Developing photocages within the phototherapeutic window is crucial for efficient photopharmacology regulation, yet it poses significant challenges. Herein, we present a photocage prodrug of doxorubicin-methylene blue (DOX-MB) linked by a urea bond, offering spatiotemporal therapeutic selectivity and reduced systemic toxicity. In particular, this photocage prodrug remains stable under physiological conditions, exhibiting reduced cytotoxicity and quenched fluorescence. Upon 660 nm laser irradiation, DOX-MB generates reactive oxygen species that selectively cleave the urea linkage, facilitating the concurrent release of an active pharmaceutical ingredient. This photoactivatable cleavage of DOX-MB allows for precise chemotherapy and photodynamic therapy and restores MB FL for real-time monitoring as well. To achieve localized tumor therapy, the DOX-MB prodrug was encapsulated into a thermosensitive hydrogel, further minimizing the systemic exposure. In vivo studies showed that this integrated platform achieved a tumor inhibition rate of 80.3%. Collectively, this study presents a precision-engineered photoactivatable prodrug that enables synergistic photochemotherapy.

Metal-organic frameworks (MOFs) possess unique structural tunability, abundant coordination sites, and outstanding biosafety, rendering them highly advantageous for the development of high-performance magnetic resonance imaging (MRI) contrast agents. In light of the significant advancements in MOF-derived theranostic platforms, a comprehensive overview focusing on their classification and clinically oriented applications is urgently required. This review provides an in-depth examination of various categories of MOF-derived contrast agents, including T1, T2, dual-mode, ratiometric and 19F imaging systems, and analyzes the correlation between structural characteristics and imaging performance. Furthermore, it highlights typical MRI-guided therapeutic applications, such as those related to atherosclerosis, bacterial infections, and cancer immunotherapy. The review systematically addresses existing challenges, including issues related to biodegradability, metabolic behavior, and biosafety. It also summarizes the rational design principles for novel MOF contrast agents, aiming to facilitate their transition from fundamental research to clinical applications.

Syringeable hydrogels have emerged as transformative tools for precise drug delivery and controlled release, capitalizing on their exceptional injectability, shape adaptability, and localized retention. This review provides an overview of the recent advancements in hydrogel-based cargo delivery systems, focusing on injectable hydrogelators with immunomodulatory functions. Design principles tailored to optimizing the gelification process are presented, compared, and discussed following detailed structural analysis, with an emphasis on hydrogel formation mechanisms and biointeractions. Next, we summarize key applications, including adoptive cell therapy, catalytic immunotherapy, cancer vaccination, proteolysis-targeting chimeras, and immunometabolic intervention. To achieve a high therapeutic index while minimizing systemic side effects, the underlying mechanisms governing the spatiotemporal release of immunomodulators are presented as well. Finally, this review systematically discusses the persistent obstacles concerning manufacturing, biological safety, and clinical translation of these regulatory frameworks.

Ultra-low friction coefficients and prolonged atmospheric lifetime for hydrogenated amorphous carbon (denoted a-C:H) films remain a significant challenge in the research of present. In this work, a reactive magnetron sputtering deposition facility was employed to fabricate sp(2)-rich a-C:H films via metal-induced self-assembly route in the presence of Ti catalyst. The microstructure and composition of the as-prepared composite films exhibited significant variability with Ti content, particularly characterized by an abundance of sp(2) nanocrystallites embedded within amorphous carbon matrix. Moreover, the tribological behaviors and mechanical properties of Ti/a-C:H composite films were explored. The results showed that the formation of sp(2)-C nanocrystallites strengthened the Ti/a-C:H composite films from 9.8 GPa to 11.2 GPa and improved the adhesion from 19.5 N to 29.7 N. Meanwhile, the as-deposited films with sp(2) nanocrystallites structure presented extremely low friction coefficient. And the characterizations of wear tracks and rubbing pairs revealed that plentiful sp(2)-C nanocrystallites that originated from Ti-promoting effect aggregate at sliding surfaces between the film and the rubbing pair, resulting in outstanding tribological behavior. Especially, the film deposited at 40 % methane flow ratio exhibited superior wear lifetime similar to 1400 m with 0.083 friction coefficient, which showed promising potential in the industrial application as the solid lubrication film.

