Molecular hydrogen (H2) shows promise for tumor treatment, whereas its therapeutic potential is seriously challenged by inadequate dosing along with unclear biological mechanisms. Herein, spurred on by the first successful report with high-pressure H2 inhalation administration, we develop a locally generated hyperbaric hydrogen platform by fabricating and leveraging crystalline β-phase magnesium hydride (MgH2) as reservoirs of superior hydrogen-releasing capacity for tumor starvation therapy. The as-synthesized particles allow crystallization-controlled, prolonged H2 generation lasting days upon reaction with water, which further achieve in-situ overpressure (> 1.8 atm) in response to the acidic tumor microenvironment (TME). We find that continuous exposure to single H2 of abundant supply can suppress energy metabolism in various types of tumor cells to inhibit proliferation and induce apoptosis. Moreover, the β-MgH2 reservoir yielding significant intratumoral H2 is demonstrated in vivo for both local and systemic administration models, of marked metabolic function disruption, and excellent antitumor efficacy without causing systemic toxicity. Mechanistically, we distinguish that locally enriched H2 plays dual roles of impairing tumor aerobic glycolysis via downregulating HIF-1α/GLUT1 axis, and eliciting mitochondrial damage associated with adenosine triphosphate (ATP) deprivation, which thereby synergistically block energy production for cancer anabolism. Collectively, our work delivers a proof of concept of "safe, local, long-acting" high-pressure hydrogen treatment modality to enable efficient cancer-selective starvation therapy.
- Article type
- Year
- Co-author
Open Access
Research Article
Issue
Open Access
Full Length Article
Issue
In the present work, highly effective Ni-MnO binary nanocomposite catalysts were designed and synthesized using a one-pot method from Ni-Mn based bi-metal organic frameworks (MOFs). These nanocomposites were introduced into MgH2 through ball milling as catalysts to enhance the hydrogen storage properties of MgH2. Through varying the Ni/Mn ratio in the bimetal MOFs, it is found that the Ni1Mn1−MOF derived catalyst showed the best promotion effect on MgH2. The MgH2–10 wt.% Ni1Mn1−MOF derivative demonstrated favorable overall performance with the low desorption peak temperature (218.2 °C) with a saturated hydrogen capacity of 6.42 wt.% and rapid hydrogen release/uptake kinetics. It can still reabsorb about 1.15 wt.% H2 within 30 min at a temperature as low as 50 °C. Both performance tests (DSC and TPD) and structural characterizations (XRD, HRTEM, etc.) revealed that the synergistic role of in situ formed Mg6MnO8 and Mg2NiH4/Mg2Ni phases for improving the hydrogen sorption properties of MgH2. Theoretical calculations reveal that Mg6MnO8 destabilizes metal-H bonds in MgH2 and Mg2NiH4, leading to an enhanced “hydrogen pump” effect of Mg2NiH4 for MgH2. This research provides a strategy to rational design and preparation of bimetal MOF derivatives for the development of advanced hydrogen storage materials.
Open Access
Review
Issue
Rechargeable magnesium-ion batteries (MIBs) are favorable substitutes for conventional lithium-ion batteries (LIBs) because of abundant magnesium reserves, a high theoretical energy density, and great inherent safety. Organic electrode materials with excellent structural tunability, unique coordination reaction mechanisms, and environmental friendliness offer great potential to promote the electrochemical performance of MIBs. However, research on organic magnesium battery cathode materials is still preliminary with many significant challenges to be resolved including low electrical conductivity and unwanted but severe dissolution in useful electrolytes. Herein, we provide a detailed overview of reported organic cathode materials for MIBs. We begin with basic properties such as charge storage mechanisms (e.g., n-, p-, and bipolar-type), moving to recent advances in various types of organic cathodes including carbonyl-, nitrogen-, and sulfur-based materials. To shed light on the diverse strategies targeting high-performance Mg-organic batteries, elaborate summaries of various approaches are presented. Generally, these strategies include molecular design, polymerization, mixing with carbon, nanosizing and electrolyte/separator optimization. This review provides insights on exploring high-performance organic cathodes in rechargeable MIBs.
Open Access
Research Article
Issue
Achieving dual regulation of the kinetics and thermodynamics of MgH2 is essential for the practical applications. In this study, a novel nanocomposite (In@Ti-MX) architected from single-/few-layered Ti3C2 MXenes and ultradispersed indium nanoparticles was prepared by a bottom-up self-assembly strategy and introduced into MgH2 to solve the above-mentioned problems. The MgH2+In@Ti-MX composites demonstrate excellent hydrogen storage performance: The resultant In@Ti-MX demonstrated a positive effect on the hydrogen storage performance of MgH2/Mg: the dehydrogenated rate of MgH2+15 wt%In@Ti-MX reached the maximum at 330 ℃, which was 47 ℃ lower than that of commercial MgH2; The hydrogenation enthalpy of the dehydrided MgH2+15 wt%In@Ti-MX and MgH2+25 wt%In@Ti-MX were determined to be −66.2 ± 1.1 and −61.7 ± 1.4 kJ·mol−1 H2. In situ high-energy synchrotron x-ray diffraction technique together with other microstructure analyses revealed that synergistic effects from Ti3C2 MXenes and In nanoparticles (NPs) contributed to the improved kinetics and thermodynamics of MgH2(Mg): Ti/TiH2 derived from Ti3C2 MXenes accelerated the dissociation and recombination of hydrogen molecule/atoms, while In NPs reduced the thermodynamic stability of MgH2 by forming the Mg-In solution. Such a strategy of using dual-active hybrid structures to modify MgH2/Mg provides a new insight for tuning both the hydrogen storage kinetics and thermodynamics of Mg-based hydrides.
Open Access
Mini Review
Issue
Hydrogen holds the advantages of high gravimetric energy density and zero emission. Effective storage and transportation of hydrogen constitute a critical and intermediate link for the advent of widespread applications of hydrogen energy. Magnesium hydride (MgH2) has been considered as one of the most promising hydrogen storage materials because of its high hydrogen storage capacity, excellent reversibility, sufficient magnesium reserves, and low cost. However, great barriers both in the thermodynamic and the kinetic properties of MgH2 limit its practical application. Doping catalysts and nanostructuring are two facile but efficient methods to prepare high-performance magnesium (Mg)-based hydrogen storage materials. Core–shell nanostructured Mg-based hydrogen storage materials synergize the strengths of the above two modification methods. This review summarizes the preparation methods and expounds the thermodynamic and kinetic properties, microstructure and phase changes during hydrogen absorption and desorption processes of core–shell nanostructured Mg-based hydrogen storage materials. We also elaborate the mechanistic effects of core–shell nanostructures on the hydrogen storage performance of Mg-based hydrogen storage materials. The goal of this review is to point out the design principles and future research trends of Mg-based hydrogen storage materials for industrial applications.
京公网安备11010802044758号