Although polarity-inversion photoelectrochemical (PEC) sensing can effectively suppress false-positive and false-negative responses induced by interferents, achieving high sensitivity remains challenging due to signal prereversal suppression and intrinsic signal quenching at DNA-modified interfaces. Herein, we propose an electron-conducting DNA track-mediated BiOI homojunction pre-enhanced platform, which not only effectively facilitates electron transfer to eliminate the inherent signal quenching effect of conventional DNA interfaces, thereby achieving pronounced pre-enhancement of the initial PEC signal, but also guides the DNA walker to achieve photoelectrochemical polarity inversion, enhancing anti-interference capability and detection sensitivity. A morphology-engineered BiOI homojunction is first constructed to generate a strong and stable baseline cathodic photocurrent by promoting efficient charge separation and interfacial transport through the electron-conducting DNA track. Upon microRNA-125b (miRNA-125b) recognition, a catalytic hairpin assembly (CHA)-amplified DNA walker is activated to migrate along the electron-conducting DNA track, directing the in situ accumulation of polydopamine (PDA) as a signal-reversal mediator and inducing a controllable photocurrent inversion from cathodic to anodic. By coupling electron-conducting DNA track-mediated pre-enhancement with walker-guided polarity inversion, this strategy establishes a high-contrast dual photocurrent window, enabling sensitive and rapid detection of miRNA-125b with a linear range from 1 pM to 1 nM and a detection limit as low as 0.13 pM. This work establishes a generalizable PEC sensing strategy that integrates electron-conducting DNA track engineering with signal-polarity modulation, providing a robust platform for quantitative detection of nucleic acids.
Electrochemical immunosensors offer an attractive platform for rapid and sensitive quantification of cancer biomarkers. Herein, a sandwich-configuration electrochemical immunosensor was designed for the ultrasensitive detection of prostate-specific antigen (PSA). Platinum nanoparticle-loaded copper molybdate (Pt@CM) was employed as a signal amplification label, leveraging the dual redox cycles between its Cu(I,II) and Mo(IV, VI) to enhance electrocatalytic performance. Gold nanoparticles (Au NPs) immobilized on polydopamine-modified halloysite nanotubes (Au-PDA@HNT) serve as a stable substrate platform, enhancing conductivity and enabling efficient immobilization of primary antibody. Under optimized conditions, the immunosensor achieved a wide linear range of 100 fg/mL to 100 ng/mL and a detection limit of 0.03 pg/mL for PSA, with excellent reproducibility, stability, and selectivity. This platform shows significant potential for early tumor biomarker screening.
Blue energy is vital for sustainable development, providing a viable alternative to fossil fuels and contributing to climate change mitigation and environmental protection. Triboelectric nanogenerators (TENGs), a novel energy-harvesting technology, have garnered significant attention, particularly for their potential in wave energy harvesting. However, enhancing the performance of solid-liquid TENGs under low-frequency excitation remains challenging. This study addresses this challenge by leveraging the volume effect to substantially enhance the effective output power of liquid-film triboelectric nanogenerators (LF-TENGs). A 5.22-fold increase in output power was achieved, reaching 95.01 mu W, compared to LF-TENGs without the volume effect. When integrated into a cathodic protection system, the LF-TENG reduced the open-circuit potential of aluminium by approximately 320 mV in a 3.5% NaCl solution. The electric energy generated from the triboelectric effect of the LF-TENG can enhance the corrosion protection of metal substrates in marine engineering through cathodic protection. Additionally, a ship shock protection sensor based on LF-TENG further validates its potential in sensing applications. These findings underscore the capability of LF-TENGs to advance marine energy harvesting and corrosion protection technologies, offering a promising solution for sustainable energy generation and infrastructure protection.
