The overuse of antibiotics and dyes presents a considerable threat to both environmental integrity and human wellness due to their persistence in aquatic environments. Thus, the developing of cost-effective and environmentally sustainable photocatalysts for the reduction of antibiotics and dyes, particularly tetracycline (TC) and methyl orange (MO), remains a significant problem. In this study, immensely effective CuO-TiO2@g-C3N4 (CuO-TiO2@g-CN) heterojunction photocatalysts have been developed through the wet impregnation method, demonstrating improved performance in eliminating antibiotic- and dye-contaminated wastewater pursuant to visible light treatment. The CuO-TiO2@g-CN revealed the improved photocatalytic potential towards TC and MO by achieving degradation of 96.1% and 98.5% in 50 min with kobs of 0.0644 and 0.0819 min(-1), higher than CuO@g-CN, TiO2@g-CN, and CuO-TiO2 photocatalysts, respectively. The development of a heterojunction substantially improves the potential of CuO-TiO2@g-CN due to enriched surface area, maximum absorption of visible light, reduced bandgap energy, and a lower recombining rate of photoinduced charges. The variables, including solution pH, photocatalyst dosage, pollutant level, and several inorganic anions affecting the abatement of TC and MO, were extensively analyzed. Additionally, radical trapping experiments demonstrated that superoxide (O-2(center dot-)) and hydroxyl radicals ((OH)-O-center dot) are the major reactive species responsible for the mitigation of TC and MO, which was corroborated by EPR investigation. CuO-TiO2@g-CN photocatalysts have remarkable reuse potential, substantially impacting sustainable development and economic efficiency. The findings highlight the effectiveness of CuO-TiO2@g-CN heterojunctions as practicable photocatalysts for alleviating wastewater contamination, offering practical alternatives for an urgent environmental problem.
Quantum dot-hydrogel (QD-HG) nanocomposites are an emerging class of smart materials that integrate the tunable optoelectronic properties of quantum dots with the biocompatible, stimuli-responsive hydrogel network. This combination offers multifunctional performance that surpasses that of its individual components. The porous structure and abundant active sites of QD-HGs enable efficient charge and energy transfer, making them highly promising for applications in sensing, catalysis, energy, and biomedicine. This review highlights recent progress in QD-HG systems within a synthesis-structure-property-application framework, emphasizing in situ and ex situ fabrication strategies and advanced design techniques for controlled QD distribution and hydrogel architecture. The discussion focuses on three main application areas: environmental remediation through photocatalysis and pollutant monitoring, energy storage via light-assisted capacitance, and biomedical theranostics integrating biosensing and drug delivery. Persistent challenges in stability, scalability, and safety are also addressed, with prospects for improvement through machine learning and 4D-printing technologies.
Electrochemical water splitting for green hydrogen production is severely hindered by the intrinsically sluggish kinetics of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), which require excessive energy input for efficient catalysis. Transition metal selenides (TMSes) have emerged as promising low-cost electrocatalysts benefiting from their metallic-like conductivity, tunable electronic configurations, and favorable d-band center positions, which enable fast charge transfer and near-optimal hydrogen adsorption free energy (Delta GH* approximate to 0). Herein, we systematically review the recent advances in rational design strategies of TMS-based electrocatalysts toward water splitting. Electronic regulation via heteroatom doping, anion engineering and defect modulation is summarized to optimize intermediate adsorption-desorption behaviors, while nanostructure engineering is discussed to enrich accessible active sites and accelerate mass transport. Heterostructure construction with conductive supports such as MXenes and graphene is also highlighted to boost interfacial charge transfer and structural stability. Furthermore, cutting-edge frontiers including single-atom selenides, highentropy selenides and photo-assisted electrocatalysis are outlined to reveal multi-component synergistic effects and maximize atomic utilization efficiency. Despite considerable progress, several critical bottlenecks remain, including insufficient long-term durability under industrial conditions, ambiguous structure-activity relationships, and lack of scalable synthetic routes. This review concludes the current research status, analyzes remaining challenges, and provides insights for the rational design of high-performance TMSes electrocatalysts toward practical green hydrogen production.
