Controllable and Low-Loss Electrochemiluminescence Waveguide Supported by a Micropipette Electrode.

One-dimensional molecular crystal waveguide (MCW) can transmit self-generated electrochemiluminescence (ECL), but heavy optical loss occurs because of the small difference in the refractive index between the crystal and its surroundings. Herein, we report a micropipette electrode-supported MCW (MPE/MCW) for precisely controlling the far-field transmission of ECL in air with a low optical loss. ECL is generated from one terminal of the MCW positioned inside the MPE, which is transmitted along the MCW to the other terminal in air. In comparison with conventional waveguides on solid substrates or in solutions, the MPE/MCW is propitious to the total internal reflection of light at the MCW/air interface, thus confining the ECL efficiently in MCW and improving the waveguide performance with an extremely low-loss coefficient of 4.49 × 10-3 dB µm-1. Moreover, by regulation of the gas atmosphere, active and passive waveguides can be resolved simultaneously inside MPE and in air. This MPE/MCW offers a unique advantage of spatially controlling and separating ECL signal readout from its generation, thus holding great promise in biosensing without or with less electrical/chemical disturbance.

Rapid Glutathione Analysis with SERS Microneedles for Deep Glioblastoma Tissue Differentiation.

Rapid tissue differentiation at the molecular level is a prerequisite for precise surgical resection, which is of special value for the treatment of malignant tumors, such as glioblastoma (GBM). Herein, a SERS-active microneedle is prepared by modifying glutathione (GSH)-responsive molecules, 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB), on the surface of Au@Ag substrates for the distinction of different GBM tissues. Since the Raman signals on the surface of the DTNB@Au@Ag microneedle can be collected by both portable and benchtop Raman spectrometers, the distribution of GSH in different tissues at centimeter scale can be displayed through Raman spectroscopy and Raman imaging, and the entire analysis process can be accomplished within 12 min. Accordingly, in vivo brain tissues of orthotopic GBM xenograft mice and ex vivo tissues of GBM patients are accurately differentiated with the microneedle, and the results are well consistent with tissue staining and postoperative pathological reports. In addition, the outline of tumor, peritumoral, and normal tissues can be indicated by the DTNB@Au@Ag microneedle for at least 56 days. Considering that the tumor tissues are quickly discriminated at the molecular level without the restriction of depth, the DTNB@Au@Ag microneedle is promising to be a powerful intraoperative diagnostic tool for surgery navigation.

Regulating the Critical Intermediates of Dual-Atom Catalysts for CO2 Electroreduction.

Electrocatalysis is a very attractive way to achieve a sustainable carbon cycle by converting CO2 into organic fuels and feedstocks. Therefore, it is crucial to design advanced electrocatalysts by understanding the reaction mechanism of electrochemical CO2 reduction reaction (eCO2RR) with multiple electron transfers. Among electrocatalysts, dual-atom catalysts (DACs) are promising candidates due to their distinct electronic structures and extremely high atomic utilization efficiency. Herein, the eCO2RR mechanism and the identification of intermediates using advanced characterization techniques, with a particular focus on regulating the critical intermediates are systematically summarized. Further, the insightful understanding of the functionality of DACs originates from the variable metrics of electronic structures including orbital structure, charge distribution, and electron spin state, which influences the active sites and critical intermediates in eCO2RR processes. Based on the intrinsic relationship between variable metrics and critical intermediates, the optimized strategies of DACs are summarized containing the participation of synergistic atoms, engineering of the atomic coordination environment, regulation of the diversity of central metal atoms, and modulation of metal-support interaction. Finally, the challenges and future opportunities of atomically dispersed catalysts for eCO2RR processes are discussed.

Extracellular vesicle dynamics in COPD: understanding the role of miR-422a, SPP1 and IL-17 A in smoking-related pathology.

