Biodegradable Nanoscale Coordination Polymers for Targeted Tumor Combination Therapy with Oxidative Stress Amplification

Nowadays various inorganic nanoparticles that generate highly reactive hydroxyl radical ( · OH) on the basis of Fenton‐like catalytic activity of metal ions have been designed for chemodynamic therapy. However, the high level of adaptive antioxidants [glutathione (GSH)] in cancer cells could effectively consume · OH to compromise the treatment efficiency and biosafety of these inorganic nanoparticles, and this is a general concern in chemodynamic therapy. Herein, a new biodegradable nanoscale coordination polymer (NCP) is developed by integration of cisplatin prodrug (DSCP) and iron (III) ions through a reverse microemulsion method. The DSCP in the NCPs could react with GSH to release free cisplatin, while the iron (III) ions could be reduced by GSH into iron (II) to enable Fenton reaction, subsequently leading to amplified intracellular oxidative stress. After surface modification of polyethylene glycol (PEG) and cyclo[Arg‐Gly‐Asp‐D‐Phe‐Lys(mpa)] peptide (cRGD), Fe‐DSCP‐PEG‐cRGD shows an excellent targeting effect against α_vβ₃‐integrin overexpressed tumor cells. Furthermore, Fe‐DSCP‐PEG‐cRGD enables significant chemo and chemodynamic therapy with dramatically enhanced therapeutic efficiency in comparison to relative monotherapies. Importantly, Fe‐DSCP‐PEG‐cRGD could be efficiently cleared out from mice through feces and urine postinjection 7 days. The NCP presented in this work is simple and economical, which shows great biodegradability and biosafety for potential clinical translation.     

Fine‐Tuning Intrinsic Strain in Penta‐Twinned Pt–Cu–Mn Nanoframes Boosts Oxygen Reduction Catalysis

Tuning the intrinsic strain of Pt‐based nanomaterials has shown great promise for improving the oxygen reduction reaction (ORR) performance. Herein, reported is a tunable surface strain in penta‐twinned ternary Pt–Cu–Mn nanoframes (NFs). Pt–Cu–Mn ultrafine NFs (UNFs) exhibit ≈1.5% compressive strain compared to Pt–Cu–Mn pentagonal NFs (PNFs) and show the superior activity toward ORR in an alkaline environment. Specifically, the specific and mass activity of Pt–Cu–Mn UNFs are 3.38 mA cm^?2 and 1.45 A mg^?1, respectively, which is 1.45 and 1.71 times higher than that of Pt–Cu–Mn PNFs, demonstrating that compressive strain in NFs structure can effectively enhance the catalytic activity of ORR. Impressively, Pt–Cu–Mn UNFs exhibit 8.67 and 9.67 times enhanced specific and mass activity compared with commercial Pt/C. Theoretical calculations reveal that compression on the surface of Pt–Cu–Mn UNFs can weaken the bonding strengths and adsorption of oxygen‐containing intermediates, resulting in an optimal condition for ORR.     

Tumor Metabolism‐Engineered Composite Nanoplatforms Potentiate Sonodynamic Therapy via Reshaping Tumor Microenvironment and Facilitating Electron–Hole Pairs’ Separation

Reactive oxygen species (ROS) depletion and low ROS production that result from the intratumoral redox metabolism equilibrium and low energy conversion efficiency from ultrasound mechanical energy to ROS‐represented chemical energy, respectively, are two vital inhibitory factors of sonodynamic therapy (SDT). To address the two concerns, a tumor metabolism‐engineered composite nanoplatform capable of intervening intratumoral ROS metabolism, breaking the redox equilibrium, and reshaping the tumor microenvironment is constructed to reinforce SDT against tumors. In this metabolism‐engineered nanoplatform, Nb₂C nanosheets serve as the scaffold to accommodate TiO₂ sonosensitizers and l ‐buthionine‐sulfoximine. Systematic experiments show that such nanoplatforms can reduce ROS depletion via suppressing glutathione synthesis and simultaneously improving ROS production via the Nb₂C‐enhanced production and separation of electron–hole pairs. Contributed by the combined effect, net ROS content can be significantly elevated, which results in the highly efficient anti‐tumor outcomes in vivo and in vitro. Moreover, the combined design principles, that is, tumor metabolism modulation for reducing ROS depletion and electron–hole pair separation for facilitating ROS production, can be extended to other ROS‐dependent therapeutic systems.     