Metal nanoclusters (MNCs) are widely used in electrochemiluminescence (ECL) immunosensors due to their unique optical properties, ultra-small size, and excellent biocompatibility. However, their practical application is limited by poor stability and low ECL efficiency, which result from insufficient excited states generation and non- radiative transition losses caused by stabilization with small capping ligands. To address these challenges, we propose a co-reaction accelerator-encapsulated aggregation-induced ECL (AE-AIECL) enhancement strategy, driven by cascade-sensitized electron transfer and radiative transitions mechanism. In this work, L-histidine-ZIF8 (L-His-ZIF-8) is employed as a co-reaction accelerator for encapsulating gold nanoclusters (AuNCs). The spatial confinement effect of L-His-ZIF-8 effectively confine the AuNCs, reducing non-radiative transition through coordination bonding between Zn2+ and carboxylate groups (-COOH), thereby enhancing the emission efficiency of AuNCs. Additionally, L-His-ZIF-8 accelerates electron transfer through its catalytic effect on the co-reactant peroxynitrite (S2O82-), further boosting the interaction efficiency between AuNCs and sulfate radicals (SO4 center dot-). This cascade-sensitized mechanism significantly enhances the ECL signal of AuNCs by nearly threefold, improving both radiative transitions and electron transfer. Using this AE-AIECL enhancement strategy, a quenching-typed ECL immunosensor was developed, utilizing AuNCs@L-His-ZIF-8 as a donor and Au-MnO2 as a quencher for quantitative detection of pro-gastrin-releasing peptide (Pro-GRP). The ECL immunosensor demonstrated excellent stability and reproducibility, a wide linear detection range of 100 fg mL-1-1 mu g mL-1 and a detection limit of 33.5 fg mL-1, providing valuable potential for the early diagnosis and prevention of small cell lung cancer (SCLC).
As a gold standard biomarker for acute myocardial infarction (AMI), cardiac troponin I (cTnI) plays a crucial role in the prevention and monitoring of this condition. Herein, an efficient sandwich-type electrochemical immunosensor is developed for the quantitative measurement of cTnI utilizing highly active trimetallic PtCuRu as a signal amplification platform and N-rich interpenetrating twin porous carbon (ITPC) decorated with gold nanoparticles (Au NPs/ITPC) as matrix material. The morphologically controlled ZIF-8-derived ITPC, synthesized via a facile and green method, features enlarged surface area and high nitrogen content, enabling effective H2O2 enrichment and Ab1 immobilization, thereby enhancing the stability and sensitivity of the biosensor. In addition, thanks to its open structure and optimized d-orbital coupling features, the meticulously designed flower-like PtCuRu (PtCuRu NF) possess efficient mass and electron transfer ability, favoring amplifying its H2O2 electroreduction activity. These intrinsic advantages of the precisely fabricated electrochemical immunosensor enable outstanding sensitivity, wide dynamic linear range (10 fg mL- 1 to 100ng mL-1) as well as ultralow detection limit (0.58 fg mL- 1) for cTnI. In addition, excellent reproducibility, ideal selectivity and long-term stability were also achieved for the cTnI detection. This work pioneered an innovative precisely designed method for sandwichtype electrochemical immunosensor enabling early, quantitative measurement and prognosis of cTnI.
