Polythiophenes (PTs) with flexible backbones possess inherent polymer behaviors, including molecular wire effects and dynamic structural changes in π-conjugated systems. The chemical sensing at the functionalized side chains can manipulate such polymer characteristics, resulting in various optical patterns depending on the analyte structures and their concentrations. The unique optical patterns derived from polymer properties contribute to group categorization over a wide concentration range for pattern recognition. This review aims to provide a concise overview of the potential of PT chemosensor arrays using actual sensing examples in environmental monitoring, medical diagnostics, and food analysis. Furthermore, this review summarizes the methodologies that use polymer gels to realize practical chemosensor array chips for onsite analysis.

Sonodynamic therapy (SDT) is a novel cancer treatment type showing the advantages of high tissue penetration ability, non-invasion, low systemic toxicity, and high selectivity. However, SDT depends on ultrasound (US) irradiation; once US is turned off, the sonosensitizer will stop producing reactive oxygen species (ROS). Moreover, most sonosensitizers generate oxygen-dependent ROS, that is, singlet oxygen (¹O₂), significantly limiting the therapeutic effect of SDT in treating deep and hypoxic tumor. Therefore, combining SDT with other treatment modalities is essential. Here, we designed and synthesized a series of cisplatin-coordinated copolythiophenes (CPT-Pts), simultaneously generating ¹O₂, superoxide anion, and hydroxyl radicals for synergistic chemotherapy and SDT of tumor. The sonodynamic toxicity and cytotoxicity of CPT-Pts were accurately regulated by tuning the monomer ratio of the polythiophene. This copolymerization strategy avoids the side effects originating from the high-dose chemotherapy drug while making up for limiting SDT relying on ultrasonic activation, effectively inhibiting cancer cells and tumors.

Robust and reliable piezo-ionic materials that are both crack resistant and selfhealable like biological skin hold great promise for applications inflexible electronics and intelligent systems with prolonged service lives. However, such a combination of high toughness, superior crack resistance, autonomous self-healing and effective control of ion dynamics is rarely seen in artificial iontronic skin because these features are seemingly incompatible in materials design. Here, we resolve this perennial mismatch through a molecularly engineered strategy of implanting carboxyl-functionalized groups into the dynamic hard domain structure of synthesized poly(urethane-urea). This design provides an ultra-high fracture energy of 211.27 kJ m^–2 that is over 123.54 times that of tough human skin, while maintaining skin-like stretchability, elasticity, and autonomous self-healing with a 96.40% healing efficiency. Moreover, the carboxyl anion group allows the dynamic confinement of ionic fluids though electrostatic interaction, thereby ensuring a remarkable pressure sensitivity of 7.03 kPa^–1 for the tactile sensors. As such, we successfully demonstrated the enormous potential ability of this skin-like piezoionic sensor for biomedical monitoring and robotic item identification, which indicates promising future uses in flexible electronics and human–machine interactions.

The low porosity of metal-organic framework glass makes it difficult to prepare membranes with high permeability. To solve this problem, we fabricated a series of self-supported zeolite glass composite membranes with different 4A zeolite loadings using the abundant pore structure of the zeolite. The 4A zeolite embedded in the zeolite glass composite membrane preserved the ligand bonds and chemical structure. The self-supported zeolite glass composite membranes exhibited good interfacial compatibility. More importantly, the incorporation of the 4A zeolite significantly improved the CO₂ adsorption capacity of the pure a_gZIF-62 membranes. In addition, gas separation performance measurements showed that the (a_gZIF-62)_0.7(4A)_0.3 membrane had a permeability of 13,329 Barrer for pure CO₂ and an ideal selectivity of 31.7 for CO₂/CH₄, which exceeded Robeson’s upper bound. The (a_gZIF-62)_0.7(4A)_0.3 membrane exhibited good operational stability in the variable pressure test and 48 h long-term continuous test. This study provides a method for preparing zeolite glass composite membranes.