Oxygen Vacancy Modulation of Bimetallic Oxynitride Anodes toward Advanced Li‐Ion Capacitors

Binary metal oxides (such as NiCo₂O₄) are regarded as attractive electrode materials for advanced energy storage devices since they offer more electrochemical activity and higher capacity than monometal oxide. However, the volume expansion and low electronic conductivity are the main bottleneck seriously hindering their application. To overcome these barriers, a novel strategy that introduces a bimetallic oxynitride layer (NiCoON) with oxygen vacancy to the surface of NiCo₂O₄ nanowires as an anode for Li‐ion capacitors (LICs) is proposed. The oxygen vacancy on the surface and the modulation of multiple valence states are investigated by the electron paramagnetic resonance, X‐ray photoelectron spectroscopy characterization, and first‐principles calculation. Benefiting from the merits of substantially improved electrical conductivity and increased concentration of active sites, the optimized NiCoON electrode delivers remarkable capacity (1855 mAh g^?1 at 0.2 A g^?1) and rate performance. The LIC device assembled by NiCoON anodes and N‐doped carbon nanowire cathodes delivers excellent rate capability, high energy density (148.5 Wh kg^?1), and outstanding power density (30 kW kg^?1). This study provides a new pathway for developing bimetallic oxides with an improved performance in electrochemical energy storage, conversion fields, and beyond.     

光动力抗菌纳米制剂研究进展

新兴的光动力抗菌疗法是一种无创激发式治疗手段,主要利用近红外光作为光源,激活富集在病灶部位的光敏剂并产生活性氧自由基,最终实现对目标病菌的杀伤。近年来,随着生物材料与纳米医学技术的发展,小分子光敏剂纳米功能化后其生物兼容性和生物安全性得到优化,量子产率和病灶部位富集率显著提升,在抗菌治疗方面有很大的临床应用前景。本文结合小分子光敏剂纳米化策略方法实例,综述了纳米技术在光动力抗菌疗法的应用和发展。     

Advance in Using Plasma Technology for Modification or Fabrication of Carbon-Based Materials and Their Applications in Environmental,Material, and Energy Fields

Plasma technology is an eco-friendly way to modify or fabricate carbon-based materials (CBMs) due to plasmas’ distinctive abilities in tuning the surface physicochemical properties by implanting functional groups or incorporating heteroatoms into the surface without changing the bulk structure. However, the mechanisms of functional groups formation on the carbon surface are still not clearly explained because of the variety of different discharge conditions and the complexity of plasma chemistry. Consequently, this paper contains a comprehensive review of plasma-treated carbon-based materials and their applications in environmental, materials, and energy fields. Plasma-treated CBMs used in these fields have been significantly enhanced in recent years because these related materials possess unique features after plasma treatment, such as higher adsorption capacity, enhanced wettability, improved electrocatalytic activity, etc. Meanwhile, this paper also summarizes possible reaction routes for the generation of functional groups on CBMs. The outlook for future research is summarized, with suggestions that plasma technology research and development shall attempt to achieve precise control of plasmas to synthesize or to modify CBMs at the atomic level.     

Effects of Fluorinated Diluents in Localized High-Concentration Electrolytes for Lithium–Oxygen Batteries

A stable electrolyte is critical for practical application of lithium–oxygen batteries (LOBs). Although the ionic conductivity and electrochemical stability of the electrolytes have been extensively investigated before, their oxygen solubility, viscosity, volatility, and the stability against singlet oxygen (¹O₂) still need to be comprehensively investigated to provide a full picture of the electrolytes, especially for an open system such as LOBs. Herein, a systematic investigation is reported on the localized high-concentration electrolytes (LHCEs) using different fluorinated diluents in comparison with those of conventional electrolytes. The physical properties and activation energies for reactions with singlet oxygen (¹O₂) of these electrolytes are calculated by density functional theory. The electrochemical performances of LOBs using these electrolytes are compared. This study reveals that the correlation between the stability of the electrolytes and their physical and electrochemical properties depends strongly on the diluents in LHCEs. Therefore, it shines light on the rational design of new electrolytes for LOBs.     

