An ultrasensitive photoelectrochemical platform is constructed by integrating plasmonic Ag@Au nanocubes with Bi2MoO6-MoS2 nanoflowers and specific group functional pillar[5]arene. The synergistic LSPR and heterojunction effects enable specific ˙OH detection down to 0.25 µM, offering promise for reactive oxygen species analysis in biological systems.
Electrochemical and photoelectrochemical detection techniques have been widely applied in fields such as bioanalysis, environmental monitoring, and food safety due to their rapid response, operational simplicity, and high sensitivity. However, achieving highly selective recognition of target analytes in complex samples, enhancing sensitivity for trace analysis, and constructing stable electrode interfaces remain core challenges in this field. As the fifth-generation macrocyclic supramolecular hosts, pillar[n]arenes possess a unique pillar-shaped symmetrical structure, an electron-rich cavity, and readily functionalizable rims, enabling highly selective recognition of guest molecules through multiple non-covalent interactions. This provides new insights into addressing the above-mentioned challenges. This Feature Article systematically reviews the research progress of pillar[n]arenes in the field of electrochemical and photoelectrochemical detection. The related research work is summarized from two dimensions: first, the construction strategies for different types of pillar[n]arene-based electrode modification materials, including pure pillar[n]arene self-assembled materials, pillar[n]arene-metal nanocomposites, pillar[n]arene-inorganic nonmetallic nanomaterials, pillar[n]arene-metal/nonmetal hybrid nanomaterials, and cooperatively assembled materials based on two distinct types of pillar[n]arenes. Second, the applications of these pillar[n]arene-functionalized electrodes in the detection of various classes of substances, including biomarkers and disease-related substances, neurotransmitters and psychoactive substances, environmental pollutants and toxins, small biomolecules and metabolites, as well as inorganic active species. Finally, future development directions for pillar[n]arene-based electrochemical sensors are discussed, aiming to provide a reference for research on the rational design and applications of high-performance supramolecular electrochemical sensors.
Abstract Photodynamic therapy (PDT) has some major problems that seriously limit its use in treating tumors. For example, the photosensitizers tend to clump together, which causes fluorescence to drop sharply. They also do not produce enough singlet oxygen, and they cannot accurately reach the specific parts of cancer cells that need to be targeted. To address these bottlenecks, we designed and fabricated a new amphiphilic metallacycle based on pillar[5]arene and Pt(II), which we named AmMeCy. This material has a special two-cavity structure that has never been reported before. One cavity comes from the pillar[5]arene part and can precisely hold targeting molecules through host-guest interaction, The other cavity is formed by the Pt-coordinated metallacycle, which helps to confine the structure and control its functions. Notably, Pt coordination effectively restricts the π-π stacking of porphyrin moieties, fundamentally eliminating aggregation-caused quenching (ACQ) and significantly boosting fluorescence emission and 1O2 photogeneration efficiency. Benefiting from its amphiphilic nature, the metallacycle can spontaneously self-assemble into uniform nanostructures in aqueous media with excellent water dispersibility and biocompatibility. After host-guest encapsulation of mitochondrial-targeted guests, the assembled nanoparticles (AmMeCy ⊃ TPP NPs) achieve precise mitochondrial localization in tumor cells. Upon light irradiation, the amplified 1O2 burst efficiently triggers mitochondrial oxidative damage and tumor cell apoptosis. This work establishes a new dual-cavity supramolecular platform via metal-ligand coordination and pillararene host-guest chemistry, providing a facile and universal strategy for the structural optimization and functional upgrading of high-efficiency tumor PDT nanotherapeutics.
4-Nitrophenol (4-NP) is a major environmental pollutant, and its health risks call for efficient recognition methods. Here, we developed a Ti3C2Tx MXene-supported cationic [2]biphenyl-extended pillar[6]arene-functionalized Fe3O4@Au platform for 4-nitrophenol detection. It relies on host-guest recognition, fast electron transfer, and Fe2+/Fe3+ catalysis, achieving excellent electrocatalytic performance in environmental applications.