Molecular recognition serves as the foundation of bioanalytical strategies. Typical recognition mechanisms include antigen−antibody binding, biotin−streptavidin interaction, aptamer−target pairing, lectin−saccharide recognition, and the chelation of metal ions with phosphate groups, among others. Among these, the chelation of metal−organic frameworks (MOFs) with phosphate groups has emerged as a particularly concise and efficient molecular recognition strategy. In recent years, MOF−phosphate interactions have been extensively exploited in diverse bioanalytical platforms, highlighting their remarkable potential for practical applications. In this review, we summarize MOF−phosphate-based bioanalytical strategies, with a focus on their use in the enrichment of phospholipids and phosphopeptides, kinase activity assays, and the detection of various phosphate-containing analytes. Furthermore, we discuss the development of multifunctional MOF composites enabled by this interaction and conclude with perspectives on the opportunities and challenges that lie ahead.
To develop high-performance and green CO2 adsorbent materials, this study introduces a dual-amine synergy strategy. A composite material was constructed by in-situ growth of NH2-MIL-53 on a polyethyleneimine (PEI)functionalized porous cellulose paper, achieving a mechanically robust adsorbent with a hierarchical pore structure. Benefiting from the synergistic effect between MOF and PEI amine sites, the composite paper PNMP-3 exhibited a CO2 adsorption capacity of 1.71 mmol/g (52 % higher than the unmodified sample), a CO2/N2 selectivity of 138.4 and excellent cyclic stability. Furthermore, theoretical simulation calculations revealed that the high capacity stems from hydrogen bonding between dual amino sites and CO2, while the high selectivity is due to the enhanced CO2 binding energy. This design, integrating synergistic adsorption sites with hierarchical pores, offers an efficient pathway for green carbon capture materials.
Aerospace matt coatings impose stringent requirements on both matting performance and weight reduction. Traditional inorganic matting agents suffer from high density and poor compatibility, whereas organic matting agents are often inadequate for lightweight applications. This study synthesized porous microspheres of polystyrene-poly(epoxypropyl methylacrylate) copolymer with polyethylene glycol dimethacrylate through expanded emulsion polymerization by regulating the ratio of crosslinking agent to porogen. The resulting microspheres exhibit not only low density (0.924 g/cm3) but also a well-defined pore structure, balanced mechanical strength, moderate particle size, and uniform dispersion characteristics. The pore structure delivers the advantage of low density, and the properly controlled size and uniform dispersibility bring excellent matting performance. Subsequently, these microspheres were combined with fluorocarbon resin to produce a composite coating exhibiting stable matting properties, hydrophobicity, and excellent environmental resistance. This approach offers an innovative solution for enhancing lightweight matting coating technology within the aerospace sector.
We report N-phenylbenzo[c]phenothiazine (PTZ-6), an organic small-molecule photocatalyst, which enables a general, metal-free, visible-light-driven Arbuzov-type α-C(sp3)-H phosphonylation of diverse cyclic and acyclic secondary amines via an intramolecular 1,5-hydrogen-atom-transfer (HAT) manifold. The protocol exhibits broad functional-group tolerance and is amenable to late-stage modification of structurally complex drugs and bioactive molecules.
The fabrication of metal−organic frameworks (MOFs) into MOF-on-MOF heterostructures is a promising method to improve their performance across diverse applications. This study presents an organized fabrication of Cu-MOF (BUT-206-Cu) on In-MOF (BUT-205) for the elimination of carbamazepine (CBZ) by the combined effect of adsorption and photocatalytic degradation. BUT-205 was prepared by a solvothermal technique and acted as a host for the in-situ progression of BUT-206-Cu, resulting in a heterostructure BUT-206-Cu@BUT-205. The BUT-206-Cu@BUT-205 exhibited a remarkable efficiency in CBZ removal, achieving a total elimination rate of 99% and adsorption capacity of 86 mg/g, surpassing the performance of pristine MOFs. The pH impact and initial carbamazepine concentration on removal efficacy was systematically investigated. Radical scavenging and EPR investigations revealed that h+ and OH• radicals are the key species involved in the degradation process. The degradation mechanism of CBZ confirmed ring cleavage, hydroxylation and carboxylation as the primary pathways. Kinetic analyses indicated that adsorption and degradation processess confirmed pseudo-second-order and pseudo-first-order models, respectively. The values of the thermodynamic variables (ΔGads, ΔHads, ΔSads) indicated that adsorption is physical, spontaneous, and exothermic in nature, resulting in increased randomness within the system. Furthermore, the BUT-206-Cu@BUT-205 demonstrate exceptional stability and reusability across five reusing cycles.