Tailoring the Redox Reactions for High-Capacity Cycling of Cation-Disordered Rocksalt Cathodes

Cation-disordered rocksalts (DRXs) have emerged as a new class of high-capacity Li-ion cathode materials. One unique advantage of the DRX chemistry is the structural flexibility that substantially lessens the elemental constraints in the crystal lattice, such as Li content, choice of transition metal redox center paired with appropriate d⁰ metal, and incorporation of F anion, which allows optimization of the key redox reactions. Herein, a series of the DRX oxyfluorides based on the Mn redox have been designed and synthesized. By tailoring the stoichiometry of the DRX compositions, high-capacity cycling by promoting the cationic Mn²⁺/Mn⁴⁺ redox reactions while suppressing those from anionic O is successfully demonstrated. A highly fluorinated DRX compound, Li_1.2Mn_0.625Nb_0.175O_1.325F_0.675 (M_0.625F_0.675), delivers a capacity of ≈170 mAh g⁻¹ at C/3 for 100 cycles. This work showcases the concept of balancing the cationic and anionic redox reactions in the DRX cathodes for improved electrochemical performance through the rational composition design.     

New Insight into Microstructure Engineering of Ni-Rich Layered Oxide Cathode for High Performance Lithium Ion Batteries

Ni-rich layered LiNi_xCo_yMn_1−x−yO₂ (LNCM) with Ni content over >90% is considered as a promising lithium ion battery (LIB) cathode, attributed by its low cost and high practical capacity. However, Ni-rich LNCM inevitably suffers rapid capacity fading at a high state of charge due to the mechanochemical breakdown; in particular, the microcrack formation has been regarded as one of the main culprits for Ni-rich layered cathode failure. To address these issues, Ni-rich layered cathodes with a textured microstructure are developed by phosphorous and boron doping. Attributed by the textured morphology, both phosphorous- and boron-doped cathodes suppress microcrack formation and show enhanced cycle stability compared to the undoped cathode. However, there exists a meaningful capacity retention difference between the doped cathodes. By adapting the various analysis techniques, it is shown that the boron-doped Ni-rich layered cathode displays better cycle stability not only by its ability to suppress microcracks during cycling but also by its primary particle morphology that is reluctant to oxygen evolution. The present work reveals that not only restraint of particle cracks but also suppression of oxygen release by developing the oxygen stable facets is important for further improvements in state-of-the-art Li ion battery Ni-rich layered cathode materials.     

High Yield Electrosynthesis of Hydrogen Peroxide from Water Using Electrospun CaSnO3@Carbon Fiber Membrane Catalysts with Abundant Oxygen Vacancy

Hydrogen peroxide (H₂O₂) production by electrochemical two-electron water oxidation reaction (2e-WOR) is a promising approach, where high-performance electrocatalysts play critical roles. Here, the synthesis of nanostructured CaSnO₃ confined in conductive carbon fiber membrane with abundant oxygen vacancy (O_V) as a new generation of 2e-WOR electrocatalyst is reported. The CaSnO₃@carbon fiber membrane can be directly used as a self-standing electrode, exhibiting a record-high H₂O₂ production rate of 39.8 µmol cm⁻² min⁻¹ and a selectivity of ≈90% (at 2.9 V vs reversible hydrogen electrode). The CaSnO₃@carbon fiber membrane design improves not only the electrical conductivity and stability of catalysts but also the inherent activity of CaSnO₃. Density functional theory calculation further indicates the crucial role of O_V in increasing the adsorption free energy toward oxygen intermediates associated with the competitive four-electron water oxidation reaction pathway, thus enhancing the activity and selectivity of 2e-WOR. The findings pave a new avenue to the rational design of electrocatalysts for H₂O₂ production from water.