Biological thiols are important small molecule bioregulators that play important roles in numerous crucial processes and are directly associated with a variety of serious diseases. Consequently, sensing and imaging thiols have emerged as key research focuses. Fluorescent probes provide an important cornerstone for investigating the multifaceted roles of active thiols at the cellular level and in vivo with high sensitivity and selectivity. This review provides a systematic overview of the classification and structural properties of the fluorophores, functional groups and detection mechanisms for thiols. We focus on interesting breakthroughs of small molecule fluorescent probes for sensitive and selective sensing and imaging of thiols. We emphasize the strategies and chemical mechanisms behind the design of fluorescent probes and primarily describe the biological imaging, diagnostics and therapeutics. This review concludes with a discussion of the challenges and perspective for fluorescent probes, highlighting future avenues of research that should enable these probes to achieve accurate detection to enrich diagnostic and therapeutic tools for biomedical research and clinical applications.

The strong localized charges at the center of BiX6 octahedra in bismuth-based halide perovskite restrict carrier migration, ultimately affecting photocatalytic performance. However, whether A-site cations could suppress strong localized charges at the center of BiX6 remains unexplored, primarily because they indirectly contribute to the band-edge orbitals of halide perovskite. In this work, we reported a strategy to disperse strong localized charges at the center of BiX6 through changing organic A-site cations with conjugative effect (thiazoline, thiazole, and benzothiazole) and inductive effect (benzoxazole and benzoselenazole), and delve into the impact of the strategy on materials' optoelectronic and photocatalytic properties. Increased conjugative and inductive effects were found to suppress localized charges of BiBr6 center, improving carrier separation and transport, as well as improving photocatalytic CO2 conversion efficiency. Among these designed halide perovskites, benzoselenazole ammonium functionalized BSABiBr4 exhibited the highest CO2 conversion rate (mu mol g-1 h-1) of 36.20 with high reusability and stability. This finding successfully overcomes the limitation of A-site cations to suppress localized charges at the center of octahedra for enhancing photocatalytic performance.

Photosensitization is an effective method for increasing metal-organic frameworks (MOFs) photocatalyst performance by improving light absorption capability, energy transfer rate and charge separation efficiency. However, enhance the photosensitization efficiency by controlling the photosensitizer (PS) introduction mode remains largely known. Herein, two cases of UiO-MOFs with different PS introduction methods, benzothiadiazole (BT) encapsulated UiO-66@H2BTDB (H2BTDB: 1.8 wt%) or BT coordinated UiO-68-BTDB (H2BTDB: 66.0 wt%), are compared. Both of them have excellent photoelectric efficiency, but interestingly, UiO-66@H2BTDB with mere 1/36 BT has superior photoelectric conversion efficiency, resulting generate twofold photoactive intermediates. In addition, their photocatalytic activities were evaluated with three amine synthesis, and the results showed that UiO-66@H2BTDB has the highest twofold photocatalytic conversion efficiency and yields. Transient absorption spectroscopy and density functional theory calculations elucidate the critical role of PS-encapsulated sensitizing frameworks in facilitating efficient intraframework energy transfer and charge separation. This work demonstrates the distinct advantages of MOF encapsulated PSs over their coordinated counterparts for constructing heterogeneous photocatalysts, thereby paving the way for advanced artificial photosynthesis systems.

Naphthalene imide dyes are a class of potential cathodic electrochromic materials due to their unique pi-conjugated structures and excellent redox properties, but poor solubility, limited modifiability, and difficulties in device assembly limit their applications in electrochromic fields. This paper reports novel naphthalene imide dye-based electrochromic materials (NI-Py-N, NI-Py-C4 and NI-Py-Bn) by incorporating electroactive naphthalene imide unit with polar and redox-active pyridinium salt to balance the solubility while enhance the electrochromic properties. The combination strategy endows NI-Py-N, NI-Py-C4 and NI-Py-Bn with enhanced solubility and better electrochromic properties compared to these control materials with only one redox-active unit (naphthalene imide or pyridinium salt). They have the advantages of both butyl-substituted naphthalenediimides (fast response and low driving voltage) and naphthalene-nucleus-extended violet-essence derivatives (high optical contrast and good cycling stability) in solution-type electrochromic devices. Among them, NI-Py-C4 performs best in cycling stability. A lower working voltage (-1.8 V), a dark purple colored state, a higher optical contrast (76% at 595 nm), and a longer fading time were obtained when NI-Py-C4 was further applied in gel-type electrochromic device. This energy-saving characteristics are promising in smart windows and displays.