As nanoscale metal-organic frameworks (MOFs) become increasingly prevalent, elucidating their fundamental interactions with proteins and cells is vital for evaluating their biological effects and biocompatibility. Herein, we investigated the protein corona (PC) formed on three representative MOFs (MIL-88, ZIF-8, UiO-66) and their impacts on macrophage uptake and cytotoxicity. Proteomic analysis revealed that the PC compositions were highly material-dependent, governed by the MOFs' distinct physicochemical properties. MIL-88 and ZIF-8 exhibited significant enrichment of acute-phase proteins and lipoproteins, whereas UiO-66 adsorbed high proportions of complement system proteins and lipoproteins. Apolipoprotein A-I (ApoA-I) was the most abundant protein across all three MOFs, while albumin was predominant on ZIF-8 and complement C3 was highly enriched on MIL-88. Functionally, PC formation reduced macrophage uptake of ZIF-8 and UiO-66 but had a negligible effect on MIL-88. The differences attributed to variations in dysopsonin/opsonin enrichment and surface charge alteration. Notably, the PC formation also significantly mitigated the cytotoxicity of ZIF-8 by reducing its cellular internalization. Together, these findings demonstrated that the PC is a pivotal factor influencing both the cellular interactions and the safety profile of MOFs, providing crucial insights for designing safer nanoparticle-based applications.

Microcrystalline diamond (MCD) coatings exhibit high friction coefficients due to their rough surface morphology with sharp protrusions, which cause substantial ploughing during sliding contact. To address this challenge, a novel in situ synthesis strategy leveraging bimetallic (Ni/Ga) synergistic catalysis was developed in this study. The growth of a dual-oriented (vertically and horizontally oriented) graphene-microcrystalline diamond (DG-MCD) was achieved via this approach, and the graphene binds the MCD via covalent bond. Compared with pure MCD, the DG-MCD coating exhibits a low friction coefficient of 0.03 and an ultra-low wear rate of 1.65 & times; 10-6 mm3/(N & sdot;m) in the simulated seawater environment, reduction of 53.8% and 56.3%, respectively. This enhancement is attributed to the unique dual-oriented graphene structure at the coating surface, which operates through two complementary mechanisms. First, it mitigates interfacial frictional chemical reactions. This reduction in chemical activity minimizes interfacial adhesion, thereby directly reducing the coating's friction coefficient. Second, the graphene structure facilitates the formation of "graphene nanoscrolls" during sliding contact, which transform the contact interface from pure sliding to hybrid sliding-rolling mode and thus effectively enhance the tribological performance. This work illustrates that engineering a dual-oriented graphene nanostructure on diamond coatings offers an effective approach for enhancing their tribological properties in simulated seawater environments.

Toll-like receptor 7/8 (TLR7/8) agonists (such as resiquimod-R848) are potent immune adjuvants. However, their clinical use is limited by severe systemic toxicity. To address this challenge, prodrug strategies have emerged as a key solution. In recent years, researchers have developed various prodrugs through chemical modifications. These prodrugs can be selectively activated within the tumor microenvironment in response to specific triggers, such as hypoxia, ultrasound, radiotherapy, or overexpressed enzymes. This approach enables spatiotemporally controlled release of the active drug and significantly reduces systemic inflammatory responses. To further enhance therapeutic efficacy and targeting precision, advanced delivery systems (protein nanoparticles, polymeric nanogels, liposomes, and nanoparticle suspensions) have been employed to carry these prodrugs. Such systems not only provide sustained release but also allow co-delivery of antigens, siRNA, or chemotherapeutic agents. This facilitates synergistic modulation of the tumor immune microenvironment. When combined with immune checkpoint inhibitors (ICIs) or chemotherapy, they exhibit strong synergistic antitumor effects and induce durable immune memory. Notably, several of these approaches have already entered clinical evaluation. By summarizing recent advances in both prodrug chemistry and sophisticated delivery platforms, this review highlights a promising path toward precise and controllable delivery of TLR7/8 agonists. We hope this integrated strategy will pave the way for safer and more effective cancer immunotherapies.