BACKGROUND: Chronic obstructive pulmonary disease (COPD) induced by smoking poses a significant global health challenge. Recent findings highlight the crucial role of extracellular vesicles (EVs) in mediating miRNA regulatory networks across various diseases. This study utilizes the GEO database to uncover distinct expression patterns of miRNAs and mRNAs, offering a comprehensive understanding of the pathogenesis of smoking-induced COPD. This study aims to investigate the mechanisms by which extracellular vesicles (EVs) mediate the molecular network of miR-422a-SPP1 to delay the onset of COPD caused by smoking. METHODS: The smoking-related miRNA chip GSE38974-GPL7723 was obtained from the GEO database, and candidate miRs were retrieved from the Vesiclepedia database. Downstream target genes of the candidate miRs were predicted using mRNA chip GSE38974-GPL4133, TargetScan, miRWalk, and RNA22 databases. This prediction was integrated with COPD-related genes from the GeneCards database, downstream target genes predicted by online databases, and key genes identified in the core module of WGCNA analysis to obtain candidate genes. The candidate genes were subjected to KEGG functional enrichment analysis using the "clusterProfiler" package in R language, and a protein interaction network was constructed. In vitro experiments involved overexpressing miRNA or extracting extracellular vesicles from bronchial epithelial cell-derived exosomes, co-culturing them with myofibroblasts to observe changes in the expression levels of the miR-422a-SPP1-IL-17 A regulatory network, and assessing protein levels of fibroblast differentiation-related factors α-SMA and collagen I using Western blot analysis. RESULTS: The differential gene analysis of chip GSE38974-GPL7723 and the retrieval results from the Vesiclepedia database identified candidate miRs, specifically miR-422a. Subsequently, an intersection was taken among the prediction results from TargetScan, miRWalk, and RNA22 databases, the COPD-related gene retrieval results from GeneCards database, the WGCNA analysis results of chip GSE38974-GPL4133, and the differential gene analysis results. This intersection, combined with KEGG functional enrichment analysis, and protein-protein interaction analysis, led to the final screening of the target gene SPP1 and its upstream regulatory gene miR-422a. KEGG functional enrichment analysis of mRNAs correlated with SPP1 revealed the IL-17 signaling pathway involved. In vitro experiments demonstrated that miR-422a inhibition targets suppressed the expression of SPP1 in myofibroblasts, inhibiting differentiation phenotype. Bronchial epithelial cells, under cigarette smoke extract (CSE) stress, could compensate for myofibroblast differentiation phenotype by altering the content of miR-422a in their Extracellular Vesicles (EVs). CONCLUSION: The differential gene analysis of Chip GSE38974-GPL7723 and the retrieval results from the Vesiclepedia database identified candidate miRs, specifically miR-422a. Further analysis involved the intersection of predictions from TargetScan, miRWalk, and RNA22 databases, gene search on COPD-related genes from the GeneCards database, WGCNA analysis from Chip GSE38974-GPL4133, and differential gene analysis, combined with KEGG functional enrichment analysis and protein interaction analysis. Ultimately, the target gene SPP1 and its upstream regulatory gene miR-422a were selected. KEGG functional enrichment analysis on mRNAs correlated with SPP1 revealed the involvement of the IL-17 signaling pathway. In vitro experiments showed that miR-422a targeted inhibition suppressed the expression of SPP1 in myofibroblast cells, inhibiting differentiation phenotype. Furthermore, bronchial epithelial cells could compensate for myofibroblast differentiation phenotype under cigarette smoke extract (CSE) stress by altering the miR-422a content in their extracellular vesicles (EVs).

Symmetry-Broken Ru Nanoparticles with Parasitic Ru-Co Dual-Single Atoms Overcome the Volmer Step of Alkaline Hydrogen Oxidation.

Efficient dual-single-atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual-single-atom site generation remains formidable challenges. Here, we break the local symmetry of ultra-small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co1 Ru1,n /rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen-affine Co atom disrupts the symmetry of ultra-small Ru nanoparticles, resulting in parasitic Ru and Co dual-single-atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H2 O. As anticipated, Co1 Ru1,n /rGO exhibits ultrahigh mass activity (7.68 A mgRu -1 ) at 50 mV and exchange current density (0.68 mA cm-2 ), which are 6 and 7 times higher than those of Ru/rGO, respectively. Notably, it also displays exceptional durability surpassing that of commercial Pt catalysts. This investigation provides valuable insights into hybrid multi-single-atom and metal nanoparticle catalysis.