Large it-conjugated system challenges the traditional notion of A-site cations non-participation in band-edge states for halide perovskites, tuning alkyl chain length to alter electrostatic interactions between the ammonium cations and octahedra, which modulates "valence band" (VB) edge states and photogenerated hole migration. However, how the conjugative and steric effects of A-site cations regulate band-edge states, particularly the photoreductive capability of photogenerated electrons at "conduction band" (CB) edge states, awaits systematic exploration. Herein, we reported a strategy for the direct regulation of band-edge states through varying A-site cations with different conjugated systems (phenyl/naphthyl). Increased conjugative effect benefits the CB edge and eliminates localized charge of BiBr6 center, while the spatially oriented 1-(2-naphthyl)meth-anamium (beta-NMA+) with minimized steric hindrance achieves deeper anchoring distance into octahedral cavity, significantly enhancing electrostatic interactions. The results reveal that beta-NMA+ functionalized perovskite (beta-NMA2BiBr5), conjugation-enhanced and low-steric-hindrance, exhibited the highest CO2 conversion efficiency which is 6.5 times higher than that of phenylmethylamium functionalized perovskite (PMA2BiBr5). This work validates a viable approach for regulating the ammonium-octahedron interaction via conjugative-steric strategy of A-site cations, significantly promoting catalytic capacity and offering a novel design pathway for efficient Bibased perovskite photocatalysts.

The development of efficient photocatalysts for carbon‑nitrogen (CN) bond formation from aldehydes is highly desirable for the synthesis of functional organic molecules but remains a significant challenge. Herein, we report a novel imidazobenzothiadiazole-based tricarboxylate compound (H2Ph-COOH, defined as "T-shaped" ligand), and successfully construct the first single-component metal-organic frameworks (MOFs, UiO-68-Ph-COOH) featuring an exposed carboxyl group. This MOFs was effectively employed in the photocatalytic synthesis of amides from aldehydes and amines. The carboxylated T-shaped ligand-based UiO-68-Ph-COOH exhibits outstanding optoelectronic properties and exceptional photocatalytic activity for amide synthesis at room temperature, achieving high yields (up to 92%) within 12 h, along with long-term durability and excellent stability. In comparison, control MOFs (UiO-68-Bt and UiO-68-Ph) derived from linear ligands showed markedly lower catalytic activity (10% and 16% yields, respectively) under identical reaction conditions. Mechanistic studies reveal that the exposed -COOH groups in UiO-68-Ph-COOH act as Brønsted acid sites, which promote the formation of key amino alcohol intermediate and concurrently facilitate the generation of superoxide radical (O2•-). This synergistic effect significantly improves the photocatalytic efficiency for amide synthesis. Additionally, UiO-68-Ph-COOH efficiently catalyzes the formation of benzothiazoles and benzimidazoles (up to 94% yield within 1.5 h). This work provides the first demonstration that a single-component MOFs can independently drive photocatalytic amide synthesis and reveals the exposed -COOH functionalization as a crucial design strategy for MOFs-based photocatalysts, thereby opening new avenues for designing efficient MOFs-based photocatalysis of CN bond formation.

Lipid droplets (LDs) are multifunctional organelles essential for lipid storage, metabolic regulation, and cellular homeostasis, and their dysregulation is closely associated with the onset and progression of metabolic dysfunction-associated steatotic liver disease (MASLD). Sensitive and specific fluorescent imaging of LDs dynamics is crucial for elucidating MASLD pathogenesis and accelerating the development of effective therapeutics. Herein, we report near-infrared fluorescent carbon dots (NIR-FCDs) with precise LDs-targeting capability and enabling high-contrast imaging of LDs distribution in AML-12 cells and MASLD mice model, exhibiting high brightness (QY: 8.6%), deep-tissue penetration (75 μm), excellent photostability (>3 h continuous irradiation), and superior signal-to-background (SBR = 26). Leveraging these properties, NIR-FCDs was applied for visualizing pathological lipid accumulation in MASLD mice models and demonstrated their utility in a drug-screening platform successfully. This work developed a robust NIR-FCDs for LDs-specific imaging and highlighted its potential to advance mechanistic studies and therapeutic discovery in metabolic liver diseases.

TiO2 photocatalysis is limited by poor solar light utilization and rapid charge recombination. In this work, a benzothiadiazole-based small molecule (BTDSCN) was designed and combined with TiO2 to form a heterojunction for the simultaneous degradation of organic dyes and the reduction of Cr(VI). The introduction of BTDSCN increases the number of oxygen vacancies (VO) in TiO2, effectively boosting the availability of photocatalytic active sites. Compared to TiO2, the BTDSCN/TiO2 heterojunction exhibits improved performance in degrading organic dyes and reducing Cr(VI). The removal efficiencies for Rhodamine B and Cr(VI) are approximately 2 times and 7 times higher than those of TiO2, respectively. The abundant VO in BTDSCN/TiO2 creates defect levels within its band gap, significantly enhancing the photocatalytic activity of TiO2.

