Designing small-molecule dyes that emit in the second near-infrared (NIR-II, 1000-1700 nm) region for multifunctional phototheranostics remains highly challenging, largely due to the intricate competition among excited-state energy dissipation pathways. Herein, we propose a donor substituent engineering strategy to precisely modulate these pathways in a series of boron difluoride (BF2) formazanate dyes (BDFOMe, BDFH, and BDFCN), thereby enabling efficient NIR-II fluorescence imaging (FLI)-guided photothermal therapy (PTT) and photodynamic therapy (PDT). Systematic experimental and theoretical analyses reveal that electron-deficient cyano substituents in BDFCN significantly suppress vibrational relaxation-mediated nonradiative decay by reducing the charge transfer magnitude (from 0.58095 e in BDFOMe to 0.54481 e in BDFCN), resulting in a two-fold enhancement in fluorescence quantum yield (QY). Meanwhile, the cyano substitution narrows the singlet-triplet energy gap (Delta ES1-T2) from 0.301 eV (BDFOMe) and 0.295 eV (BDFH) to 0.241 eV, thereby facilitating intersystem crossing (ISC) and enhancing reactive oxygen species (ROS) generation. Upon 808 nm photo-irradiation, BDFCN nanoparticles exhibit superior integrated phototheranostic efficacy, achieving effective NIR-II FLI-guided tumor eradication through combined PTT and PDT. This work establishes donor substituent modulation as a powerful design principle for balancing radiative and nonradiative de-excitation processes, providing new molecular insights for developing small-molecule NIR-II dyes toward precision phototheranostics.
Doxorubicin (DOX)-induced cardiotoxicity (DIC) is a major dose-limiting complication of chemotherapy, in which pyroptosis is considered a key pathological mechanism. The natural stilbene compound pterostilbene (PTE) has demonstrated cardioprotective potential, but its role in DOX-induced pyroptosis remains unclear. This study, using both in vitro H9C2 cardiomyocyte and in vivo C57BL/6 mouse models of DIC, confirmed that PTE effectively inhibits DOX-induced cardiomyocyte pyroptosis and alleviates cardiac injury. Mechanistically, DOX activates the IL-6/STAT3 signaling pathway, promoting the nuclear translocation of phosphorylated STAT3 (pSTAT3). CUT&Tag and dual-luciferase reporter assays further revealed that activated STAT3 directly binds to the core promoter regions of the caspase-3 and Gasdermin E (GSDME) genes, thereby upregulating their expression at the transcriptional level and ultimately activating the caspase-3/GSDME-mediated pyroptosis pathway. PTE effectively blocks this pyroptotic execution pathway by inhibiting the activation of the IL-6/STAT3 pathway. Furthermore, this study elucidated a critical interaction between cardiomyocytes and immune cells: GSDME-mediated cardiomyocyte pyroptosis releases various soluble factors, with IL-6 being a key cytokine that drives the polarization of macrophages toward the pro-inflammatory M1 phenotype, thereby amplifying the myocardial inflammatory response. By inhibiting cardiomyocyte pyroptosis, particularly by reducing IL-6 release, PTE effectively interrupts this “cardiomyocyte pyroptosis-M1 macrophage polarization” vicious cycle and restores myocardial homeostasis. In summary, our research elucidates a signaling cascade driving DOX-induced cardiotoxicity: IL-6/STAT3-caspase-3/GSDME. We confirmed that PTE is an effective inhibitor of this pathway, not only directly protecting cardiomyocytes but also suppressing the subsequent pyroptosis-driven inflammatory response, thereby highlighting its significant therapeutic potential in mitigating DIC.