Melanoma is one of the most lethal cancers in the clinic; cationic peptides have shown great potential in the treatment of melanoma. The large pore volume and high specific surface area of mesoporous silica nanoparticles (MSNs) allow for efficient loading of drugs, while surface-functionalized MSNs can further improve drug stability and carrier targeting. Polydopamine (PDA) coating is an effective surface modification method that provides an additional protective layer to prevent premature drug release during delivery and can prolong the treatment time. Hyaluronic acid (HA) is a commonly used tumor-targeting molecule that binds to HA receptors on the surface of tumor cells, thereby facilitating drug internalization and enhancing the therapeutic effect of the drug. In this paper, the cationic short peptide RKIIIRW, which can effectively inhibit B16F10 cells, was successfully screened by solid-phase synthesis combined with MTT assay and cell membrane chromatography. By combining the cationic short peptide RKIIIRW with MSNs and further surface modification with PDA coating and HA targeting molecules, a nanodrug delivery system with targeted and controllable release characteristics was prepared. This drug-delivery system enhances the efficacy of cationic short peptides while minimizing side effects, offering a more effective therapeutic strategy for melanoma.
Lung cancer has the highest global incidence and mortality, with nonsmall cell lung cancer (NSCLC) as the predominant subtype. Traditional therapies are limited by drug resistance, systemic toxicity, and poor precision. Active ingredients from Chinese herbs offer promising alternatives. This work identified kaempferol (KAE) from Tetrastigma hemsleyanum Diels et Gilg as an anti-NSCLC agent and developed a pH/photothermal dual-responsive nanocarrier (KMPB@PL-HA) for targeted therapy. The nanocarrier uses mesoporous Prussian blue (MPB) as the photothermal core, polylysine (PLL), and ultra-active hyaluronic acid (UL-HA) as the pH-responsive shell. In the tumor microenvironment (TME), UL-HA binds to CD44 receptors overexpressed on NSCLC cells and dissociates, while PLL enhances cellular uptake via electrostatic adsorption. KAE induces mitochondrial apoptosis via p-Akt inhibition, Bax/Bcl-2 regulation, and caspase cascade activation, and downregulates VEGF and modulates TME redox homeostasis for synergistic antitumor effects. This study provides a novel chemo-photothermal synergistic strategy for NSCLC.
A visible‐light‐induced direct synthesis of allylamines has been achieved under transition‐metal‐free and photocatalyst‐free conditions. This method enables efficient coupling of alkenyl sulfonium salts with N ‐arylglycines at room temperature, affording a range of allylamine derivatives in a facile and green manner. Remarkably, the reaction proceeds under exceptionally mild conditions, requires no additional catalysts, and exhibits good functional group tolerance. This strategy offers a sustainable and practical approach to allylamine synthesis, highlighting its potential as an environmentally benign alternative to conventional catalytic systems.
Iodine and its compounds are widely used in radical or ionic iodination of alkenes. In the present work, we opened a new type of iodine-mediated photocatalytic process of alkene functionalization, where iodine atom is not present in the product molecule. Employing NaN3 as an inexpensive and convenient azide source and NH4I/g-C3N4/air as an oxidative system under visible light, regioselective azidohydroxylation of vinylarenes was achieved at room temperature. Presumably, the discovered process involves the generation of azide radicals, their addition to the C = C double bond of a vinylarene, and the interception of resultant benzylic radicals by iodine or molecular oxygen. Noteworthy, both peroxide and iodine-containing intermediates smoothly converted to the target azidohydroxy compounds under optimized conditions without side processes of radical scission or side nucleophile addition.