The conventional nitration process, which relies on concentrated nitric acid as a reagent, presents significant challenges including high safety risks and substantial environmental burdens. To address these issues, this study developed a novel dual-base modified composite catalyst (TS-1@Ti-MWW-OH), which enables the efficient synthesis of 2-nitropropane via the ammoxidation/oxidation of acetone under mild conditions using ammonia and hydrogen peroxide. The core innovation of this work lies in the precise design of dual active sites with complementary functions, establishing a “synergistic relay” catalytic mechanism: the Ti4+ sites in Ti-MWW preferentially catalyze the conversion of acetone to acetone oxime, followed by the Ti4+ sites in TS-1 catalyzing the subsequent transformation of acetone oxime to 2-nitropropane. Through modification with 4-methoxypyridine/ethanolamine dual bases, the specific surface area and pore volume of the catalyst were significantly enhanced, thereby substantially improving reaction mass transfer efficiency and accessibility to active sites. Process simulation based on Aspen Plus V14 confirmed the potential for industrial scale-up of this route, achieving an annual production of 13000 tons of 2-nitropropane with a purity of no less than 99.99
Carcinoembryonic antigen (CEA), a clinically critical tumor biomarker, enables early cancer screening and diagnosis. Here, we describe a sandwich-structured electrochemical immunosensing platform enabling supersensitive CEA quantification, leveraging synergistic signal amplification by sea urchin-like PdAg nanostructures and Au NPs/N-C@CNTs substrates. The urchin-like morphology of PdAg endows the material additional catalytic active sites for hydrogen peroxide reduction, which has remarkable electrochemical performance. Moreover, PdAg with superior biocompatibility can effectively immobilize the secondary antibody. Polydopamine-coated carbon nanotubes are carbonized to yield nitrogen-doped carbon nanotubes (N-C@CNTs), which are bound to gold nanoparticles (Au NPs) via stable AuN bonds, thereby facilitating the subsequent binding of primary antibodies to the Au NPs. Optimized assays demonstrated a broad dynamic range (50 fg mL-1-100 ng mL-1) with low detection limits (1.04 fg mL-1, S/N = 3), coupled with exceptional reproducibility, selectivity, and stability. This platform holds significant promise for the screening of early-stage tumor biomarkers.
The global demand for rapid and non-invasive diagnostic methods for respiratory diseases has significantly intensified due to the wide spread of respiratory infectious diseases. Recent advancements in respiratory disease diagnosis through the analysis of exhaled breath and saliva has attracted great attention all over the world. Among various analytical methods, biosensors can offer non-invasive, efficient, and cost-effective diagnostic capabilities, emerging as promising tools in this area. This review intends to provide a comprehensive overview of various biosensors for the detection of respiratory disease related biomarkers in exhaled breath and saliva. Firstly, the characteristics of exhaled breath and saliva, including their generation, composition, and relevant biomarkers are introduced. Subsequently, the design and application of various biosensors for detecting these biomarkers are presented, along with the innovative materials employed as sensitive components. Different types of biosensors are reviewed, including electrochemical, optical, piezoelectric, semiconductor, and other novel biosensors. At last, the challenges, limitations, and future trends of these biosensors are discussed. It is anticipated that biosensors will play a significant role in respiratory disease diagnosis in the future.
The precise embedding of metal species within specific sites of zeolite frameworks and their unique microenvironments exert fascinating influences on catalytic performance. Herein, we report the rational design of a highly efficient Co-Cu@CTS-1 catalyst through the strategic incorporation of Co, Cu, and Ce into TS-1 zeolite, where Ce is doped at silicon atomic sites while Co and Cu are encapsulated within the zeolite cages. Mechanistic investigations reveal that the synergistic interplay among Co, Cu, and Ce is pivotal for catalytic activity: Co facilitates molecular oxygen activation to generate reactive oxygen species (O⁻), while Ce(III) enhances oxygen vacancy concentration, significantly boosting styrene conversion. Moreover, the distinctive electronic interaction between Ce and Cu markedly improves the selectivity toward styrene oxide. The optimized Co-Cu@CTS-1 catalyst exhibits exceptional performance in the aerobic epoxidation of styrene, achieving a remarkable conversion of 78.11
Herein, an enzyme-free and highly efficient sandwich-type electrochemical immunosensor for cTnI detection was developed using covalent organic framework (COF) confined Co3O4 nanoparticles (NPs) as the signal probe and enhancing the sensitivity with electrochemical-chemical-chemical (ECC) redox cycle amplification (RCA) strategy. The multifunctional COF, with high surface area and rich nitrogen, serves not only as a substrate material but also as a scaffold for Co2+ entrapment, enabling the confined growth and uniform distribution of ultrafine Co3O4 NPs as signal amplification platform, thereby providing abundant catalytic active sites for ECC redox cycling reactions. COF confined Co3O4 NPs with variable valence states (Co3+/Co2+) serve as a redox-active electrode material that can enhance the current signal substantially. The ECC redox cycle is triggered by the redox reaction between Co3+ at the electrode and electroactive hydroquinone (HQ), while HQ was regenerated by the reducing agent tris (2-carboxyethyl) phosphine (TCEP), resulting in a significant amplification of the current signal for cTnI analysis. The constructed immunosensor exhibited excellent performance with a wide linear range from 1 fg mL-1 to 100 ng mL-1, and a low detection limit of 0.88 fg mL-1. Furthermore, the immunosensor successfully applied to detected cTnI in human serum, proving its clinical potential.