Phase control of alloy nanomaterials can modulate their atomic/electronic structures towards various electrocatalytic applications. However, the controlled synthesis of high-entropy nanoalloys (HENAs) with unconventional phase remains challenging. Here we report the one-pot synthesis of RhCuNiInSb HENAs with the unconventional 2H phase through regulating the nucleation/growth kinetics. Compared with the face-centred cubic phase counterpart, 2H RhCuNiInSb HENAs exhibit superior electrocatalytic nitrate reduction performance at low nitrate concentration. Ex/in situ studies reveal the accelerated deoxygenation/hydrogenation kinetics and distinct reaction pathway. Theoretical calculations demonstrate the electronic optimizations induced by the face-centred-cubic-to-2H phase transition, where the electronic redistribution and p–d elemental interactions improve the surface electroactivity. When operated in flow cell, 0.5 l of simulated wastewater can be efficiently converted into the value-added ammonia-derived product within 10 h. With a 20-h electrolysis, the NO3−-N concentration in real industrial and agricultural wastewater can be both reduced above the World Health Organization standard for drinking water. Phase engineering of high-entropy nanoalloys can enhance electrocatalysis. A one-pot synthesized 2H RhCuNiInSb nanoalloy outperformed its face-centred cubic counterpart for nitrate reduction, enabling efficient NH3 production and wastewater denitrification through an optimized electronic structure.
Long-term physiological signal monitoring is critical for accurate diagnosis and effective management of chronic diseases. However, current electrode technologies face significant drawbacks: dry electrodes exhibit high electrochemical impedance and poor adhesion to skin, while wet electrodes suffer from short service lifetimes due to water loss. Inspired by the hygroscopic properties of spider webs, we developed an electronically conductive hygroscopic adhesive (termed as “hygrotrode”) that continuously absorbs ambient moisture through a cross-linked, three-dimensional hygroscopic polymer network. This design maintains a low interface impedance and high adhesion energy for over a year, facilitated by absorbed intermediate water that electrochemically bridges the conducting polymer and skin tissue. The specific impedance of hygrotrode is 82.4 times lower compared with wet electrodes after 1 year. We further demonstrate hygrotrode’s suitability for chronic biopotential monitoring and electromyography-based gesture recognition, highlighting its wide-ranging applicability in long-term wearable electronics and human-machine interfaces.
Type I photosensitizers capable of generating cytotoxic reactive oxygen species (ROS), with reduced oxygen dependence under photoirradiation, are regarded as a promising phototherapeutic approach for hypoxic solid tumors. Herein, based on the electron donor of 9-phenyl-carbazole (Cz) and the electron acceptor of anthraquinone (AQ), photosensitizer AQCzBF, which mainly produced superoxide anion-free radical (O2 -center dot), was developed for hypoxia-resistant photodynamic therapy (PDT). Compared with AQCz without the boron difluoride chelation, photosensitizer AQCzBF showed not only redshifted absorption and pronounced intramolecular charge transfer (ICT) but also enhanced O2 -center dot generation. Theoretical calculations revealed a smaller Delta E ST (0.13 eV), a larger SOC matrix element (7.80 cm-1), and more efficient intersystem crossing (ISC) for AQCzBF. Compared to AQCz NPs, AQCzBF NPs demonstrated significantly enhanced ROS generation, exhibiting 4-fold higher total ROS and 7.16-fold greater O2 -center dot production. In vivo experiments verified the outstanding tumor suppression efficacy of AQCzBF NPs. This work presented an innovative molecular design of aminoanthraquinone photosensitizers through boron difluoride chelation to conquer tumor hypoxia for PDT. I(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(ROS)(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(PDT),(sic)(sic)(sic)(sic)9-(sic)(sic)(sic)(sic)(Cz)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(AQ)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(O2 -center dot)(sic)(sic)(sic)ROS(sic)(sic)(sic)(sic)(sic)(sic)AQCzBF.(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)AQCz(sic)(sic),AQCzBF(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(ICT)(sic)(sic),(sic)O2 -center dot(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic),AQCzBF(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)-(sic)(sic)(sic)(sic)(sic)(sic)(Delta E ST,0.13 eV),(sic)(sic)(sic)(sic)(sic)-(sic)(sic)(sic)(sic)(sic)(sic)(sic)(SOC, 7.80 cm-1),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(ISC)(sic)(sic).(sic)(sic)(sic)AQCz NPs, AQCzBF NPs(sic)ROS(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic):(sic)(sic)(sic)ROS(sic)(sic)(sic)(sic)4(sic),O2 -center dot(sic)(sic)(sic)(sic)(sic)(sic)7.16(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)AQCzBF NPs(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)PDT(sic)(sic)(sic)(sic)(sic)(sic).
Tailoring the coordination environment of single-atom catalysts is a pivotal strategy for optimising their catalytic performance. A porous carbon-supported single-atom catalyst (SAC) with an asymmetric Co-N3B1 coordination structure exhibits superior performance to its boron-free counterparts in the selective hydrogenation of p-chloronitrobenzene. Boron doping creates an electron-rich Co centre that enhances nitro-group activation.