Photodynamic therapy (PDT) has become a promising method for tumor treatment due to its non-invasive and high spatiotemporal selectivity. However, PDT is still hindered by reactive oxygen species deficiency, because solid tumors feature a hypoxic microenvironment. PDT combined with hypoxia-activated chemotherapy drugs can effectively induce tumor death, overcoming the limitations of the sole PDT for the fight against hypoxia. Herein, we designed a nanosystem (PCe6AZOM) that enhances the release of hypoxia-activated drugs (AZOM) by PDT. Under hypoxic conditions, the azo bond of AZOM is cleaved by azo reductase, releasing highly cytotoxic AZOM and resulting in a significant increase in intratumor drug concentration. Meanwhile, the commercial photosensitizer Ce6 can aggravate the oxygen-poor state during the PDT process and further cause more AZOM release. Moreover, the cascade reactions in the nanosystem could activate singlet oxygen and enhance drug release through 660 nm light laser irradiation, contributing to more effective induction of tumor apoptosis and tumor growth retardation in vitro and in vivo.

Enzymes with active sites involving histidine selectively utilize either the δ- or ϵ-nitrogen atom (N_δ or N_ϵ) of the histidine imidazole for catalysis. However, evaluating the impact of N_δ and N_ϵ is difficult, and directly integrating noncanonical Nmethylated histidine within enzymes poses risks due to laborious procedures. In this study, we present the self-assembly of Fmoc-Histidine (Fmoc-His) with hemin to create a peroxidase-mimetic catalyst, in which either the N_ϵ or N_δ of histidine is methylated to modify the tautomeric preferences, thereby tuning hemin catalysis. UV-vis spectra, ¹H-NMR, and fluorescence experiments elucidate that the Nmethylation of histidine alters the self-assembly propensity of Fmoc-His, and affects the binding affinity of histidine to hemin iron, with Fmoc-_δmHis/hemin exhibiting stronger binding than Fmoc-_ϵmHis/hemin. Theoretical simulation results suggest that _ϵmHis and _δmHis ligation produce a saddled structure and planar structure of hemin, respectively, stemming from the disparity of steric hindrance at the N_ϵ and N_δ positions. The significant inhibition of hemin’s oxidative activity by Fmoc-_δmHis is observed, likely due to the strong binding of Fmoc-_δmHis, potentially hindering access of the substrate, H₂O₂, to the hemin iron. Conversely, Fmoc-_ϵmHis enhances hemin catalysis, surpassing even Fmoc-His alone. This differential impact of Fmoc-_ϵmHis and Fmoc-_δmHis on hemin activity is further corroborated by apparent activation energy and kinetic parameters (k_cat, k_cat/K_m). This study sheds light on the heterogeneous biological effects at the nitrogen positions of histidine imidazole and offers insights into designing supramolecular metalloenzymes.

Conductive polymer hydrogels (CPHs) are promising in cutting-edge applications including bioelectronics and tissue engineering. However, the precise regulation of the spatial distribution of the conductive polymer (CP) in the hydrogel network is still an issue for designing a smart material. Herein, we propose a facile method for preparing CPH-based smart materials by controlling the distribution of Fe³⁺ initiator with UV light irradiation. Thus, designable polypyrrole (PPy) conductive patterns in the polyvinyl alcohol/sodium alginate (PVA/SA) semi-interpenetrating hydrogel network are demonstrated by controlling the concentration of Fe³⁺ ions coordinated with carboxylate groups. Depending on the irradiation time, the reduction of Fe³⁺ to Fe²⁺ occurs in different extents. As a result, the controllable polymerization of pyrrole only initiated by Fe³⁺ is achieved to form desirable CPH patterns, which are confirmed by the characterization results of Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy. Moreover, the developed hydrogel with PPy patterns is illustrated for the application in smart conductive circuit and information encryption. The simple procedure and the controllable conductive patterning of the proposed method make it a promising route in developing smart hydrogel materials, which can be extended to other Fe³⁺ initiated CP patterns.

Prostate-specific membrane antigen (PSMA) is known to be overexpressed in prostate cancer (PCa). The development of precise and rapid imaging technologies to monitor PSMA is crucial for early diagnosis and therapy. Fluorescence imaging in the second near-infrared window (NIR-II) has emerged as a powerful tool for real-time tracking and in vivo visualization, offering high sensitivity and resolution. However, there is a lack of stable, bright and easy-to-implement NIR-II fluorescent probes for PSMA targeting. Herein, we presented a PSMA-targeting NIR-II fluorescent probe FC-PSMA based on π-conjugated crossbreeding dyed strategy that affords high stability, large extinction coefficient, and good brightness. As demonstrated, FC-PSMA displayed a high fluorescence quantum yield in fetal bovine serum (FBS). Following intravenous injection of FC-PSMA, the tumor-to-normal ratio of fluorescence intensity steadily increased over time, reaching a peak at 48 h (tumor-to-leg ratio = 12.16 ± 0.90). This advancement enables precise identification of PC through NIR-II fluorescence imaging, facilitating high-performance guidance for prostate cancer resection surgery.