Homotypic Membrane-Enhanced Blood-Brain Barrier Crossing and Glioblastoma Targeting for Precise Surgical Resection and Photothermal Therapy.

The crossing of blood-brain barrier (BBB) is essential for glioblastoma (GBM) therapy, and homotypic targeting is an effective strategy to achieve BBB crossing. In this work, GBM patient-derived tumor cell membrane (GBM-PDTCM) is prepared to cloak gold nanorods (AuNRs). Relying on the high homology of the GBM-PDTCM to the brain cell membrane, GBM-PDTCM@AuNRs realize efficient BBB crossing and selective GBM targeting. Meanwhile, owing to the functionalization of Raman reporter and lipophilic fluorophore, GBM-PDTCM@AuNRs are able to generate fluorescence and Raman signals at GBM lesion, and almost all tumor can be precisely resected in 15 min by the guidance of dual signals, ameliorating the surgical treatment for advanced GBM. In addition, photothermal therapy for orthotopic xenograft mice is accomplished by intravenous injection of GBM-PDTCM@AuNRs, doubling the median survival time of the mice, which improves the nonsurgical treatment for early GBM. Therefore, benefiting from homotypic membrane-enhanced BBB crossing and GBM targeting, all-stage GBM can be treated with GBM-PDTCM@AuNRs in distinct ways, providing an alternative idea for the therapy of tumor in the brain.

Gold Microbeads Enabled Proximity Electrochemiluminescence for Highly Sensitive and Size-Encoded Multiplex Immunoassays.

Developing highly sensitive multiplex immunoassays is urgently needed to guide medical research and improve clinical diagnosis. Here, we report the proximity electrochemiluminescence (ECL) generation enabled by gold microbeads (GMBs) for improving the detection sensitivity and multiplexing capacity of ECL immunoassays (ECLIAs). As demonstrated by microscopy and finite element simulation, GMBs can function as spherical ultramicroelectrodes for triggering ECL reactions in solutions. Employing GMBs as solid carriers in the bead-based ECLIA, the electrochemical oxidation of a coreactant can occur at both the GMB surface and the substrate electrode, allowing the coreactant radicals to diffuse only a short distance of ∼100 nm to react with ECL luminophores that are labeled on the GMB surface. The ECL generation via this proximity low oxidation potential (LOP) route results in a 21.7-fold increase in the turnover frequency of ECL generation compared with the non-conductive microbeads that rely exclusively on the conventional LOP route. Moreover, the proximity ECL generation is not restricted by the diffusion distance of short-lived coreactant radicals, which enables the simultaneous determination of multiple acute myocardial infarction biomarkers using size-encoded GMB-based multiplex ECLIAs. This work brings new insight into the understanding of ECL mechanisms and may advance the practical use of multiplex ECLIAs.

Multicolor Iridium(III) Complexes with Host-Guest Recognition Motifs for Enhanced Electrochemiluminescence and Modular Labeling.

Cyclometalated Ir(III) complexes with high electrochemiluminescence (ECL) efficiency and appropriate bioconjugation sites are urgently needed in ECL immunoassays (ECLIA). Herein, we report the synthesis, photophysics, electrochemistry, and ECL of six new Ir(III) complexes bearing naphthyl (nap) or adamantane phenyl (adap) substitutions, four of which emit cyan, green, or red light and display 1.7- to 7.5-fold increases in ECL intensity. In combination with DFT/TDDFT calculations, this enhancement is rationalized to the augmented radiative rate that arises from both the strengthened spin-orbit coupling (SOC) and the increased transition dipole moment. In addition, the adap-based Ir(III) complex shows high binding affinity with ß-cyclodextrin (ß-CD) due to the strong hydrophobic interaction, which enables us to develop a modular strategy for the labeling of Ir(III) complexes with biomolecules and to use hydrophobic luminophores in the aqueous-phase detection. As demonstrated, a novel ECLIA is built up and exhibits a wide linear range from 1 ng/mL to 10 µg/mL and a detection limit of 72 pg/mL for the determination of C-reactive protein (CRP). These findings provide new insights into the design, synthesis, and bio-labeling of highly emissive Ir(III) complexes and pave the way for the development of novel ECLIA based on host-guest recognition motifs.