The Zn(solvents)x2+, with high desolvation energy barriers, leads to the formation of H+ and partial desolvated Zn2+ simultaneously intercalated into the MnO2 cathode. A single-atom Ni catalyst on nitrogen-doped carbon (SANi-NC) is introduced to achieve stepwise atom-level catalytic desolvation of Zn(H2O)x2+, which enables more insertion of Zn2+, thereby achieving high-performance Zn-MnO2 batteries.
Intermolecular charge-transfer complexes (CTCs) are attractive for phototheranostics in the second near-infrared window (NIR-II) but suffer from intrinsic instability that undermines optical and therapeutic performance. Here, we introduce an electrostatic reinforcement-based supramolecular strategy to construct a stable NIR-II CTC, FBDFCTC nanoparticles (NPs), by co-assembling the NIR-II dye FBDF4NMe (donor) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ, acceptor) at a ratio of 1:2. The resulting FBDFCTC NPs feature intense NIR-II absorption (epsilon 1064 nm = 1.73 & times; 104 M-1 cm-1) and exceptional photothermal conversion efficiency (eta = 56.3%) under 1064 nm irradiation. Beyond efficient photothermal therapy (PTT), the strong electrophilicity of F4TCNQ enables selective depletion of intracellular glutathione and cysteine, thereby amplifying oxidative stress and triggering exogenous iron-free ferroptosis. Notably, unlike conventional CTCs, FBDFCTC NPs retain robust NIR-II photothermal activity even after partial CTC dissociation, ensuring durable therapeutic performance in tumor environments. In vivo, FBDFCTC NPs afford high-contrast NIR-II photoacoustic imaging (PAI) for precise tumor localization and vascular mapping, followed by PAI-guided photothermal ablation. This work establishes electrostatic reinforcement of CTCs as a generalizable paradigm to achieve multifunctional NIR-II platforms that integrate deep-tissue PTT with tumor microenvironment modulation, opening new avenues for precise, durable, and safe cancer therapy.
Abstract Imaging increasingly serves as a multiscale framework for linking molecular mechanisms to cellular behavior, tissue architecture, and organ phenotypes in biology and unraveling fundamental processes in chemistry, physics and materials science. This Perspective highlights recent advances in chemical and biomedical imaging across macro-, micro-, and nanoscales, using representative examples published in Chemical and Biomedical Imaging (CBMI). At the macroscale, we discuss chemically selective MRI, including endogenous and exogenous CEST strategies, together with photoacoustic imaging as a hybrid modality with functional and chemical contrast. At the microscale, we consider fluorescence, label-free optical and vibrational imaging, and selected X-ray approaches that expand sensitivity, specificity, and temporal resolution in biological and materials systems. At the nanoscale, we highlight super-resolution fluorescence microscopy, single-molecule methods, tip-enhanced Raman spectroscopy, and correlative imaging strategies that resolve local heterogeneity and molecular organization. Across scales, a common theme emerges that advances in probes, contrast mechanisms, instrumentation, and sample handling are enabling chemically informed imaging that connects molecular specificity with biological context.
Photocatalytic CO2 reduction to methane (CH4) offers a strategically route for mitigating energy sustainability and carbon emission challenges. However, its practical deployment is impeded by suboptimal activity and selectivity narrow light absorption, slow electron transfer, and unstable intermediates. Herein, we develop a ternary Au-In2O3/TiO2 photocatalyst by selectively depositing Au nanoparticles (NPs) onto an S-scheme In2O3/ TiO2 heterojunction, achieving a effectively CH4 production rate of 245.5 mu mol g- 1 h- 1 with 92% electron selectivity. This yields a 6-fold activity enhancement over the bare heterojunction, resulting from synergistic plasmonic sensitization that extends absorption into the visible region, optimized adsorption energetics of key intermediates, and multiple charge transfer pathways. In situ spectroscopic and theoretical calculation studies reveal accelerated CO2 activation and selective protonation pathways, while Au NPs inherently suppress hydrogen evolution reaction to minimize side reactions. This systematic approach establishes a transferable design paradigm for heterojunction-nanoparticle composite catalysts, advancing efficient catalytic systems for selective transformations.