Selective sites within the nanoconfined spaces of nanofluidic devices play a crucial role in ion selectivity, molecular recognition, and energy conversion. However, the mechanism underlying how the types and density of selective sites govern ion selectivity remains unclear, limiting the design and construction of high-performance nanofluidic devices. Herein, lamellar C3N4/polyethylene terephthalate (C3N4/PET) heterogeneous membranes featuring tunable selective sites (-SO3-, –OH, –COOH) are developed by intercalating poly (sodium-p-styrene sulfonate) (PSS), polyvinyl alcohol (PVA), or polyacrylic acid (PAA) into the light-sensitive C3N4 channels. Experimental results demonstrate that the C3N4-PSS/PET heterogeneous membrane achieves the highest ion selectivity and power output of 0.81 and 5.22 W/m2, respectively. Furthermore, both experimental and theoretical analyses reveal that the superior performance can be attributed to the strong electrostatic and ion-channel interactions between ion and –SO3- sites. Moreover, the density of –SO3- sites significantly affects ion selectivity and ion flux. When the density of –SO3- sites is 2.12∗1028, the heterogeneous membrane achieves optimal selectivity and permeability due to the balance between the space-occupancy effect and the electrostatic effect. Importantly, the C3N4-PSS3/PET heterogeneous membrane exhibits bidirectional light-controlled ion transport, which stems from the light-induced electric field. Notably, an 8.78% improvement in energy conversion performance is obtained upon irradiation of the low-concentration side. This work provides a strategy for constructing highly efficient nanofluidic devices by optimizing selective sites for enhanced ion transport and osmotic energy conversion.
The rapid global demand for innovative, sustainable materials capable of driving advances in energy, environmental remediation, catalysis, and pharmaceutical technologies has intensified the search for greener alternatives to conventional molecular media. In this context, deep eutectic solvents (DESs), particularly those constructed from carboxylic acids, have emerged as a promising new class of functional materials distinguished by low toxicity, tunable physicochemical properties, and broad applicability across materials science and chemical engineering. Traditional volatile organic solvents used in industrial and pharmaceutical applications continue to raise serious concerns due to their toxicity, volatility, and long-term environmental persistence. Carboxylic acid-based DESs offer a sustainable replacement, mitigating these issues while delivering enhanced solubilization, improved drug bioavailability, and safer media for chemical transformations and separations. Despite their growing importance, a comprehensive, class-specific understanding of carboxylic acid DESs has remained underdeveloped. This review systematically compiles and critically assesses the state-of-the-art in carboxylic acid DES formulations, highlighting their synthesis with diverse hydrogen-bond donors (HBDs) and acceptors (HBAs), structural diversity, and physicochemical behaviour. Across various applications, carboxylic acid-based DESs consistently outperform conventional excipients and solvents, offering higher solubility, improved biocompatibility, and a reduced environmental burden. Importantly, this work provides the first unified framework linking formulation strategies with emerging performance trends, identifying critical gaps in understanding their biological compatibility and long-term environmental fate. By consolidating scattered data into a coherent, class-specific analysis, this review establishes rational design principles for next-generation, carboxylic acid-based DESs and positions them as versatile, sustainable materials poised to advance synthetic chemistry, analytical technologies, and materials engineering.
Direct carboamination of alkenes to access structurally complex fluorinated amines remains challenging, particularly when simultaneously installing a trifluoromethyl ketone and a primary amine. With a bifunctional reagent that combines a trifluoromethyl ketal and an imine functionality, we established a metal-free photocatalytic energy-transfer (EnT) strategy for the bifunctionalization of alkenes. Using thioxanthone as the photocatalyst, the reaction accommodates diverse alkene substrates and applies to continuous-flow synthesis.
To address the critical issues of poor biocompatibility and phototoxicity in traditional UV-shielding materials, a functionalized chitosan derivative (CS-MCD) featuring unsaturated aldehyde conjugated moieties was successfully prepared by covalently grafting trans-4-methoxycinnamaldehyde (MCD) onto chitosan (CS) via a Schiff base reaction. The conjugated structure of MCD enables CS-MCD to exhibit strong UV absorption in the range of 280-350 nm, thereby delivering efficient UV-shielding performance. Meanwhile, CS not only improves the water dispersibility of the composite but also mitigates the potential toxicity of MCD while enhancing its biocompatibility. Furthermore, CS-MCD displays prominent antioxidant activity and broad-spectrum antibacterial activity against both Staphylococcus aureus and Escherichia coli. This simple, green preparation strategy endows CS-MCD with great application potential in skin protection, implant surface modification, wound dressings, and packaging materials.