The clinical approval of platinum-based drugs has prompted the development of novel metallo-complexes during the last several decades, while severe problems, especially for poor water solubility, drug resistance and toxicity in patients, greatly hindered the clinical trials and curative efficacy. To address these issues, the concept of metallo-prodrugs has been proposed for oncology. Some stimuliactivable metallo-prodrugs provide new insights for designing and preparing site-specific prodrugs with maximized therapeutic efficacy and negligible unfavorable by-effects. In this review, recent progress in stimuli-activable metalloprodrugs in the past 20 years has been overviewed, where endogenous and exogenous stimuli have been involved. Typical examples of smart stimuli-activable metallo-prodrugs are discussed regarding to their molecular structure, activation mechanism, and promising biomedical applications. In the end, challenges and future perspectives in metallo-prodrugs have been discussed.

In situ precise detection of bioactive molecules with high sensitivity and spatiotemporal resolution is essential for studying physiological events and disease diagnosis. The utilization of versatile fluorescent probes in fluorescence imaging offers a powerful tool for in vivo imaging of biomarkers closely associated with pathological conditions. However, the dynamic behavior leading to rapid clearance of small molecule probes from regions of interest severely compromises their potential for precise imaging. Notably, self-immobilizing fluorescent probes that selectively recognize diseased tissues while improving in situ retention and enrichment enable accurate high-fidelity fluorescence imaging. In this review, we aim to summarize the strategies employed for recent advances in the performance and precision of in vivo fluorescence imaging using self-immobilizing techniques. Lastly, we discuss the prospects and potential challenges associated with selfimmobilizing fluorescent probes to promote further development and application of more delicate fluorescent probes.

Precision medicine calls for advanced theranostics that integrate controllable diagnostic and therapeutic capabilities into one platform for disease treatment in the early stage. Phototheranostics such as fluorescence imaging (FLI), photoacoustic imaging (PAI), photodynamic therapy (PDT), and photothermal therapy (PTT) have attracted considerable attention in recent years, which mainly employ different excited-state energy dissipation pathways of a chromophore. According to the Jablonski diagram, FLI is related to the radiative process, PAI and PTT are derived from the nonradiative thermal deactivation, and PDT originates from the triplet state energy, in which these processes are usually competitive. Therefore, it is critically important to precisely tune the photophysical energy transformation processes to realize certain diagnosis and treatment properties in optimal state for boosting biomedical applications. Currently, there are mainly two strategies including chemical structure and aggregate behavior changes that relate to the regulation of excited state energy dissipation. In this review, we will discuss the recent advances of smart molecular probes that the photophysical properties can be regulated by external triggers and their applications in biomedical fields. We will summarize the development of activatable phototheranostic molecular probes in response to stimuli such as reactive oxygen species, pH, light, hypoxia, enzyme and gas. The assembly and disassembly of molecular aggregates that greatly affect the photophysical energy transformation processes will also be highlighted. This review aims to provide valuable insights into the development of more accurate diagnostic and therapeutic systems, thereby advancing the emerging field of smart medicine.

Organic afterglow materials have drawn increasing attention for their great potential in practical applications. Until now, most of them just show the lifetimes in milliseconds or seconds, while the realization of long persistent luminescence (LPL) lasting for minutes or even hours is difficult. In 2017, Adachi and Kabe successfully realize the LPL with a duration longer than 1 hour in a purely organic system, which can be even comparable to some excellent inorganic materials. However, partially for the unclear structure-property relationship, organic LPL materials are still rather scarce, especially for the stable ones in air or aqueous solution. In this review, we present the recent progress in organic LPL, mainly focusing on the material design strategy and internal mechanism. It is anticipated that the deep understanding can be beneficial for the further development of organic LPL materials with good stability in air and even aqueous phase.