This study reports the development and characterization of a novel optical fiber sensor designed for the sensitive detection of dissolved oxygen. The sensing architecture was fabricated on the distal end of an optical fiber using a dip-coating technique. The core sensing layer consists of the oxygen-responsive luminophore, ruthenium(II)-tris(4,7-diphenyl-1,10-phenanthroline) dichloride (Ru(dpp)3Cl2), physically immobilized within a fluorinated xerogel matrix derived from the co-condensation of 3,3,3-trifluoropropyltrimethoxysilane (TFP-TMOS) and propyltriethoxysilane (PTEOS). To enhance durability and prevent indicator leakage, a secondary layer of cellulose acetate was applied as a protective barrier over the sensing film. Comprehensive structural and morphological analyses of the resulting composite film were conducted utilizing Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), while optical properties were evaluated via fluorescence spectrophotometry. The sensor operates on the principle of fluorescence quenching, demonstrating a robust response to oxygen in aqueous environments. Analytical performance testing revealed excellent linearity in the Stern-Volmer plot (I0/I) across a broad dissolved oxygen concentration range of 0 to 30.7 mg L-1. The device achieved a low detection limit of 0.05 mg L-1 and a rapid response time of 5 seconds. Furthermore, the prepared sensor exhibited superior stability and resistance to dye leaching, confirming its significant potential for reliable, long-term monitoring of dissolved oxygen in diverse aquatic applications.
Artificial light-harvesting systems (ALHSs) inspired by the antenna function of natural photosynthesis provide molecular platforms for collecting excitation energy and directing it to emissive or reactive acceptors. In many supramolecular ALHSs, however, practical performance is limited by poorly defined donor-acceptor orientation, aggregation-caused quenching (ACQ), interfacial defects, and limited stability in aqueous or complex media. Supramolecular macrocycles-particularly pillar[n]arenes (PAs), cucurbit[n]urils (CBs), calixarenes (CAs), cyclodextrins (CDs), and supramolecular coordination complexes (SCCs)-offer a useful design space because their cavities, pre-organized scaffolds, and reversible non-covalent interactions can confine chromophores, tune local donor/acceptor ratios, and modulate Förster resonance energy transfer (FRET). This Review systematically examines the unique structural advantages and assembly mechanisms of the five macrocyclic families, with an emphasis on their use in constructing ALHSs-from single-step to cascaded FRET-and in advancing aqueous photocatalysis, near-infrared bioimaging, panchromatic fluorescence modulation, and singlet oxygen generation. The resulting structure-property-application framework is intended to guide the rational design of macrocycle-assisted photofunctional materials while avoiding overextension of the photosynthesis analogy.
Molecular recognition plays an important role in biological systems and is closely related to the origin of life. Macrocyclic hosts, such as cyclodextrins, cucurbiturils, calixarenes, and pillar[n]arenes, have permitted seminal advances in molecular recognition. Incorporated macrocyclic hosts into covalent-organic frameworks (COFs) will offer both permanent accessible pores and selective molecular recognition capability. In this work, we designed and fabricated a pillar[5]arene incorporated covalent-organic frameworks (P5COF) from 4-aminophenyl-modify pillar[5]arene (P5NH2) and tetra-(4-benzaldehyde)-tetraphenylethylene (TPECHO) as an efficient cancer therapy platform. The target molecule G (N-biotinyl-1,6-hexanediamine) can be easily introduced into P5COF to form P5COF?G NPs through host-guest molecular recognition. P5COF?G NPs demonstrated excellent cell imaging performance, owing to the incorporation of tetraphenylethylene (TPE) units. Then, drug molecules DOX can be further loaded efficiently to form P5COF?G/DOX particles through inherent porous structure of COFs. With the assistance of target molecule G, P5COF?G/DOX can effectively enrich tumor tissue and release drugs in the weak acidic environment to achieve targeted therapy. This work provides a new strategy to combine host-guest molecular recognition and covalent-organic frameworks, which will inspire more strategies for precise cancer therapy.
Two unprecedented rim-differentiated extended pillar[6]arene (RdEP6) derivatives are successfully synthesized for the first time. Their slight structural differences induce completely different crystal self-assembly properties, further leading to obvious divergences in their catalytic activities.
An oxime-functionalized pillar[5]arene-based supramolecular polymer was constructed via orthogonal host-guest interactions and metal coordination. Antimicrobial activity assays demonstrated that the resulting Ag NP-doped polymer exhibits significant antibacterial efficacy against both Staphylococcus aureus and Escherichia coli.
A targeted nanoplatform was developed by formulating a polydopamine-prodrug conjugate with pillar[5]arene, achieving targeted and synergistic combination of CDT, PTT, and CT.
