yet are limited by their off-target toxicity. The link between CSCs and non-CSCs interconversion is difficult to sever. In this work, a nanotherapeutic strategy based on MnO_x-loaded polydopamine (MnO_x/PDA) nanobombs with chemodynamic, photodynamic, photothermal and biodegradation properties to inhibit CSCs and non-CSCs concurrently is reported. The MnO_x/PDA nanobombs can directly disrupt the microenvironment and tumorigenic capacity of CSCs by generating hyperthermia, oxidative stress and alleviating hypoxia. The markers of CSCs are subsequently downregulated, leading to the clearance of CSCs. Meanwhile, the synergistic therapy mediated by MnO_x/PDA nanobombs can directly ablate the bulk tumor cells, thus cutting off the supply of CSCs transformation. For tumor targeting, MnO_x/PDA is coated with macrophage membrane. The final tumor inhibition rate of the synergistic therapy is 70.8% in colorectal cancer (CRC) model. Taken together, the present work may open up the exploration of nanomaterial-based synergistic therapy for the simultaneous elimination of therapeutically resistant CSCs and non-CSCs.     

La-modification of multiferroic BiFeO<Subscript>3</Subscript> by hydrothermal method at low temperature

This study reports the effect of La doping on structural, morphological and magnetic characteristics of BiFeO₃ synthesized under mild hydrothermal conditions at 200°C for 16 h using the KOH concentration of 4 M. The as-synthesized powders of Bi_1−x La _x FeO₃ for x = 0.05, 0.10, and 0.15 were characterized by X-ray powder diffraction scanning electron microscope and the vibrating sample magnetometer. The formation mechanism of Bi_1−x La _x FeO₃ powders can be expressed by “dissolution-nucleation-crystallization” process. The magnetism of Bi_1−x La _x FeO₃ increased with increase of La content due mainly to increscent suppressing spiral magnetic structure and magnetic contribution of La.     

Near-Infrared Regulated Nanozymatic/Photothermal/Photodynamic Triple-Therapy for Combating Multidrug-Resistant Bacterial Infections via Oxygen-Vacancy Molybdenum Trioxide Nanodots

Bacterial infections have become a major danger to public health because of the appearance of the antibiotic resistance. The synergistic combination of multiple therapies should be more effective compared with the respective one alone, but has been rarely demonstrated in combating bacterial infections till now. Herein, oxygen-vacancy molybdenum trioxide nanodots (MoO_3−x NDs) are proposed as an efficient and safe bacteriostatic. The MoO_3−x NDs alone possess triple-therapy synergistic efficiency based on the single near-infrared irradiation (808 nm) regulated combination of photodynamic, photothermal, and peroxidase-like enzymatic activities. Therein, photodynamic and photothermal therapies can be both achieved under the excitation of a single wavelength light source (808 nm). Both the photodynamic and nanozyme activity can result in the generation of reactive oxygen species (ROS) to reach the broad-spectrum sterilization. Interestingly, the photothermal effect can regulate the MoO_3−x NDs to their optimum enzymatic temperature (50 °C) to give sufficient ROS generation in low concentration of H₂O₂ (100 µm ). The MoO_3−x NDs show excellent antibacterial efficiency against drug-resistance extended spectrum β-lactamases producing Escherichia coli and methicillin-resistant Staphylococcus aureus (MRSA). Animal experiments further indicate that the MoO_3−x NDs can effectively treat wounds infected with MRSA in living systems.     

2D‐Black‐Phosphorus‐Reinforced 3D‐Printed Scaffolds:A Stepwise Countermeasure for Osteosarcoma

With the ever‐deeper understanding of nano–bio interactions and the development of fabrication methodologies of nanomaterials, various therapeutic platforms based on nanomaterials have been developed for next‐generation oncological applications, such as osteosarcoma therapy. In this work, a black phosphorus (BP) reinforced 3D‐printed scaffold is designed and prepared to provide a feasible countermeasure for the efficient localized treatment of osteosarcoma. The in situ phosphorus‐driven, calcium‐extracted biomineralization of the intra‐scaffold BP nanosheets enables both photothermal ablation of osteosarcoma and the subsequent material‐guided bone regeneration in physiological microenvironment, and in the meantime endows the scaffolds with unique physicochemical properties favoring the whole stepwise therapeutic process. Additionally, a corrugated structure analogous to Haversian canals is found on newborn cranial bone tissue of Sprague–Dawley rats, which may provide much inspiration for the future research of bone‐tissue engineering.     