Polarity Conversion of the Ag2S/AgInS2 Heterojunction by Radical-Induced Positive Feedback Polydopamine Adhesion for Signal-Switchable Photoelectrochemical Biosensing.

Efficient tuning of the polarity of photoactive nanomaterials is of great importance in improving the performance of photoelectrochemical (PEC) sensing platforms. Herein, polarity of the Ag2S/AgInS2 heterojunction is converted by radical-induced positive feedback polydopamine (PDA) adhesion, which is further employed to develop a signal-switchable PEC biosensor. In the nanocomposites, Ag2S and AgInS2 achieve electron-hole separation, exhibiting a strong anodic PEC response. Under the irradiation of light, the Ag2S/AgInS2 heterojunction is able to produce superoxide radical and hydroxyl radical intermediate species, leading to the polymerization of dopamine (DA) and the subsequent adhesion of PDA onto the Ag2S/AgInS2 heterojunction (Ag2S/AgInS2@PDA). By constructing a new electron-transfer pathway with PDA, the polarity of the Ag2S/AgInS2 heterojunction is converted, and the PEC response changes from anodic to cathodic photocurrents. In addition, since the photoreduction activity of PDA is stronger than that of the Ag2S/AgInS2 heterojunction, more superoxide radical can be produced by Ag2S/AgInS2@PDA once PDA is generated, thereby promoting the generation of PDA. Consequently, a positive feedback mechanism is established to enhance the polarity conversion of the Ag2S/AgInS2 heterojunction and amplify the responding to DA. As a result, the bioanalytical method is capable of sensitively quantifying DA in 10 orders of magnitude with an ultralow limit of detection. Moreover, the applicability of this biosensor in real samples is identified by measuring DA in fetal bovine serum and compared with a commercial ELISA method. Overall, this work offers an alternative perspective for adjusting photogenerated carriers of nanomaterials and designing high-performance PEC biosensors.

Functionalized biological metal-organic framework with nanosized coronal structure and hierarchical wrapping pattern for enhanced targeting therapy.

Inefficient tumor-targeted delivery and uncontrolled drug release are the major obstacles in cancer chemotherapy. Herein, inspired by the targeting advantage of coronavirus from its size and coronal structure, a coronal biological metal-organic framework nanovehicle (named as corona-BioMOF) is constructed for improving its precise cancer targeting ability. The designed corona-BioMOF is constructed as the carriers-encapsulated carrier model by inner coated with abundant protein-nanocaged doxorubicin particles and external decorated with high-affinity apoferritin proteins to form the spiky surface for constructing the specific coronal structure. The corona-BioMOF shows a higher affinity and an enhanced targeting ability towards receptor-positive cancer cells compared to that of MOF-drug composites without spiky surface. It also exhibits the hierarchical wrapping pattern-endowed controlled lysosome-specific drug release and remarkable tumor lethality in vivo. Moreover, water-induced surface defect-based protein handle mechanism is first proposed to shape the coronal-BioMOF. This work will provide a better inspiration for nanovehicle construction and be broadly useful for clinical precision nanomedicine.

Chemical Mechanism-Dominated and Reporter-Tunable Surface-Enhanced Raman Scattering via Directional Supramolecular Assembly.