Electrolysis of water is an environmentally conscious technique for synthesizing extremely pristine hydrogen, indispensable to accommodating the power and renewable source requirements of modern-day civilization. The real-world implications of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) suffer from being restricted owing to their sluggish kinetics and dependence on catalysts incorporating noble metals (IrO2, Pt, and RuO2). Recently, cobalt-based nanomaterials have garnered significant interest attributable to their distinguished electronic configuration and inexpensiveness, while demonstrating extensive potential applications in catalytic processes. Nonetheless, the poor conductance, inconsistent inherent catalytic activity, and constrained sites of action of cobalt-based catalysts hinder their practical applicability. The review comprehensively examines design methodologies that strengthen the inherent catalytic activity of cobalt-based catalysts, encompassing morphological and framework management, non-metal heteroatom doping, metal heteroatom doping, anion vacancies and cation vacancies, oxygen/selenium vacancies, and interface engineering. A comprehensive evaluation is presented on diverse approaches to synthesizing heteroatom-doped cobalt-based electrocatalysts. Recent developments in cobalt-based nanomaterials for the electrolysis of water are subsequently evaluated, emphasizing the structure property relationship. The primary objective is the manipulation of cobalt oxide electrocatalysts that contain non-metal (anion) and metal (cation) components. Both the constraints and future implications of cobalt-based electrocatalysts are highlighted.
A novel heterogeneous polyoxometalate-based catalytic strategy for inserting a nitrogen atom into alpha-substituted indanones/cyclopentenones to synthesize isoquinolinones/pyridinones was established. This protocol features mild conditions without stoichiometric oxidants, bases, or acids and tolerates a diverse array of alpha-ester, alkyl, aryl, and hydroxyl groups, harnessing CsHPMo-PEG600 ([PMo12O40](3-)) as a hydrogen atom transfer (HAT) catalyst. Notably, the CsHPMo-PEG600 catalyst maintains high catalytic activity with no significant loss in the reaction yield after at least six consecutive reuse cycles, highlighting its potential as a sustainable and economical alternative to homogeneous systems. Further mechanistic investigations reveal that the nitrogen atom insertion is enabled via a tandem HAT/1,4-H shift/1,2-acyl migration process.
Zwitterionic compounds exhibit strong hydrophilicity, act as hydrogen bond receptors and donors, and form robust hydration layers through ionic solvation, which effectively prevent unwanted protein adsorption. To reduce nonspecific interactions between analytes and the inner surface of the separation compartment and then improve detection sensitivity and separation efficiency, it is essential to modify fused silica capillaries with functional groups. In this study, we synthesized a zwitterionic antifouling peptide (Glu-Lys)3Glu using solid-phase peptide synthesis. Then, we bound the peptide to the inner surface of a fused silica capillary using diazo resin as a coupling agent, resulting in stable and excellent antifouling and separation abilities. To evaluate the properties of the coating, we conducted fluorescent protein adsorption and electrophoresis experiments. The obtained results demonstrated that the coating effectively prevented protein adsorption and made it possible to separate five standard proteins in 20 min. Moreover, three proteins of egg white were separated within 15 min. These findings confirmed the very good anti-protein adsorption performance of the peptide-coated capillary and its practical value for various applications.
Cyanomethylated oxindoles represent an important class of heterocyclic scaffolds. However, previous synthetic methods often suffer from harsh conditions, such as high temperatures, precious metal catalysts, or toxic cyanating sources, coupled with challenges in catalyst recovery. Herein, we report a novel heterogeneous photocatalytic strategy using the double perovskite Cs2AgBiBr6 as a photocatalyst. This methodology enables the visible-light-induced radical cascade cyclization of N-aryl acrylamides with acetonitrile, efficiently producing diverse cyanomethylated oxindoles. This work not only provides a sustainable alternative for the synthesis of these valuable compounds but also highlights the potential of double perovskites in organic photosynthesis.