Two-dimensional porphyrin-based metal-organic frameworks (2D Por-MOFs) have emerged as promising candidates in biomedical applications due to their ultrathin morphology, high surface area, tunable electronic properties, and excellent optical characteristics. This review systematically summarizes recent advances in their utilization for cancer therapy, antibacterial treatment, and biosensing. In oncology, 2D Por-MOFs serve as efficient photosensitizers for photodynamic therapy (PDT) by generating reactive oxygen species (ROS) to eradicate tumor cells, while also enabling synergistic therapeutic outcomes through integration with chemodynamic therapy (CDT), chemotherapy, immunotherapy, sonodynamic therapy (SDT), and novel mechanisms such as copper-dependent cell death. For antibacterial applications, these materials enhance ROS production via size engineering, single-atom modification, or nanozyme loading, effectively killing pathogens and promoting wound healing, as well as being incorporated into smart dressings to achieve combined hemostatic and antimicrobial functions. In biosensing, 2D Por-MOFs act as ideal platforms for photoelectrochemical signal transduction or fluorescent probes, facilitating the development of highly sensitive fiber-optic SPR, electrochemical, and fluorescence sensors capable of detecting disease biomarkers, pathogens, small-molecule metabolites, and ions with high sensitivity. Finally, the current challenges and future prospects for the clinical translation of 2D Por-MOFs are discussed.

Covalent organic frameworks (COFs) have emerged as promising candidates in cancer immunotherapy, owing to their tunable pore structures, versatile functionality, and favorable biocompatibility. This review systematically highlights recent advances in COF-based materials that enhance immunotherapeutic efficacy through multiple strategies. Particular emphasis is placed on functionalized COFs for remodeling the immunosuppressive tumor microenvironment, by alleviating hypoxia and depleting glutathione, and their role as core sensitizers in various therapeutic modalities, including photodynamic, sonodynamic, radiotherapy, and chemodynamic therapy, to efficiently trigger immunogenic cell death (ICD). In addition, we comprehensively summarize how strategic structural engineering enhances phototherapeutic efficacy. This includes modulating the metal ions incorporated into the COF, controlling COF stacking modes, and adjusting the planarity or conformational twist of the building units to precisely tune bandgap energy and light absorption properties, thereby promoting stronger ICD induction. Furthermore, COFs serve as intelligent delivery platforms capable of controlled release of immune adjuvants and checkpoint inhibitors. The discussion also extends to cutting-edge applications, such as imaging-guided therapy, induction of tertiary lymphoid structure (TLS) formation, and activation of abscopal effects. These developments discussed in this review underscore the immense potential of COFs as multifunctional nanoplatforms in advancing effective and precise combination cancer immunotherapy. The insights provided in this review offer valuable reference for the biomedical applications of COFs, particularly in the integrated development of multimodal therapies and immunotherapy.

The tumor microenvironment (TME) represents a sophisticated ecosystem wherein resident biomaterials orchestrate therapeutic resistance, and immune evasion, making it a critical target for cancer immunotherapy. This review underscores the central role of the TME in immunomodulation and the potential of TME-activatable immunomodulators to revolutionize cancer immunotherapy. We first provide an overview of the characteristics and components within the TME that drive tumor growth and metastasis, including immune cells, stromal cells, and metabolic factors. Next, we summarize the design principles and responsive mechanisms of TME-activatable immunomodulators, covering pH, glutathione, hydrogen peroxide, enzymes, and hypoxia to enhance tumor penetration and reduce off-target effects. Preclinical successes of emerging technologies, such as immune checkpoint inhibitors, chimeric antigen receptors, mRNA vaccines, stimulator of interferon genes agonists, and proteolysis-targeting chimeras, highlight the importance of spatiotemporally controllable immunomodulator delivery leveraging these pathophysiological signals. Finally, we discuss current limitations, including TME-induced resistance mechanisms and biosafety considerations, and outline future directions for TME-activatable immunomodulators. Integrated stimuli-responsive characteristics have proven to be effective in precisely controlling the delivery and activation of immunomodulators within the complex microenvironment.