Molecular resonance can be strengthened by charge transfer, profiting chemical mechanism (CM)-related surface-enhanced Raman scattering (SERS). Herein a supramolecular assembly enabled SERS system is established by functionalizing para-sulfonatocalix[4]arene (pSC4) onto Au3Cu nanocrystals (NCs). Due to the cooperation of Au and Cu, pSC4 is directionally assembled on the surface of Au3Cu NCs via van der Waals force, enabling photoinduced and hydrogen bond-induced charge transfer, which remarkably enhances the Raman scattering of methylene blue (MB) captured by pSC4. In particular, for the C-N and C-C stretching of MB, the contributions of resonance Raman scattering increase up to 80%. In addition, the SERS system is able to display affinities of different host-guest interactions, and further employed to evaluate effects of drugs for Alzheimer's disease. In this work, charge transfer is realized by performing supramolecular assembly on the surface of plasmonic nanomaterials, providing an avenue to design CM-related and reporter-tunable SERS systems.

Enhancing Photoelectric Response of an Au@Ag/AgI Schottky Contact through Regulation of Localized Surface Plasmon Resonance.

Carrier generation and migration are both pivotal to photoelectric (PE) response. Formation of a Schottky contact is conducive to promote carrier migration but cannot fundamentally magnify carrier generation, limiting the eventual PE performance. In this work, an Au@Ag/AgI Schottky contact is established by in situ growth of AgI nanotriangles on the surface of Au@Ag nanoparticles (NPs), and PE enhancement of the Schottky contact is realized by regulating localized surface plasmon resonance (LSPR) properties. In comparison with Ag/AgI Schottky contact, assembly of Au NPs in the center of Ag NPs adjusts the dominated LSPR property from hot-electron transfer (HET) to plasmon-induced resonance energy transfer (PIRET). With the concurrent manipulation of HET and PIRET, additional energy can be employed for carrier generation, while photogenerated electrons offset by hot electrons are reduced, which jointly enlarges PE responses of the Au@Ag/AgI Schottky contact up to 4 times. Benefitted from the etching of thiols to Ag-based materials, the Au@Ag/AgI Schottky contact is further applied to the construction of a photoelectrochemical cysteine sensor. This work proposes a general strategy to enhance PE responses of Schottky contacts, which may advance the design of LSPR-related PE systems.

Modulating Polarization of Perovskite-Based Heterostructures via In Situ Semiconductor Generation and Enzyme Catalysis for Signal-Switchable Photoelectrochemical Biosensing.

Polarization of photoactive materials in current photoelectric (PE) systems is difficult to be adjusted, and thus electron-transfer routes of these systems are unchangeable, which limits their performance in photoelectrochemical (PEC) analysis. Herein, we attempted to modulate the polarization of perovskite-based heterostructures by both in situ semiconductor generation and enzyme catalysis. Owing to their band alignments, Cs3Bi2Br9 quantum dots (QDs) and BiOBr are confirmed to construct a Z-scheme structure, leading to a large anodic photocurrent. In the presence of ascorbic acid 2-phosphate (AAP), BiPO4 is generated on the surface of the Cs3Bi2Br9 QDs/BiOBr heterostructure, reassigning energy bands of BiOBr. Accordingly, polarization of the photoactive materials is converted, and a new Z-scheme structure with a reversed electron-transfer route is constructed, which leads to an evident cathodic photocurrent. Furthermore, abundant electron donors can be obtained by catalyzing AAP with alkaline phosphatase (ALP). In this case, photogenerated holes in BiOBr are preferentially annihilated by electron donors, thereby blocking transfer of photogenerated electrons in the Cs3Bi2Br9 QDs/BiOBr/BiPO4 heterostructure. Consequently, a second polarization conversion is triggered by enzyme catalysis, resulting in the recovery of an anodic photocurrent. Benefited from the polarization conversion, a PEC biosensor with a feature of two-wing signal switch is designed, which remarkably enlarges the range of the signal response and subsequently improves the analytical performance. As a result, ALP in small volume of human serum can be quantified with this method. In this work, polarization of perovskite-based photoactive materials is tuned, proposing an alternative perspective on the design of advanced PE systems.

Co-Quenching Effect between Lanthanum Metal-Organic Frameworks Luminophore and Crystal Violet for Enhanced Electrochemiluminescence Gene Detection.