Inorganic lead halide perovskite quantum dots (PQDs) feature exceptional optoelectronic properties but suffer from poor stability, limiting their commercial viability. This study employs a mechanochemical synthesis route utilizing shared cesium ion to synthesize CsPbBr3 PQDs within supramolecular γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs). The resulting CsPbBr3@γ-CD-MOFs achieves high photoluminescence quantum yield (73%) alongside exceptional thermal, photochemical, and environmental stabilities. Mechanistic investigations reveal synergistic augmentation effects: multianchored defect passivation via γ-CD hydroxyl groups, enhanced radiative recombination through type-I heterojunction-driven directional carrier injection, and suppression of ion migration and phase separation by MOFs' physical barriers and interfacial chemical bonds. The composite was successfully applied in white light-emitting diodes, boasting color rendering index of 90.1 and color gamut coverage of 115%. Furthermore, benefiting from the good biocompatibility imparted by γ-CD-MOFs, the composite serves as fluorescent probe for specific labeling and imaging of lysosomes in living cells. This supramolecular-MOFs strategy provides design principles for developing stable, efficient, and biologically compatible PQDs, accelerating their optoelectronic and bioimaging applications.

ABSTRACT Prostate cancer (PCa) is a leading malignancy in men globally. Although serum prostate‐specific antigen (PSA) testing is prevalent for PCa screening, its inherent limitation in specificity and sensitivity frequently leads to high false‐positive and false‐negative diagnoses. To address this challenge, we present a PSA+ strategy that integrates a clinically defined PSA threshold (10 ng/mL) with a pair of complementary near‐infrared (NIR) fluorescent probes: a zinc‐complex‐based probe (Cy‐O‐NS‐a‐Zn) targeting the zinc transporter solute carrier family 39 member 1 (SLC39A1), and a glutamate‐urea‐lysine (Glu‐Urea‐Lys) ligand‐based probe (Cy‐S‐Glu) targeting prostate‐specific membrane antigen (PSMA). This combinatorial approach accurately discriminates PCa from normal prostate cells, delineates tumor margins in patient‐derived xenograft (PDX) mouse models with robust tumor‐to‐background ratios (TBR), and enables fluorescence‐guided surgery. Importantly, a double‐blind histopathological validation using 70 cases of human prostate tissue specimens revealed that the PSA+ strategy substantially outperformed PSA testing alone, improving diagnostic specificity from 70% to 97.6% and sensitivity from 75% to 96.8%. Collectively, this work provides a rapid, accurate, and comprehensive diagnostic paradigm that complements standard PSA testing, thereby refining clinical diagnosis and decision‐making in PCa.

Solar-driven photocatalytic CO2-to-CH4 conversion represents a promising strategy to mitigate the energy and climate crisis. However, it is still challenging to achieve efficient CO2 conversion due to the difficulties of CO2 activation, sluggish kinetics of water oxidation half-reaction and high cost of sacrificial agents in conventional reaction systems. Herein, by precisely integrating bimetallic sulfide with functionalized UiO-66 to construct a Cu0.1Zn0.9S/Bim-UiO-66 S-scheme heterojunction photocatalyst, which innovatively accomplished complete CO2 methanation and benzimidazole synthesis in one redox cycle. Experimental results reveal that the optimized photocatalyst exhibited an exceptional CH4 production rate of 35.2 mu mol h- 1 g- 1 (selectivity of 100 %) and 92 % benzimidazole conversion under simulated solar irradiation. Mechanistic studies demonstrate that the S-scheme heterojunction significantly enhances photogenerated charge carrier separation efficiency through the establishment of a built-in electric field, while preserving the strongest redox potentials of the two semiconductors. Remarkably, the benzimidazole synthesis process replaced conventional H2O oxidation, proving beneficial for CO2-to-CH4 conversion. This work provides new insights into designing high-performance photocatalysts for CO2 conversion and the synthesis of fine chemicals.

Fluorescence imaging-guided photodynamic therapy (PDT) offers immense clinical potential for cancer treatment. However, their therapeutic efficacy and biosafety are compromised by the high oxygen dependency of traditional Type II photosensitizers and insufficient targeting accuracy. Herein, we present a tumor-organelle-targeted and activatable phototheranostic platform (termed NO2/BDP-BT), which was engineered via an atom-economical all-in-one design strategy. The NO2/BDP-BT gathers exceptional tumor-organelle targeting ability, nitroreductase (NTR)-activated fluorescence enhancement, allowing it to monitor hypoxia levels in biosystems (living cells, clinical patient tissues, and in vivo). Moreover, it enables the generation of Type I/II reactive oxygen species (ROS) in situ after NTR activation, thereby suppressing tumor growth with an inhibition rate of 93.2 % via mitochondria-mediated apoptosis and potentiating the antitumor immunity response. Cocrystal structural analysis of the NTR protein in complex with the precursor of NO2/BDP-BT (PDB: 7XWW; resolution: 2.80 Å) first reveals that multiple non-covalent interactions (e.g., hydrogen bonding and π-π stacking) make it anchor in the catalytic environment with high affinity. Moreover, NO2/BDP-BT can be expanded to a Type I PDT photosensitizer (NO2/BDPS-BT) by introducing a thiophene unit, conquering hypoxia restriction in PDT. This work establishes a molecular platform of activatable phototheranostic sensor with potent therapeutic efficacy and biosafety, which would effectively address both hypoxia resistance and targeting deficiencies inherent in conventional PDT.