Yan-Shi-Qiang-Xin decoction (YSQXD), a traditional Chinese medicine formula, is clinically effective in treating chronic heart failure, yet its bioactive constituents remain unclear. To address this, a sensitive and reliable UHPLC-Q-Exactive Orbitrap HRMS method was established to separate and identify the chemical constituents in YSQXD and its absorbed constituents in rat serum, heart and liver following oral administration of YSQXD. With the optimized conditions, a total of 134 chemical components were tentatively identified, including 41 terpenoids, 34 flavonoids, 19 alkaloids, nine organic acids, eight amino acids, seven coumarins, six nucleotides, two sterols, and eight other compounds, based on retention times, MS/MS spectra, and literature references. Furthermore, 29, 10, 17 constituents were identified in the rat serum, heart and liver, respectively. Finally, the network pharmacology analysis based on absorbable components indicated that polyporenic acid, bavachalcone, albiflorin, biatractylolide, psoralen, angelicin, neobavaisoflavone, dictysine, isotalatizidine, and 26-hydroxyporicoic acid G exhibited high degree values, suggesting their potential as active ingredients for chronic heart failure treatment. These findings provide a comprehensive chemical profile of YSQXD and its absorbed components, offering valuable insights into its pharmacologically active substances.
Conventional nitration methods using concentrated nitric acid pose significant safety and environmental risks. To address this, a dual-base-modified composite catalyst (TS-1@Ti-MWW-OH) was designed for efficient 2-nitropropane synthesis via acetone ammoxidation/oxidation. Structural characterization confirmed that compositing TS-1 with Ti-MWW and modifying with 4-methoxypyridine/ethanolamine increased specific surface area (32%), pore volume (28%), and pore size (1.8 nm), enhancing mass transfer and active site accessibility. Mechanistic studies revealed a synergistic relay catalysis: Ti 4+ sites on Ti-MWW catalyzed acetone→acetone oxime conversion, while Ti 4+ on TS-1 oxidized oxime→2-nitropropane, achieving 92.2% yield. Process simulation via Aspen Plus V14 demonstrated industrial-scale production of 13,000 t/year 2-nitropropane (≥ 99.99 wt%) and 760 t/year acetone oxime (≥ 99.8 wt%), with stable operation ≥ 8,000 h/year validated by RADFRAC and tray hydraulics analysis. Additionally, column sizing (height and diameter) and tray hydraulics analysis performed using the Tray Sizing module confirmed that the maximum flooding ratio remains within permissible operating limits.This work provides a sustainable strategy for nitroalkane production through tailored catalyst design and optimized process engineering.
An electrochemical immunosensor based on the novel high efficiency catalytic cycle amplification strategy for the sensitive detection of cardiac troponin I (cTnI). With its variable valence metal elements and spiny yolk structure, the Cu 2 O/CuO@CeO 2 nanohybrid exhibits high speed charge mobility and exceptional electrochemical performance. Notably, fluorite -like cubic crystal CeO 2 shell would undergo redox reaction with Cu 2 O core, which successfully ensures the continuous recycling occurrence of "fresh" Cu (II)/Cu (I) and Ce (IV)/Ce (III) pairs at the electrode interface. The "fresh" active sites continue to emerge constantly, resulting in a significant increase in the current signal. In light of the electrochemical characterization, the electron transfer pathway and catalytic cycle mechanism among CeO 2 , Cu 2 O and CuO were further discussed. The developed electrochemical immunosensor detected cTnI from 100 fg/mL to 100 ng/mL with a LOD of 15.85 fg/mL under optimal conditions. The analysis results indicate that the immunosensor would hold promise for broad application prospects in the biological detection for other biomarkers.