Exploring new electrochemiluminescence (ECL) luminophores to construct high-efficiency sensing systems is always a hot direction for developing ECL sensors. Compared with other luminophores, metal-organic frameworks (MOFs) exhibit high mass transfer ability for accelerating the reactivity in its pore channels, which is conducive to improving the performance of ECL sensors. In this work, La3+ -BTC MOFs (LaMOFs) are prepared as the highly active reactor and novel ECL luminophore. On this basis, a novel co-quenching effect mechanism is proposed based on double-stranded DNA (dsDNA) triggered cooperation between LaMOFs and crystal violet (CV) molecules. Under the confined pore channels of LaMOFs, CV can play an important role as the photon-acceptor due to the matched absorption spectrum with the ECL spectrum of LaMOFs, and the electron-acceptor on account of its lowest unoccupied molecular orbital level. Based on the proposed co-quenching effect mechanism, a constructed ECL gene sensor shows good assay performance toward p53 gene in the detection range of 1 pm to 100 nm with a detection limit of 0.33 pm. The co-quenching effect integrating LaMOFs with CV is expected to be a versatile approach in the construction of ECL gene sensor, which has good prospect in expanding the application range of ECL technology.

Applications of DNA-nanozyme-based sensors.

Since the discovery of the enzyme-like activities of nanomaterials, the study of nanozymes has become one of the most popular research frontiers of diverse areas including biosensors. DNA also plays a very important role in the construction of biosensors. Thus, the idea of combined applications of nanozymes with DNA (DNA-nanozyme) is very attractive for the development of nanozyme-based biosensors, which has attracted considerable interest of researchers. To date, many sensors based on DNA-functionalized or templated nanozymes have been reported for the detection of various targets and highly accelerated the development of nanozyme-based sensors. In this review, we summarize the main applications and advances of DNA-nanozyme-based sensors. Additionally, perspectives and challenges are also discussed at the end of the review.

Dysregulated N6-methyladenosine (m6A) processing in hepatocellular carcinoma.

N6-methyladenosine (m6A) is the most thoroughly studied type of internal RNA modification, as this epigenetic modification is the most abundant in eukaryotic RNAs to date. This modification occurs in various types of RNAs and plays significant roles in dominant RNA-related processes, such as translation, splicing, export and degradation. These processes are catalyzed by three types of prominent enzymes: writers, erasers and readers. Increasing evidence has shown that m6A modification is vital for the regulation of gene expression, carcinogenesis, tumor progression and other abnormal changes, and recent studies have shown that m6A is important in the development of hepatocellular carcinoma (HCC). Herein, we summarize the nature and regulatory mechanisms of m6A modification, including its role in the pathogenesis of HCC and related chronic liver diseases. We also highlight the clinical significance and future strategies involving RNA m6A modifications in HCC.

Construction of Molecular Sensing and Logic Systems Based on Site-Occupying Effect-Modulated MOF-DNA Interaction.

Interactions between metal-organic frameworks (MOFs) and nucleic acids are of great importance in molecular assembly. However, current MOF-nucleic acid interactions lack diversity and are normally realized in an uncontrollable manner. Herein, the interaction of zirconium-based MOFs (Zr-MOFs) with nucleic acids is enabled by the formation of Zr-O-P bonds and further manipulated by a phosphate-induced site-occupying effect. Covering Zr ions in clusters of MOFs with phosphates impedes the formation of Zr-O-P bonds with nucleic acids, rendering the MOF-nucleic acid interaction tunable and stimulus-responsive. Notably, the experimental results demonstrate that various phosphates, Zr-MOFs, and nucleic acids can all be adopted in the tunable interaction. On the basis of these findings, fluorescent DNA and typical Zr-MOFs are proposed as functional probe-quencher pairs to establish molecular sensing and logic systems. Accordingly, alkaline phosphatase and inorganic pyrophosphatase can be quantified simultaneously, and the overall relation of different phosphates and phosphatases is facilely displayed. The work provides a general strategy for modulating MOF-nucleic acid interactions, which is conducive to the development of molecular intelligent systems.