Carcinoembryonic antigen (CEA), a well-established tumor biomarker, is a human glycoprotein involved in cell adhesion that is highly expressed during fetal development. In this work, we present an innovative photo-electrochemical immunosensor constructed from an AuPt@NP5/BiOI-MoS2 heterostructure for the ultrasensitive detection of CEA. The sensor design integrates multiple functional components that operate synergistically to enhance photoelectrochemical performance. Specifically, the AuPt bimetallic nanocomposite amplifies light absorption and facilitates charge transfer via localized surface plasmon resonance (LSPR) and electronic coupling effects. Concurrently, the BiOI-MoS2 heterojunction combines the high electrical conductivity of BiOI with the extensive specific surface area of MoS2; their staggered band alignment promotes efficient separation of photogenerated electron-hole pairs and significantly suppresses charge recombination. Further functionalization with aminated pillar[5]arene (NP5) introduces host-guest molecular recognition capabilities, enabling selective capture of target analytes, while its incorporation with AuPt inhibits nanoparticle aggregation and enhances photocurrent generation. Owing to these coordinated features, the AuPt@NP5/BiOI-MoS2 immunosensor demonstrates exceptional analytical performance, achieving an ultra-low detection limit of 0.33 pg/mL (S/N = 3) and a wide linear detection range from 0.001 to 50 ng/mL. This advanced sensing platform thus exhibits considerable potential for clinical application, providing a highly sensitive and reliable tool for early cancer diagnosis and monitoring.
Metal nanomaterials (MeNPs) possess advantages such as high specific surface areas, excellent optical properties, good electrical and thermal conductivity, tunable magnetic properties, high chemical reactivity, and biocompatibility. These advantages enable metal nanomaterials to have broad applications in various fields. Pillar[n]arenes, the newest class of classical synthetic macrocycles with rich host-guest properties, have recently sparked extensive research interest among scientists. The combination of metal nanomaterials and pillar[n]arenes is expected to integrate and enhance the respective excellent properties of both. This Review systematically outlines the recent progress in the fabrication strategies and important applications of pillar[n]arene-mediated metal nanomaterials in sensing, drug delivery, cancer therapy, and catalysis. A brief outlook on the future development of pillar[n]arene-mediated metal nanomaterials is also presented.
Radio-resistance poses a significant challenge in meningioma treatment. This study aimed to establish radio-resistant meningioma cell lines and uncover molecular mechanisms driving radio-resistance to identify potential biomarkers and therapeutic targets. Radio-resistant meningioma cell lines (IOMM-Lee-RR, CH157-RR) were developed using a progressive radiation dose (cumulative 90 Gy). Cell morphology, radiosensitivity, apoptosis, viability, migration, invasion, cell cycle, and DNA damage repair were analyzed via clonogenic assays, flow cytometry, and Western blotting. Transcriptome sequencing was performed to identify differentially expressed genes (DEGs), followed by KEGG and GO enrichment analyses. Protein-protein interaction (PPI) analysis was conducted to identify hub genes. TK1 expression was further validated in a cohort of 350 meningiomas and the GSE189672 dataset. Radio-resistant meningioma cell lines exhibited enhanced survival, reduced apoptosis, increased cell viability, and superior migratory and invasive abilities compared to parental cells. Under radiation, these cells showed G0/G1 phase accumulation and reduced G2/M phase arrest, along with enhanced DNA repair capacity, as evidenced by lower γ-H2AX expression and fewer DNA damage foci. Transcriptome analysis revealed significant enrichment in metabolic pathways, DNA repair, and cell cycle regulation. Among 34 hub genes identified, TK1 emerged as a key gene, being highly expressed in recurrent and high-grade meningiomas and positively correlated with Ki67. Analysis of the GSE189672 dataset confirmed TK1 as a poor prognostic factor associated with tumor recurrence. Radio-resistant meningioma cells exhibit enhanced DNA repair, migration, invasion, and altered cell cycle dynamics. TK1 was identified as a promising biomarker and therapeutic target for overcoming radio-resistance in meningiomas.