A ternary ECL system was constructed with Ce2Sn2O7@MSN 2 Sn 2 O 7 @MSN composite as luminophore, potassium persulfate as co-reactant and Au@NiO-CeO2 2 as co-reaction accelerator to realize ultra-sensitive biosensing detection of prostate specific antigen (PSA). The abundant oxygen vacancies in Ce2Sn2O7 2 Sn 2 O 7 endow it with powerful electrochemical redox ability, accelerate energy transfer, and ensure Ce2Sn2O7 2 Sn 2 O 7 excellent electrochemical luminescence performance as a luminophore. Furthermore, to optimize the luminescence energy, enhance stability, and reduce the background signal to improve its signal-to-noise ratio, a highly selective Ce2Sn2O7@MSN 2 Sn 2 O 7 @MSN biological probe was obtained by coating cerium stannate (Ce2Sn2O7) 2 Sn 2 O 7 ) with mesoporous silica nanospheres (MSN). Au@NiO-CeO2 2 with a large specific surface area and high oxygen vacancy activity was synthesized as the co-reaction accelerator, which promoted the generation of SO4 4 center dot- through the rapid reversible oxidation and reduction of Ce4+/Ce3+, 4+ /Ce 3+ , thereby the ECL signal amplified effectively. Under optimal conditions, the linear detection range of PSA spans from 100fg mL- 1 to 100 ng mL-1,- 1 , with a remarkable lowest detection limit of 0.037pg mL-1,- 1 , showcasing significant application potential. This study provides a valuable reference for pyrochlore to be used as luminophore in the detection of various biomarkers by ECL biosensing.
Oxaliplatin (OXA) is the first-line drug for the treatment of colorectal cancer (CRC), and susceptibility to drug resistance affects patient prognosis. However, the exact underlying mechanisms remain unclear. Platinum-acquired resistance in CRC is a continuous transition process; though, current research has mainly focused on the end state of drug resistance, and the early events of drug resistance have been ignored. In this study, single-cell transcriptome sequencing is combined with a dynamic network biomarker (DNB), and found that the functional inhibition of the mitochondrial electron transport chain complex I occur early in the development of attained resistance to OXA in CRC cells, as evidenced by a decrease in the levels of subunit proteins, primarily NDUFB8. Specifically, the mouse double minute 2 homologue (MDM2) mediates the ubiquitination and degradation of NDUFB8, reducing intracellular reactive oxygen species (ROS) generation under chemotherapeutic stress, consequently contributing to drug resistance. Based on this, the study constructs engineered extracellular vesicles carrying siMDM2 by electroporation and validates the application of EV-siMDM2 to improve the efficacy of OXA-based chemotherapy by inhibiting the MDM2/NDUFB8/ROS signaling axis in patient-derived xenograft (PDX) and hepatic and pulmonary metastasis mouse models, thus providing new ideas and an experimental basis for the platinum-resistant treatment of CRC.
PurposeOur study aimed to develop a relatively accurate gastric cancer (GC) screening score system for urban residents and to validate the screening efficacy.MethodsThe present study included a derivation cohort (n = 3406) and a validation cohort (n = 868) of urban residents. Applying the full-stack engineering intelligent system platform of Hualian Health Big Data of Shandong University, the clinical physical examination data of subjects were collected. Univariate and multivariate analyses were used to identify risk factors for GC, and subsequently, an optimal prediction rule was established to create three distinct scoring systems.ResultsIn the GC-risk scoring system I, age, plateletocrit (PCT), carcinoembryonic antigen (CEA), glucose, albumin, creatinine were independent risk factors of GC, with scores ranging from 0 to 28 and optimal cut-off was 15.5. The second scoring system consisted of age, PCT, RDW-CV, CEA, glucose, albumin, and creatinine, with scores ranging from 0 to 31. The optimal cut-off point was determined to be 15.5. The scoring system III comprise of age, sex, PCT, RDW CV, CEA, glucose, with scores ranging from 0 to 21 and optimal cut-off was 10.5. All three scoring systems demonstrated excellent discrimination for GC, achieving an AUC of 0.884, 0.89, and 0.876, respectively. In external validation, the AUC values were 0.654, 0.658, and 0.714. Notably, the GC-risk scoring system III exhibited the highest screening efficiency.ConclusionsUrban residents benefited from the effective and verified GC-risk scoring systems, which demonstrated excellent performance in identifying individuals with an elevated risk of GC.