Ratiometric Fluorescent Quantum Dot-Based Biosensor for Chlorothalonil Detection via an Inner-Filter Effect.

A new sensitive sensor for detecting chlorothalonil (CHL) based on the inner-filter effect (IFE) between gold nanoparticles (AuNPs) and ratiometric fluorescent quantum dots (RF-QDs) was developed. Here, RF-QDs were designed by two different color CdTe QDs. Based on the IFE, the AuNPs can quench the fluorescence of the RF-QDs. Because of the electrostatic attraction between protamine (PRO) and the AuNPs, the PRO can restore fluorescence effectively. Papain (PAP) can easily hydrolyze PRO and causes the quench of fluorescence quenching. The addition of CHL can inhibit PAP activity and restore the fluorescent signal. Through the characterization of the structural changes of PAP, the inhibition and mechanism of CHL on PAP activity were studied. The ability of CHL to inhibit PAP activity was evaluated by measuring the fluorescence of the RF-QDs. Under the optimal conditions, this sensing platform shows a response to CHL in the range of 0.34-2320 ng/mL and a detection limit of 0.0017 ng/mL. Based on the CHL inhibition of PAP activity, the RF-QDs showed good selectivity for CHL. The practical application of the proposed system was demonstrated by detecting CHL in food and environmental samples with satisfying results.

Colloidal-sized zirconium porphyrin metal-organic frameworks with improved peroxidase-mimicking catalytic activity, stability and dispersity.

Metal-organic frameworks (MOFs) have attracted great attention as enzyme mimic materials in colorimetric hydrogen peroxide (H2O2) detection. At present, it is highly desirable but remains challenging to prepare MOFs with high stability and dispersity to further improve their peroxidase-mimicking catalytic activity. In this work, we developed a new and facile method for the synthesis of a sub-100 nm peroxidase-mimicking zirconium porphyrin metal-organic framework (Zr-PorMOF) via a solvothermal method. The experimental results indicated that compared with the micron-sized crystals obtained using a classical synthesis method, the catalytic activity, stability and dispersity in water of the colloidal Zr-PorMOF were obviously enhanced. The as-synthesized colloidal Zr-PorMOF was further successfully applied in colorimetric H2O2 detection, and satisfactory detection performance was obtained. Furthermore, the colloidal Zr-PorMOF was also successfully employed in the construction of a peroxidase-based tandem catalysis system. Taking glucose oxidase as an example, this system was successfully applied for glucose sensing in real human serum samples, which proved its practical feasibility in diabetes diagnosis and indicates its high potential feasibility in peroxidase-related applications in complex biomatrix.

Sensitive determination of formamidopyrimidine DNA glucosylase based on phosphate group-modulated multi-enzyme catalysis and fluorescent copper nanoclusters.

In this work, a method for quantifying the activity of formamidopyrimidine DNA glucosylase (Fpg) was designed based on phosphate group (P)-modulated multi-enzyme catalysis and fluorescent copper nanoclusters (CuNCs). By eliminating 8-oxoguanine from double-stranded DNA, Fpg generates a nick with P at both 3' and 5' termini. Subsequently, part of the DNA is digested by 5'P-activated lambda exonuclease (λ Exo), and the generated 3'P disables exonuclease I (Exo I), resulting in the generation of single-stranded DNA containing poly(thymine) (poly(T)). Using poly(T) as templates, CuNCs were prepared to emit intense fluorescence as the readout of this method. However, in the absence of Fpg, the originally modified 5'P triggers the digestion of λ Exo. In this case, fluorescence emission is not obtained because CuNCs cannot be formed without DNA templates. Therefore, the catalysis of λ Exo and Exo I can be tuned by 5'P and 3'P, which can be further used to determine the activity of Fpg. The fluorescent Fpg biosensor works in a "signal-on" manner with the feature of "zero" background noise, and thus shows desirable analytical features and good performance. Besides, Fpg in serum samples and cell lysate could be accurately detected with the biosensor, indicating the great value of the proposed system in practical and clinical analysis.