Tissue-engineered hair follicle regeneration offers a promising method for increasing hair follicle count, yet it faces challenges such as difficulty with hair emergence through the skin and the potential for clustered and disordered growth. Achieving biomimetic regeneration of single or double hair follicular units is therefore essential. Microneedle arrays (MNs) can mimic natural hair density, enabling controlled hair regeneration in direction and density. However, most MNs for hair regeneration are designed for drug delivery, which can only modulate the hair cycle of existing follicles and cannot generate de novo hair follicles in bald areas. MNs designed for tissue-engineered hair follicle delivery are rare and face challenges in sustaining cellular vitality and achieving epidermal breakthrough. Thus, a novel approach based on core-shell MN technology and hair follicle organoids (HFOs) culture was developed for hair follicle unit regeneration. In this study, degradable core-shell cryomicroneedles (CryoMNs) with uniform walls and multiple small channels were loaded with HFOs. When applied to nude mice, the core-shell CryoMNs supported biomimetic follicular unit growth, mimicking natural hair regeneration. Controllably degradable core-shell CryoMNs offer nutrient channels for HFOs and cutaneous channels for hair growth, controlling hair growth direction and spacing, and enabling orderly follicular unit regeneration in patients with baldness. This study introduces novel ideas and strategies for the subcutaneous delivery of organoids and the systematic regeneration of tissue-engineered hair follicles.
In recent years, phototherapy has experienced unprecedented development and is regarded as an irreplaceable modality for noninvasive cancer therapy. Stimuli-responsive injectable hydrogels provide an efficacious strategy for overcoming some disadvantages of cancer phototherapy, such as high rate off-target accumulation, potential biotoxicity, and limited tumor retention time. In this review, we aim to provide detailed descriptions and discussions on the injectable hydrogels for cancer phototherapy in combination with other therapeutic modalities. First, we introduce the fabrication methods and stimuli-responsive properties of various injectable hydrogels. Then, currently developed phototherapeutic injectable hydrogels are classified, focusing on their therapeutic modalities and chemical/biological mechanisms. Finally, the limitations of current injectable phototherapeutic hydrogels and future research directions are summarized and discussed.
Antibiotic contamination in aquatic environments presents significant challenges to ecological sustainability and public health through antimicrobial resistance proliferation. Current monitoring approaches remain constrained by limited sensitivity and electrode degradation issues. Herein, we report a sustainable catalytic electrochemical sensor featuring a hierarchical three-dimensional architecture integrating Ti3C2TX MXene, silver nanowires, and reduced graphene oxide (rGO/AgNWs@Ti3C2TX). This catalytic interface demonstrates exceptional charge-transfer efficiency (136.8 Omega) with ultralow detection limits (<1 mu mol/L) across four antibiotic classes, wide dynamic ranges (1-1000 mu mol/L), and outstanding reproducibility (RSD = 2.7 %). Differential pulse voltammetry ensures selective detection with minimal interference from common water contaminants. Statistical correlation analyses (Mantel and rank-sum tests) reveal distinctive redox fingerprints among different antibiotic classes, enabling multiplexed detection capabilities. Density functional theory calculations confirm that the MXene-graphene catalytic interfaces significantly enhance charge separation and electron transfer pathways, while AgNWs effectively mitigate MXene restacking, collectively suppressing electrode fouling during extended operations. This sustainable catalytic approach addresses critical limitations in environmental electrochemical sensing, offering an energy-efficient platform for real-time water quality monitoring with potential applications in antibiotic contamination assessment and remediation.
Abstract Natural enzymes are widely used in theranostics, but they suffer from poor stability, high costs, and nontunable monofunctionality, driving the development of artificial enzymes, in particular single-atom nanozymes (SAzymes). However, conventional SAzymes struggle to handle multistep redox reactions effectively. Herein, we present atomically dispersed zinc−phosphorus (Zn−P) catalytic pairs (CPs) anchored on acid-resistant carbon nanosheets (Zn−P/CNS) that display greatly enhanced multienzyme-like activities, particularly for superoxide radical dismutation and hydrogen peroxide decomposition. Density functional theory reveals that P primarily serves as an additional catalytic site to facilitate substrate binding and intermediate stabilization, while also modulating the local electronic structure of Zn and aiding proton transfer, thereby lowering energy barriers in the multistep redox pathways. In a dextran sulfate sodium-induced colitis model, oral administration of this Zn−P/CNS markedly reduces oxidative damage and inflammation, demonstrating the promise of metal−nonmetal CPs as a versatile platform for designing high-performance nanozymes for biomedical applications.