Sensitive detection of dopamine (DA) and uric acid (UA) is essential because the abnormal levels of them may trigger parkinson's and gout. In this study, a photoelectrical chemical-colorimetric dual-mode sensor platform was constructed based on Au@BP5/Ni-NiO-polyaniline (PANI) for the detection of DA and UA. In the photoelectrical chemical mode, on account of the localized surface plasmon resonance (LSPR) effect of Au NPs, the excellent photo-electron transfer ability of Ni-NiO-PANI and the adsorption ability of a sulfhydryl-borateester modified A1/B1 type pillar[5]arene (BP5) to guest molecules, the photoelectrochemical response to DA and UA is greatly enhanced. In colorimetric mode, 3,3 ',5,5'-Tetramethylbenzidine (TMB) turns blue in the presence of substrate hydrogen peroxide TMBox due to the action of NiO nanozymes. With the addition of DA and UA, TMBox was reduced to TMB and the UV-Vis absorption peak decreased. Under optimal conditions, the detection limits of DA and UA were as low as 0.017 mu M and 0.17 mu M (PEC), 0.33 mu M and 6.67 mu M (colorimetric mode). Simultaneously, the constructed sensor has a high response to DA and UA in both modes and provides a sensitive and accurate platform for DA and UA detection. Also, the high selectivity and sensitivity further demonstrate that the dual-mode sensor platform could extend to more applications to detect bioactive molecules.
A hyaluronic acid-modified nanotheranostic platform (Fe-DALN@HA) was constructed via Fe3+-coordinated self-assembly of a GSH-responsive SO2 prodrug, enabling tumor-targeted delivery and synergistic induction of gas-enhanced ferroptosis through SO2 gas release and the Fenton reaction for effective cancer therapy.
Most of non-fullerene acceptors used in organic solar cells are synthesized through cross-coupling reactions, which require expensive transition metal catalysts, harsh reaction conditions and complex purification processes, making large-scale production high cost. Here, two azomethine-based perylene diimides (PDIs) are designed and synthesized through a simple and economical Schiff base condensation reaction with water as the only byproduct. As the non-fullerene acceptors for organic solar cells, power conversion efficiencies exceeding 4.3 % were reached. Furthermore, the cost estimations show that the material cost of azomethine-based PDIs is about two orders of magnitude lower. In addition, the synthesis of azomethine-based PDIs also reduces the toxic chemical waste, thus greatly reducing the environmental impact. Our results pave the way for low-cost, environmentally friendly and efficient non-fullerene acceptors.
An intelligent INH@ZIF@MnO2/HA nanotherapeutic platform, ingeniously engineered to augment tumor-specific oxidative stress in chemodynamic therapy, effectively harnesses the isoniazid (INH)-mediated generation of highly reactive non-Fenton-type hydroxyl radicals (˙OH) catalyzed by Mn2+ ions.
A GSH-responsive nanoplatform (Fe-DALN@HA) is constructed via coordinated self-assembly for tumor-targeted SO 2 release and Fe 2+ self-supply, which synergistically enhances gas therapy and ferroptosis.
To address the challenges of precise calcium regulation and limited efficacy in MOF-based nanomedicine, we developed a biodegradable Ca-MOF platform (Ca-MOF@MnCO/HA) coated with hyaluronic acid (HA) and loaded with a H2O2-responsive CO prodrug, manganese carbonyl (MnCO). This system enables CD44-mediated tumor targeting, followed by acid-triggered biodegradation in the tumor microenvironment (TME) to release Ca2+ and MnCO. Intracellular H2O2 then promotes CO release, inducing mitochondrial dysfunction and impairing calcium efflux. The concurrent release of Ca2+ and CO causes sustained calcium overload, intensifying oxidative stress, activating apoptosis, and triggering tumor-specific calcification. This gas-ion synergy highlights the potential of programmable inorganic nanomedicines for improved anticancer therapy.
The hydroxyl radical (•OH), one of the most reactive oxygen species (ROS), exhibits unparalleled oxidative capacity, inducing direct damage to proteins, lipids, and DNA, thereby triggering cellular dysfunction and death. Herein, we develop a triple-signal-amplified biosensor based on N-(2-hydroxyphenyl)acetamido- and sulfhydryl-modified pillar[5]arene (HE/SH-P5)-functionalized gold nanoparticles (Au@HE/SH-P5 NPs) for the highly specific detection of •OH under visible light irradiation. HE/SH-P5 confers specificity and enables signal amplification through the reaction of its functional groups with •OH. Notably, the host molecule concentrates hydroxyl radicals within its cavity via host-guest complexation, while the localized surface plasmon resonance of gold nanoparticles synergistically enhances photoelectrochemical (PEC) signal amplification. The sensor achieves pH-dependent ultralow detection limits (0.3 μM at pH 2; 0.1 μM at pH 7.4, S/N = 3) and a broad linear range (1-250 μM at pH 2; 0.3-100 μM at pH 7.4). Significantly, the PEC platform demonstrates exceptional performance in monitoring •OH within HeLa cells, underscoring its considerable potential for fundamental ROS research, pathophysiological studies, and clinical diagnostics.