Abstract Near-infrared second-window fluorescence imaging (NIR-II FI)-guided synergistic photothermal therapy (PTT) and type-I photodynamic therapy (PDT) hold great promise for noninvasive tumor treatment. However, it is remains highly challenging to develop phototheranostic agents with desired performances, and the systematic exploration of naphthalene diimide (NDI)-based conjugated polymers in this field is still limited. Herein, three NDI-based semiconducting polymers (Si-NDI, C-NDI, and N-NDI)-derived Pdots with various bridge atoms (C, N, and Si) in the cyclopentadithiophene donor units are rationally constructed by nanoprecipitation. These Pdots exhibit uniform spherical morphologies with hydrodynamic diameters of ∼30−40 nm, excellent colloidal stability, and efficient passive tumor targeting via the enhanced permeability and retention (EPR) effect. Among them, C-NDI Pdots exhibit the most superior performance, including robust NIR-II fluorescence, efficient type I reactive oxygen species (O2•−/•OH) generation, and high photothermal conversion efficiency (58.8%). The as-prepared C-NDI Pdots are further applied for efficient tumor cell ablation in vitro and achieve NIR-II imaging-guided synergistic PTT/PDT tumor ablation in 4T1 tumor-bearing nude mouse with satisfactory results. We believe that this work not only provides outstanding NDI Pdots-based phototheranostic nanoagents for non-invasive tumor treatment but also offers a bridge atom tuning strategy for the design of high-performance multimodality phototheranostic nanoagents.
Abstract The application of flexible sensors in long-term wearable activity and micro-expression monitoring is limited by signal drift due to interface delamination, material damage, and insufficient sensitivity. To address this challenge, an ionically conductive hydrogel (PAMTC-Zr) integrating self-adhesion, self-healing, and high sensitivity enabled by its nanoscale features was developed in this study using digital light processing (DLP) three-dimensional (3D) printing. This hydrogel was developed based on a copolymer network of acrylamide and core−shell nanostructured tannic acid-coated cellulose nanocrystals (TA@CNC) that provide abundant nanoscale interactions. The hydrogel-based sensors accurately detected intense movements of joints, such as fingers and wrists, while precisely distinguishing subtle movements, such as smiling and cheek bulging. The integration of this hydrogel with DLP 3D printing for the fabrication of customized curved surfaces, holds promise for the developing conformable, real-time, multimodal skin patches. This study provides a practical nanoscale design strategy for developing next-generation flexible health monitoring sensors that can simultaneously monitor macroscopic movements and microscopic facial expressions.
Abstract A series of CoNi bimetallic borates [NixCo1−x(1-ipIM)3·B6O7(OH)6]·[H3BO3]·3.5H2O (x = 0.9, 0.7, 0.5, 0.3) have been synthesized, in which the oxoboron clusters in the structure contain abundant hydrogen-bonding sites, which are prone to form an open framework and a supramolecular porous structure, providing sufficient free space for catalytic reactions. The borates were converted into CoNi alloy nanocrystals loaded on amorphous carbon via in-situ pyrolysis. Notably, these are the first CoNi alloy nanocrystal oxygen reduction reaction (ORR) catalysts derived from borate precursors that exhibited excellent ORR activity in alkaline media with a half-wave potential as high as 0.881 V, which is slightly better than commercial Pt/C. When applied in zinc−air batteries (ZABs), they exhibited outstanding electrochemical performance, especially a cycling stability of up to 800 h. The superior catalytic performance is attributed to the synergistic effect between Co and Ni, which provides ideas for the development of efficient borate-based ORR catalysts through multi-metallic synergy and promotes their application in high-performance ZABs.
Abstract Graphitic carbon nitride (g-C3N4 and g-CN) is a promising metal-free semiconductor for photocatalytic solar energy conversion, yet its practical application is hindered by high charge recombination rates, limited visible light absorption, and lack of catalytic centers. Molecular doping offers an effective strategy to address these limitations by incorporating functional molecular fragments within the CN nanosheet, enhancing charge separation and electronic properties without the interfacial losses typical of heterojunctions. In this work, we report the rational design of an integrated porphyrin-CN covalent hybrid catalyst via a molecular doping approach. A meso-tetrakis(4-cyanophenyl)porphyrin derivative is functionalized to form polymerizable 2,4-diamino-1,3,5-triazine (DAT) domains, enabling copolymerization with melamine. The resulting porphyrin-doped CN hybrids with intrinsic catalytic centers exhibited extended light absorption and suppressed radiative recombination. Post-synthetic metalation at intrinsically integrated catalytic sites with Ni2+ or Co2+ ions yields efficient solar-driven H2 Evolution. This strategy demonstrates a versatile platform for constructing multifunctional molecular CN hybrids tailored for solar-energy applications. Under photocatalytic conditions using visible light, the Ni- and Co-based porphyrin-modified CN hybrids show a hydrogen evolution reaction (HER) rate of 640 μmol·g−1 h−1 and 720 μmol·g−1 h−1, respectively, in the presence of ascorbic acid as a sacrificial agent.
Abstract Overall water splitting powered by low-cost and efficient electrocatalysts offers a promising pathway for the sustainable production of H2 energy. Here, we have successfully designed and prepared a C-SnO2-MoSe2/MoS2 composite material comprising carbon-doped SnO2 and layered 2D materials (MoSe2 and MoS2) for overall water splitting. The composite exhibited attractive electrocatalytic activities for both HER and OER, possessing very low overpotentials and Tafel slopes, along with high faradaic efficiencies. Notably, the prepared composite material demonstrated bifunctional electrocatalytic activity for efficient overall water splitting, achieving a low cell potential of 1.72 V at 10 mA cm−2. Along with this high electrocatalytic efficiency, the composite presented long-term operational stability up to 90 h in overall water splitting.