Black Bioceramics: Combining Regeneration with Therapy

Bioceramics have been developed from bioinert to bioactive or biodegradable materials in the past few decades. However, at present, traditional bioceramics are still mainly used in bone tissue regeneration and dental restoration. In this work, a new generation of “black bioceramics,” extending the applications from tissue regeneration to disease therapy, is presented. Black bioceramics, through magnesium thermal reduction of traditional white ceramics, including silicate-based (e.g., CaSiO₃, MgSiO₃) and phosphate-based (e.g., Ca₃(PO₄)₂, Ca₅(PO₄)₃(OH)), are successfully synthesized. Due to the presence of oxygen vacancies and structural defects, the black bioceramics possess photothermal functionality while maintaining their initial high bioactivity and regenerative capacity. These black bioceramics show excellent photothermal antitumor effects for both skin and bone tumors. At the same time, they have significantly improved bioactivity for skin/bone tissue repair in vitro and in vivo. These fascinating properties award the black bioceramics with profound applications in both tumor therapy and tissue regeneration, which should greatly promote the scientific relevance and clinical application of bioceramics, representing a promising new direction of cell-instructive biomaterials.     

Specific features of the processes of thermal desorption and HDDR in the Zr<Subscript>3</Subscript>FeO<Subscript>x</Subscript>H<Subscript>y</Subscript> system

We study the processes of thermal desorption of hydrogen and hydride disproportionation for the Zr₃FeO_x (x = 0–1.0 ) intermetallic compounds depending on the amount of oxygen. As the oxygen content of the Zr₃FeO_x compounds increases, their susceptibility to disproportionation at room temperature decreases. It is shown that, for the Zr₃FeO_x compounds, the character of thermal desorption of hydrogen in a vacuum and the character of disproportionation in hydrogen at high temperatures strongly depend on the oxygen content. __________ Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 43, No. 5, pp. 81–84, September–October, 2007.     

Investigation on Electrical and Magnetic Properties of Gd-doped BiFeO<Subscript>3</Subscript>

Multiferroic ceramic samples of Bi_1−x Gd _x FeO₃ (x=0, 0.05, 0.1 and 0.15) have been prepared by rapid liquid-phase sintering technique. The effect of Gd substitution on ferroelectric and magnetic properties of Bi_1−x Gd _x FeO₃ ceramics has been investigated. The results of X-ray diffraction (XRD) patterns show that the single-phase BiFeO₃ sample has a rhombohedral structure and Gd³⁺ substitution for Bi³⁺ has not affected its structure. Experimental results suggest that for Bi_1−x Gd _x FeO₃ system, the ferroelectric and magnetic properties of BiFeO₃ are improved by Gd doping and the loop area increases with the Gd content. When x=0.15, saturated ferroelectric hysteresis loop is observed at room temperature with the maximal 2Pr=1.62 μC/cm², which is about 578.6% higher than that of BiFeO₃.     

Ultrasmall Cu2‐xS Nanodots for Highly Efficient Photoacoustic Imaging‐Guided Photothermal Therapy

Monodisperse, ultrasmall (<5 nm) Cu_2?xS nanodots (u‐Cu_2?xS NDs) with significantly strong near‐infrared absorption and conversion are successfully demonstrated for effective deep‐tissue photoacoustic imaging‐guided photothermal therapy both in vitro and in vivo. Owing to ultrasmall nanoparticle size and high water dispersibility as well as long stability, such nanodots possess a prolonged circulation in blood and good passive accumulation within tumors through the enhanced permeability and retention effect. These u‐Cu_2?xS NDs have negligible side effects to both blood and normal tissues according to in vivo toxicity evaluations for up to 3 months, showing excellent hemo/histocompatibility. Furthermore, these u‐Cu_2?xS NDs can be thoroughly cleared through feces and urine within 5 days, showing high biosafety for further potential clinical translation. This novel photoacoustic imaging‐guided photothermal therapy based on u‐Cu_2?xS NDs composed of a single component shows great prospects as a multifunctional nanoplatform with integration and multifunction for cancer diagnosis and therapy.     

