Latest ArticlesHerein, a simple and effective outer-surface interactions assisted supramolecular hierarchical assembly has been first exploited to uniformly distribute tungstosilicic acid (TSA) inside the porous structure of cucurbit[10]uril-based single-layer 2D supramolecular-organic-frameworks (Q[10]-SOFs) in water. Importantly, the 2D Q[10]-SOFs can further serve as light harvesting antenna, achieving fast energy transfer to the embedded redox-active TSA upon photoexcitation, resulting in efficient visible light-driven selective oxidation of benzyl alcohols into the corresponding aldehydes in high yield at room temperature. Further studies revealed that the integrated of 2D Q[10]-SOFs and TSA played a key role in the catalytic process, due to the presence of a novel stepwise electron transfer route in the single-layer hybrid 2D structures.
The separation of alicyclic ketones and alicyclic alcohols is one of the challenges in the field of petrochemical industry. However, traditional separation methods suffer from excessive energy consumption, complicated operation, and unsatisfactory separation efficiency for substances with similar boiling points. Herein, we offer an innovative method for the separation of alicyclic ketones and alicyclic alcohols employing nonporous adaptive crystals (NACs) of perethylated pillar[5]arene (EtP5) and perethylated pillar[6]arene (EtP6). NACs of EtP5 cannot adsorb either alicyclic ketones or alicyclic alcohols because of the small cavity size of EtP5. By contrast, NACs of EtP6 can separate cyclopentanone from the vapor mixture of cyclopentanone/cyclopentanol (v:v = 1:1) and cyclohexanone from the vapor mixture of cyclohexanone/cyclohexanol (v:v = 1:1) with purities of 99.1% and 100%, respectively. Density functional theory calculations show that the selectivity comes from the thermodynamic stability of the newly formed crystal structure after adsorption of the preferred guest molecule. Moreover, NACs of EtP6 can be reused without losing selectivity and performance.
Pt(Ⅱ)−salophen complexes (S-1~S-4) and 9,10-diphenylanthracene (DPA) tethering pillar[5]arene derivatives (A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion (TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer (PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3, and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated, TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive guests.
ZnIn2S4, a typical n-type semiconductor, has received intensive attention due to its suitable bandgap, excellent visible light absorption performance, and simple and flexible preparation methods. However, its application is curbed by photo-generated carrier recombination and photo corrosion. Although constructing S-scheme heterojunctions by combining ZnIn2S4 with other semiconductors can solve these problems, the photocatalytic activity of S-scheme heterojunctions can be further improved. Therefore, this short review summarizes modification strategies of ZnIn2S4-based S-scheme heterojunctions. This article also introduces the concept, design principles, and characterization methods of ZnIn2S4-based S-scheme heterojunction. Finally, current challenges and future research focuses related to ZnIn2S4-based S-scheme heterojunctions are discussed and summarized, including the utilization of advanced in-situ characterization techniques to further illuminate the photocatalytic mechanism, the DFT-assisted design of catalysts to increase the selectivity of products during photocatalytic CO2 reduction, and extending the photo-response of ZnIn2S4-based S-scheme heterojunction to near-infrared range, etc.
Lung cancer-derived exosomes are a kind of valuable and clinically-predictable biomarkers for lung cancer, but they have the limitations in individual differences when being applied in liquid biopsy. To improve their application value and accuracy in clinical diagnosis, a dual-labelled electrochemical method is herein reported for precise assessment of lung cancer-derived exosomes. To do so, two probes are prepared for the dual labeling of exosome membrane to run DNA assembly reactions: One is modified with cholesterol and can insert into exosome membrane through hydrophobic interaction; another one is linked with programmed death ligand-1 (PD-L1) antibody and can bind to exosome surface-expressing PD-L1 via specific immunoreaction. Quantum dots-tagged signal strands are used to collect respective DNA products, and produce stripping signals corresponding to the amounts of total exosome and surface-expressing PD-L1, respectively. A wide linear relationship is established for the quantitative determination of lung cancer-derived exosomes in the range from 103 to 1010 particles/mL, whereas the ratiometric value of the two stripping signals is proven to have a better diagnostic use in screening and staging of lung cancer when being applied to clinical samples. Therefore, our method might provide a new insight into precise diagnosis of lung cancer, and offer sufficient information to reflect the biomarker level and guide the personalized treatment level even at an early stage in clinic.