A modular protocol that achieved the efficient synthesis of imidazo[2,1-b][1,3,4]thiadiazoles/selenadiazoles via using easily available N-tosylhydrazones, chalcone derivatives, and KSCN/KSeCN is proposed. The method overcomes the elongated synthesis steps and prefunctionalized synthons of previous methods. It solves the problem of traditional preparation methods, which makes it difficult to synthesize thickened selenium-containing heterocyclic molecules, further expanding the number of members in its family. The fluorescence of these compounds also reveals the potential values of the scaffolds we synthesized.

Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15-25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for CR after 14 runs, and 90% for Cr(VI) after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.

Selecting metal nodes on the basis of their electronic configurations is crucial for enhancing the photocatalytic performance of Metal-organic frameworks (MOFs). However, regulation of the inherent structure-performance relationship of MOFs by rational selection of metal nodes remains largely unknown. To address this issue, two boron dipyrromethene (BODIPY)-based MOFs, Co-MOF and Zn-MOF, featuring identical ligands but distinct metal centers, were constructed. Replacing Zn(II) with Co(II) transforms the framework from a dense 3-fold interpenetrating structure to a more open 2-fold interpenetrating structure, which increases the pore size and solvent-accessible volume (25.6% vs 40.2%). Moreover, the 3d7 electronic configuration of Co(II) facilitates rapid ligand-to-metal charge transfer (LMCT) and enhances photogenerated charge separation. Consequently, compared with the Zn-MOF, the Co-MOF demonstrates superior photocatalytic activity in both N-demethylation of tertiary amines and C-3 formylation of indoles. Particularly, this is the first time that MOFs based on BODIPY ligands have achieved photocatalytic conversion in these two organic reactions. This work discusses that the selection of metal nodes is a key factor in achieving the synergistic regulation of the structure and photoelectric properties of MOFs.

Copper and palladium exhibit excellent catalytic performance for the electrochemical reduction of CO2 (CO2RR). Here, a PdxCu4-x (x = 2, 3) cluster was supported on CeO2 with different sites to form three kinds of novel nanocatalysts, namely, Pd2Cu2/CeO2, Pd3Cu/CeO2 (Pd-Pd), and Pd3Cu/CeO2 (Pd-Cu). Based on density functional theory, the catalytic performance and selective mechanisms were studied systematically. During the process of CO2RR, *CO was hydrogenated to produce deeply reduced products such as CH4 or CH3OH due to its strong adsorption energies on all three catalysts (Pd3Cu/CeO2(Pd-Pd) for 0.95 eV, Pd3Cu/CeO2(Pd-Cu) for 0.89 eV, and Pd2Cu2/CeO2 for 1.22 eV). The overpotential to form the CH4 or CH3OH product can be changed by varying the atomic ratio or anchoring sites of PdxCu4-x clusters on CeO2. In particular, the CO2RR on Pd2Cu2/CeO2 showed the lowest overpotentiontial (-0.60 eV) compared to the other two Pd3Cu/CeO2 catalysts. This study extends the family of CO2RR catalysts and the application scenarios of bimetallic catalysts, which provides new insights into the design and preparation of composite nanocatalysts.

Accurate quantification of cisplatin (cDDP) in body fluids (blood, urine, and ascites) is crucial in monitoring therapeutic processes, assessing drug metabolism, and optimizing treatment schedules for cancer patients. Nonetheless, due to the inherent fluorescence and complexity of the body fluid matrix, along with the low cDDP concentrations in these fluids during treatment, using fluorescent sensors for fluid detection remains a subject of ongoing research. Herein, a series of water-soluble cDDP-activatable fluorescent sensors was rationally constructed by introducing thioether groups to the xanthene skeleton based on the chalcogenophilicity of platinum. These sensors exhibit excellent sensitivity and certain anti-interference capabilities for sensing cDDP in living cells, rat tissues, and zebrafish. Especially, with a simplified sample pretreatment procedure, for the first time, Rh3 and Rh4 have enabled quantitative detection of cDDP levels in diversiform body fluids from clinical ovarian and bladder cancer patients. These results are highly consistent with those obtained by ICP-MS detection. This work paves the way for utilizing fluorescent sensors in clinical body fluid analysis, thus potentially revolutionizing the monitoring methods of cDDP in clinic settings.