An electrochemiluminescence energy resonance transfer system based on CdS NCs and COFs and its application for CA242 detection.
Amyloid-beta protein (A beta) is a unique biomarker for Alzheimer's disease (AD). The sandwich-type electro-chemical immunosensor, one of the key tools for detecting biomarkers, relies on a high-performance signal amplification approach to enhance its sensitivity. Ni/PdH nanodendrites (Ni/PdH NDs) have increased catalytic activity due to their unique interaction with palladium hydride and their nickel-rich surface, tunable shape and high specific surface area. Modified halloysite nanotubes (mHNT)-loaded with polypyrrole (PPy@mHNT) possess excellent dispersion and a large surface area. This enables the formation of a conductive network to prevent the accumulation of Ni/PdH NDs. Additionally, it exposes more electrocatalytic active centers, effectively amplifying electrical signals. By utilizing Ni/PdH@PPy@mHNT as the labeling material, it shows a consistent and remarkable electrocatalytic activity in H2O2 reduction, leading to signal amplification. The acid-etched HNT coated with polyaniline (PANI@eHNT) exhibits an exceptionally low background signal and outstanding con-ductivity. This not only accelerates electron transfer on the electrode surface, but also ensures the stable incu-bation of biomolecules post-amino grafting. Utilizing NH2-PANI@eHNT as a substrate material can guarantee stable biomolecule incubation, offer a stable sensing platform and enhance immunosensor performance. The signal can be amplified and the immunosensor's sensitivity can be raised through the efficient cooperation of the aforementioned nanomaterials. Under optimum circumstances, the electrochemical immunosensor had the lowest detection limit of 5.53 fg mL-1 and a linear range of 50 fg mL-1 to 100 ng mL-1. Based on the outstanding performance previously mentioned, this immunosensor is anticipated to aid in the early detection of AD.
Electrochemical immunosensors have gained considerable attention in detecting human disease markers due to their excellent specificity, high sensitivity, and facile operation. Herein, a rational-designed sandwich -type electrochemical immunosensor is constructed for the sensitive detection of cardiac troponin I (cTnI) using nitrogen-doped carbon nanotubes loaded with gold nanoparticles (Au NPs/N-CNTs) as substrate and highly active mesoporous palladium-nitrogen nanocubes (meso-PdN NCs) as secondary antibody markers. Benefitting from its large specific surface area (638.04 m 2 g -1 ) and high nitrogen content, novel polydopamine (PDA)/ halloysite nanotubes (HNTs) hybrid derived one -dimensional (1D) N-CNTs can provide more binding sites for the in -situ growth of Au NPs to connect Ab 1 . Furthermore, as an ideal substrate material, Au NPs/N-CNTs exhibit finely tuned mesoporous structures and outstanding conductivity, which facilitate the mass and electron transfer during the electrocatalysis process. Besides, highly concave surfaces and crystalline mesopores of meso-PdN NCs expose more surfaces and crevices, providing abundant reactive sites for H 2 O 2 reduction. Remarkably, the asobtained immunosensor presented a wide linear range (from 10 fg mL -1 to 100 ng mL -1 ) and an excellent low detection limit (9.85 fg mL -1 ). This study may offer new insights into the precise fabrication of efficient electrochemical immunosensors for various clinical diagnosis applications.