The design and synthesis of a novel π-conjugated fluorescent framework by external ligand-assisted C−H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein. These novel fluorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule white-light materials with high fluorescence quantum yields. The robust organic and low-cost white light-emitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared (NIR) fluorescence materials with large Stokes shifts based on the olefination of heterocycles.
An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.
Utilizing small molecules as markers for specific cells or organs within biosystems is a crucial approach for studying and regulating physiological processes. However, current tagging strategies, due to the presence of exposed highly reactive groups, suffer from drawbacks such as low tagging efficiency or insufficient spatial specificity, thereby diminishing their expected effectiveness. Consequently, there is a pressing need to develop a strategy capable of in situ labeling of active groups in response to cellular or in vivo stimuli, ensuring both high tagging efficiency and spatial specificity. In this work, we devised a strategy for releasing aldehyde groups activated by hypochlorous acid (HOCl). Compounds synthesized through this strategy can release the fluorophore methylene blue (MB) and aldehyde-based compounds upon HOCl activation. Given high reactivity of the released aldehyde group, it can effectively interact with macromolecules in biological systems, facilitating tagging and enabling prolonged imaging. To validate this concept, we further incorporated a naphthalimide structure with stable light emission to create SW-110. SW-110 can specifically respond to in vitro and endogenous HOCl, when release MB, it also releases naphthalimide fluorophore with highly reactive aldehyde group for tagging within cells. This strategy provides a simple but efficient strategy for proximity tagging in situ.
Tuning the nanozyme′s activity and specificity is very crucial for developing highly sensitive sensors for various applications. Herein, selenium-doped porous N-doped carbon skeletons (Se/NC) nanozymes with highly specific peroxidase-like activity were synthesized by a MOF-pyrolysis-doping protocol. Se doping adjusted the electronic structure of NC by introducing more vacancies, defective carbon and graphitic N, and endowed the resultant Se/NC enhanced charge transfer and substrate affinity. The Se/NC exhibited specific peroxidase-mimicking activity and could catalyze 3,3′,5,5′-tetramethylbenzidine oxidation by H2O2. Density functional theory (DFT) calculations and experimental trials indicated that both Se=O and C–Se–C species were the main active sites of Se/NC. The C–Se–C bond is the main catalytic active site endowing Se/NC with the property of nanozyme, while the Se=O bond effectively enhances its affinity to H2O2 and accelerate H2O2 dissociation. The Se/NC showed an approximately 185-fold increase in peroxidase-like activity compared to NC. Based on the inhibition of the peroxidase-like activity of Se/NC by methimazole, a colorimetric sensor was developed to achieve its sensitive detection with 2 nmol/L of limit of detection. It was successfully used for detecting methimazole in real samples. Current Se doping strategy simplifies the fabrication process of high performance specific nanozyme and promises great potential for environmental analysis.
MicroRNA-133a (miRNA-133a) and cardiac troponin I (cTnI) are different-type crucial biomarkers of acute myocardial infarction (AMI), whose levels are great significance for AMI diagnosis and treatment. Herein, a novel photoelectrochemical-electrochemical (PEC-EC) dual-mode biosensing platform for dual-target assays of miRNA-133a and cTnI was developed. In which, a PEC-EC dual-mode sensing platform for miRNA-133a was constructed based on the changes of the photocurrent inhibition effect and the electrochemical signal of Fc on the Fc-hairpin DNA probe (Fc-HP)/ZnCdS-quantum dots (QDs)/ITO electrode. Furthermore, under magnetic separation and the specific interaction between cTnI and its aptamer, the N-doped porous carbon-ZnO polyhedra (NPC-ZnO)-hemin-capture DNA probe hybrid (NH-CP) was obtained and introduced to the Fc-HP/ZnCdS-QDs/ITO electrode via hybridization between NH-CP and Fc-HP. The hemin molecules encapsulated in NH-CP could effectively induce the photocurrent-polarity-switching of the Fc-HP/ZnCdS-QDs/ITO electrode and generate a new electrochemical signal originating from hemin. Thus, cTnI was assayed sensitively and selectively by the PEC-EC dual-mode biosensing platform. Here, Fc and hemin not only serve as the electrochemical indicators, but also respectively inhibit the photocurrent and switch the photocurrent polarity of ZnCdS-QDs. Furthermore, the proposed biosensing platform could be easily expanded to the detection of other multiplex-type biomarkers via the change of the sequences of the related DNA probes, implying its significant potential in clinical diagnosis and biological analysis.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62662699(Operation and Technical Support)
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