Interaction of Dioxyzirconium Ceramics with the Sacrificial Material of the European Reactor Trap

The present paper discusses the complications that can arise in using in the core melt trap of the European nuclear reactor being designed a sacrificial material of 40% FeO _x –60% SiO₂ composition. The investigation of the interaction of zirconium dioxide ceramics with the sacrificial material has permitted the conclusion that at a local baring of the refractory layer its destruction can occur. The addition of neodymium oxide to the melts lowers erosion and excludes regeneration of the ceramics structure.     

Characterizations of trimetallic heteronuclear Bi1−x La x [Fe(CN)6]·n(H2O) complexes and their thermal decomposition products

Heteronuclear Bi_1−x La _x [Fe(CN)₆]·nH₂O complexes were synthesized, and their crystal structures and thermal decomposition process were investigated by X-ray diffraction (XRD), thermogravimetry analysis (TGA), Auger electron spectroscopy (AES) with scanning electron microscope (SEM), and transmission electron microscopy (TEM). The crystal system of the complexes was orthorhombic having n = 4 for x = 0–0.7 and was hexagonal having n = 5 for x = 1.0. Their mixture was confirmed for x = 0.8 and 0.9. The lattice parameters for the orthorhombic increased with increasing the x value for the complexes. The single phase of trimetallic perovskite-type Bi_1−x La _x FeO₃ was obtained by its thermal decomposition at low temperature. The crystal system was hexagonal for BiFeO₃ (x = 0) and orthorhombic for x = 0.1–1.0. In the case of the decomposed perovskite sample, the lattice parameters decreased with increasing x values for Bi_1−x La _x FeO₃. The particle size was ca. 30 nm for Bi_0.2La_0.8FeO₃ obtained by thermal decomposition at 500 °C and it grew with an increase in decomposition temperature. For the Bi_0.5La_0.5FeO₃, AES showed that the elemental distributions of Bi, La, and Fe on the surface were very homogeneous for the sample decomposed at 700 °C.     

Preparation of nanocrystalline VMg(OH)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and VO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> · MgO from organometallic precursors

A process is proposed for the synthesis of nanocrystalline VMg(OH) _x and VO _x · MgO with specific surface areas of up to 1200 and 470 m²/g, respectively. The synthesized VO _x · MgO oxides consist of nanocrystals (2′–5 nm), which form platelike agglomerates. As distinct from conventional impregnation of magnesium oxide, the aerogel process for VO _x · MgO synthesis ensures a uniform vanadium distribution in MgO.     

Study of dielectric, magnetic and ferroelectric properties in Bi1 − xGdxFeO3

Gd-doped BiFeO₃ polycrystalline ceramics were synthesized by solid-state reaction method and their dielectric and magnetic properties were investigated. X-ray diffraction pattern showed that Bi_1 − xGd_xFeO₃ (x = 0, 0.05 and 0.1) ceramics were rhombohedral. The Gd substitution has suppressed the usual impurity peaks present in the parent compound and we obtained single phase Bi_0.9Gd_0.1FeO₃ ceramic. Gd substitution reduced the antiferromagnetic Néel temperature (T_N) in Bi_1 − xGd_x FeO_3. An anomaly in the dielectric constant(ε) and dielectric loss(tan (δ)) in the vicinity of the antiferromagnetic Néel temperature (T_N) was observed. Ferroelectric and magnetic hysteresis loops measured at room temperature indicated the coexistence of ferroelectricity and magnetism. The room temperature magnetic hysteresis loops were not saturated, but the magnetic moment was found to increase with increase in Gd concentration.