Conventional cancer immunotherapy frequently encounters limitations such as suboptimal clinical responses, systemic adverse effects, and acquired immunologic tolerance. Rationally designed smart nanomaterials, engineered to recognize tumor-specific stimuli, target immune cells, and remodel the tumor microenvironment, offer significant potential in overcoming these formidable challenges in metastatic tumors. In this review, we summarize the latest advancements in efficacious therapeutic interventions for the purpose of improving pharmaceutical properties, remodeling tumor immune microenvironment, and achieving combined immunotherapy. Then, we provide a brief overview of the most recent combinational immunotherapy corresponding clinical management, highlighting the clinically validated combinations that elicit systemic antitumor immunity and long-term immunomodulatory memory. Furthermore, we outline key molecular mechanisms and signaling pathways for organ-specific metastasis, and discuss certain preclinical advancements in the realm of smart nanomaterials integrated with existing treatment modalities and immunomodulatory strategies. Additionally, the discussion includes present challenges and future opportunities in designing functional nanomaterials, emphasizing the critical factors related to material design, safety concerns, and regulatory mechanisms. Overall, this review synthesizes preclinical and clinical findings to demonstrate how smart nanomaterials can enhance the therapeutic index through multi-target immunomodulation, and it examines the major challenges and future possibilities of immunotherapy combinations.

Indocyanine green (ICG) is a small molecule approved by the U.S. Food and Drug Administration (FDA) for liver function imaging and angiography. ICG can be used not only for near-infrared imaging but also for photodynamic and photothermal therapy. However, the hydrophilicity of ICG leads to a relatively short blood circulation time, and it is easily cleared by organs such as the liver. Moreover, it lacks the targeting ability to the diseased sites. By using the natural porous metal-organic frameworks (MOFs) as the carrier, high-efficiency loading of ICG molecule can be achieved, which has significantly broadened its biomedical applications. This review comprehensively summarizes the research work in recent years regarding the utilization of MOF as a carrier to load ICG in the bioapplication such as malignant cancer inhibition, antibacterial treatment, and the treatment of Alzheimer’s disease. It focuses on summarizing the design concepts of different types of MOF carriers for loading ICG molecules. Meanwhile, it emphasizes the enhanced therapeutic effects achieved when multiple treatment modalities realized through post-modification are combined with ICG-mediated phototherapy. It is expected that through the summary of this review, the biomedical applications of ICG in the field of disease treatment can be further promoted.

Covalent organic frameworks (COFs) offer structural tunability and intrinsic porosity, yet precise nanoscale fabrication of COF-based photosensitizers remains challenging. In this study, we report a mixed-solvent-mediated one-pot strategy to synthesize chlorin (TPC)-incorporated COF nanoparticles with tunable size by adjusting solvent composition and TPC feed ratio. Azo-based ligands confer hypoxia sensitivity to the framework. The optimized TPCCOF morphology was used to load tirapazamine (TPZ), forming the biocompatible TPCCOF@TPZ nanoplatform. Upon light irradiation, TPCCOF@TPZ enables concurrent photodynamic (PDT) and photothermal therapy (PTT). PDT exacerbates tumor hypoxia, triggering TPZ release and hypoxia-activated chemotherapy. This synergistic PDT/PTT/chemotherapy combination effectively suppresses 4T1 tumor cell proliferation under both normoxic and hypoxic conditions. Our work advances nanoscale COF design for multimodal cancer therapy and supports preclinical development of porphyrin-based photosensitizers.

Increasing threats of data forgery breaches necessitate the development of advanced encryption strategies beyond traditional cryptographic methods. Fluorescence encryption has emerged as a promising alternative, yet current systems suffer from low security due to simple, reversible stimuli responses. Here, we introduce a novel lock-and-key encryption system using a chiral cyclodextrin metal–organic framework (CDMOF), termed Zole@CDMOF (Zole = acetylated benzoimidazole), for enantioselective discrimination of phenylethylamine (PEA) enantiomers.Confined Zole serves as the lock, while PEA enantiomers act as the key, selectively triggering fluorescence turn-on via acetyl─O bond cleavage and restoring excited-state intramolecular proton transfer (ESIPT) of deacetylated Zole. Mechanistic studies reveal that enantioselectivity arises from thermodynamic differences and distinct hydrogen-bonding interactions between PEA enantiomers. To enhance practical application, Zole@CDMOF is fabricated into a flexible sensor via scotch tape strategy, enabling visual indexing of enantiomeric excess. Additionally, we propose a barcode chiral encryption model, establishing a quadruply encrypted system with ultra-high security—allowing only one out of approximately two million keys to decrypt. This study pioneers the first chiral cryptographic key in fluorescence encryption, paving the way for ultra-secure encryption, advanced chiral sensing, and stimuli-responsive materials.