Developing noble-metal-free electrocatalyst for oxygen evolution reaction in a proton exchange membrane water electrolyzer is a key to sustainable and economical hydrogen production. Herein, we rationally design and develop a chromium and neodymium co-doped cobalt oxide (CrNd-Co3O4) electrocatalyst that exhibits high activity and durability in the acidic oxygen evolution reaction condition. Furthermore, an in-situ acid circulation strategy is proposed to tackle the ubiquitous issue of membrane poisoning by leached cations in proton exchange membrane water electrolyzers. Consequently, the proton exchange membrane water electrolyzer with CrNd-Co3O4 anode achieves a stable operating current density of 2 amperes per square centimeter at 2.27 volts and 4 amperes per square centimeter at 2.54 volts for 1,000 hours.
Copper chalcogenides containing Cuδ+ (0 < δ < 2) species are efficient catalysts to produce ethanol in CO2 electroreduction, during which it generally involves 12 e− transfer plus 6 hydrogenation steps. Improving surface *H coverage on Cuδ+ sites is critical to enhance CC coupling and the following hydrogenation of *C2 intermediates toward ethanol. Traditional strategies such as doping palladium or nickel may increase *H coverage and result in a severe side hydrogen evolution reaction due to enhanced HH coupling. In this work, surface high-valence Re6+ doping was demonstrated to enable introducing *OH as Brønsted acid for providing direct local proton to achieve selective and rapid nucleophilic attack toward *OCHCH3 intermediates adsorbed on adjacent Cu site in Cu2Se and inhibit HH coupling, thus improving ethanol selectivity and simultaneously suppressed other C2+ products (i.e., ethylene) and by-product of H2 formation. As a result, Re6+ doped Cu2Se exhibits excellent partial current density of −506 mA cm−2 and a peak Faradaic efficiency of 53.9% for ethanol product, far exceeding raw Cu2Se and Pd (or Ni)-doped Cu2Se catalysts without surface Brønsted acid as well as other most of previously reported catalysts.
Psoriasis remains clinically incurable due to its complex etiology. Topical immunosuppressive therapies offer limited effectiveness partly because of poor skin permeability, and can cause severe side effects. To address these challenges, we developed a novel transdermal hydrogen therapy that targets the mutually-reinforcing coupling between oxidative stress and inflammation in psoriasis. Specifically, we designed a double-conical microneedle with high loading capacity and effective skin penetration to efficiently deliver MgH2 powders, enabling the sustained release of molecular hydrogen within the skin tissue. This minimally invasive, self-administrable treatment significantly outperformed calcipotriol cream, a current standard topical therapy. The transdermal hydrogen therapy greatly relieved oxidative damages, pro-inflammatory cytokine expression, immune cell infiltration, and ultimately mitigated keratinocyte hyperproliferation and systemic symptoms. Furthermore, the mechanistic investigations provide valuable insights into psoriasis pathogenesis. More broadly, this study demonstrates a new solution for treating inflammatory skin diseases and a new strategy for microneedle-based transdermal therapeutic delivery.
Aqueous rechargeable Zn–CO2 batteries are emerging as a promising technology for sustainable energy storage and carbon dioxide (CO2) utilization, owing to their high safety, theoretical capacity, and product diversity. Despite their significant theoretical potential, the application of Zn–CO2 batteries is hindered due to several challenges, including low product‐added value, low current density, poor cycle stability, and excessively high overpotential. These issues hinder the widespread use of Zn–CO2 batteries. Cathode bifunctional catalysts, which can promote the CO2 reduction reaction while lowering the reaction energy barrier for the oxygen evolution reaction, have garnered research interest in recent years. However, a systematic summary is rarely reported. This review mainly focuses on the cathode catalysts of aqueous rechargeable Zn–CO2 batteries, summarizing current research progress in terms of devices, reaction mechanisms, and bifunctional catalysts. This review also discusses existing challenges and prospects, offering enlightenment for the future research of Zn–CO2 batteries.