Glycolaldehyde, a simple yet crucial organic compound, plays an important role in atmospheric chemistry and prebiotic studies. In this study, we examine the formation and thermal dissociation of protonated glycolaldehyde and its isomers. To achieve this, we develop comprehensive reaction networks using a novel approach based on ab initio molecular dynamics simulations, and analyze their behavior across thermal and hyperthermal temperature regimes. This approach offers valuable insights into the free energy landscape, reaction pathways, and temperature-dependent mechanisms of molecular formation. Our results demonstrate that the reaction network is highly temperature-dependent. Above 400 K, the transition to the product predominantly occurs through a direct pathway from reactant to product, primarily driven by transient high-temperature effects. This work highlights the potential of molecular dynamics simulations to enhance our understanding of atmospheric and interstellar chemistry, surpassing the limitations of conventional models.

The development of innovative materials capable of detecting heavy metal ions is a crucial goal in the field of environmental remediation. However, achieving high selectivity for specific metal ions remains a challenge. This study designs a novel imine-based COF via Schiff base condensation for efficient detection of cobalt ions (Co2+) in environmental samples. The π-conjugation system provides excellent fluorescence properties. The COF contains tertiary amine and imine structures with nitrogen and oxygen atoms, enabling coordination with Co2+ as a Lewis base. This interaction disrupts the conjugated structure, causing fluorescence quenching. The experimental results demonstrate that our proposed method stands out in Co2+ detection, distinguished by its remarkable simplicity, exceptional sensitivity, rapid response time, and easy operability. The novel imine-based COF sensor exhibits high sensitivity (limit of detection = 8.5 × 10-13 M), excellent selectivity and stability in fluorescence detection, enabling accurate identification of Co2+ in complex environments. This research not only presents an efficient and practical approach for the detection of Co2+ but also offers novel theoretical perspectives on the design and application of imine-based COF. The findings lay a solid foundation for the development of COF-based environmental monitoring technologies.

Porphyrin and its derivatives are widely used in cancer therapy due to their strong photon absorption capabilities and moderate light stability. Due to their hydrophobic nature, porphyrins with tetrapyrrolic macrocycles ease self-aggregation in physiological conditions. Instead, exploiting the C4 symmetry structure for self-assembly is beneficial to improve the bioavailability of porphyrin and its derivatives. Herein, this Review outlines porphyrin-based nanoformulations for therapeutic applications in cancer treatment. The typical pharmaceutical application of the integrated porphyrinic structure is systematically summarized, focusing on the typical synthetic methodologies and structure-functionality relationship. Additionally, therapeutic modalities (e.g., photothermal, photodynamic, and sonodynamic) and their synergy mechanism in regulated cell death are overviewed. Special attention is given to emerging technologies in nanocatalytic therapy, therapeutic vaccines, and proteolysis-targeting chimeras, which align with the trend toward personalization and minimal invasiveness in healthcare. Finally, we discuss the challenges and limitations of porphyrinic nanoformulations and explore their future directions in the healthcare sector, aiming to bridge the gap between research and practical clinical application.

Despite showing great potential in lead-free green energy, tin-based perovskite materials still face challenges such as inherent material instability and energy level misalignment with the hole transport layer (HTL), which limits the advancement of tin-based perovskite solar cells (Sn-PSCs). In this work, a natural antioxidant organic small molecule, thiolactic acid (TA), is used to modify the interface between PEDOT:PSS and the tin-based perovskite film. The TA molecule can cross-link to form a network polymer and regulate the microstructure and photoelectrical characteristics of PEDOT:PSS. Meanwhile, TA contains C═O and C─S groups, which can interact with Sn2+ to inhibit its oxidation. Moreover, the introduction of TA interfacial modification effectively improves the morphology of the perovskite film, suppresses interfacial charge recombination, and promotes carrier transport. Thus, TA-modified Sn-PSCs achieve a champion power conversion efficiency of 9.03%, surpassing 6.92% of the control PSCs. Even after being stored for 1000 h in a nitrogen atmosphere, the unencapsulated devices with TA modification still maintain 95.4% of their original PCE, compared to only 66.5% of the control devices. This study demonstrates the significance of the PEDOT:PSS/tin-perovskite interfacial modification on the efficiency and stability of Sn-PSCs.