Analytical Chemistry最新文献

{"title":"Synergistic Inhibition of Nonspecific Binding for Accurate Detection of Escherichia coli O157:H7 and Multilevel Signal Discrimination","authors":"Yang Zhang,&nbsp;, ,&nbsp;Feng Hu,&nbsp;, ,&nbsp;Kaiyi Zheng,&nbsp;, ,&nbsp;Haoran Li,&nbsp;, ,&nbsp;Tianxi Yang,&nbsp;, ,&nbsp;Chuping Zhao,&nbsp;, ,&nbsp;Roujia Zhang,&nbsp;, ,&nbsp;Xiaodong Zhai,&nbsp;, ,&nbsp;Junjun Zhang,&nbsp;, ,&nbsp;Ruiyun Zhou,&nbsp;, ,&nbsp;Xiaowei Huang,&nbsp;, ,&nbsp;Zhihua Li,&nbsp;, ,&nbsp;Jiyong Shi,&nbsp;, ,&nbsp;Zhiming Guo*,&nbsp;, ,&nbsp;Shipeng Gao*,&nbsp;, and ,&nbsp;Xiaobo Zou*,&nbsp;","doi":"10.1021/acs.analchem.5c04495","DOIUrl":"10.1021/acs.analchem.5c04495","url":null,"abstract":"<p >Pathogenic <i>Escherichia coli</i> (<i>E. coli</i>), particularly <i>E. coli</i> O157:H7, is a major foodborne pathogen with significant clinical relevance, necessitating accurate and rapid subtype identification. However, the high genetic variability and biological similarity among <i>E. coli</i> strains pose challenges for conventional signal-strain detection methods, often resulting in false-positive outcomes. In this study, we developed a novel biosensing strategy based on plasmonic nanostructures functionalized with heterogeneous recognition elements that target two distinct epitopes of <i>E. coli</i> O157:H7. The sensor incorporates biological silent Raman tags for ratiometric signal output and magnetic enrichment to improve selectivity and minimize interference from nontarget bacteria. This design ensures excellent reproducibility and operational stability. The biosensor demonstrated an impressive limit of detection (LOD) of 1.2 CFU/mL, outperforming most existing methods. Furthermore, a cutoff value of 0.32 for the signal ratio yielded a positive predictive value of 98% and a negative predictive value of 94%, demonstrating a clear signal boundary and high accuracy for various types of signals. These results highlight the potential of our plasmonic biosensor as a rapid, ultrasensitive, and reliable point-of-care diagnostic tool for pathogen detection in complex food matrices.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22308–22317"},"PeriodicalIF":6.7,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly Sensitive and Multiplexed Detection of Low-Frequency Mutation in Fragmented ctDNA by a Dual-Role Mediator Blocker Amplification Strategy","authors":"Rui Zhang,&nbsp;, ,&nbsp;Zhening Pu,&nbsp;, ,&nbsp;Daxing Xu,&nbsp;, ,&nbsp;Ying Yin,&nbsp;, ,&nbsp;Bingbing Wei*,&nbsp;, ,&nbsp;Lei Wang*,&nbsp;, and ,&nbsp;Zhaocheng Liu*,&nbsp;","doi":"10.1021/acs.analchem.5c04894","DOIUrl":"10.1021/acs.analchem.5c04894","url":null,"abstract":"<p >The detection of mutations in circulating tumor DNA (ctDNA) is challenging due to the significant fragmentation of ctDNA and the high prevalence of the wild-type template. Additionally, variant detection through qPCR is typically dependent on target-specific fluorescence probes, and no more than five targets can be identified in a single reaction due to the limited fluorescence colors in thermal cyclers. To address these limitations, we introduce the Dual-Role Mediator Blocker Amplification (DMBA) strategy, enabling sensitive and multiplex mutation detection without reliance on specific fluorescence probes. This strategy is applicable in both qPCR and melting curve analysis (MCA) platforms. The mediator blockers in DMBA play dual roles: enhancing discrimination between wild-type and mutant DNA and releasing mediator primers. These mediator primers extend the helper target and cleave universal fluorescence probes in qPCR, enabling the detection of mutations at variant allele fractions (VAFs) as low as 0.01%. The DMBA MCA method can identify multiple mutations, overcoming limitations in fluorescence channels by using mediator primers to extend universal fluorescence probes, producing fluorescent double strands with different <i>T</i>_m’s and colors. Multiplexed DMBA-MCA was developed to detect seven variants at 0.1–0.5% VAF in one tube. Our innovative method offers advantages including exceptional sensitivity, elimination of the requirement for specific fluorescence probes, shorter amplicons, and high multiplexing capacity, potentially revolutionizing clinical practice and precision medicine.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22407–22417"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Clicking Fluorometric Probes on Micropatterned Glass Microfiber Filters for ppb-Level Copper Quantitation","authors":"Ladan Yeganeh Rad,&nbsp;, ,&nbsp;Tsz Yan Leung,&nbsp;, and ,&nbsp;Hua-Zhong Yu*,&nbsp;","doi":"10.1021/acs.analchem.5c04274","DOIUrl":"10.1021/acs.analchem.5c04274","url":null,"abstract":"<p >In this work, we demonstrated the efficacy of combining covalent modification via the click reaction and benchtop machine-cutting of glass microfiber filters (GMFs) to fabricate microfluidic paper-based analytical devices (μPADs) for performing ultrasensitive fluorometric assays. This has been accomplished by activating the GMF surface through the self-assembly of propargyl-PEG3-triethoxysilane (PPTES) and the click reaction to immobilize fluorometric probes (i.e., 3-azido-7-hydroxycoumarin, A-7-HC). Specifically for making the device, mini-discs of GMF (<i>d</i> = 0.5 cm or any other shape and size) are machine-cut and treated with a low concentration of PPTES in dichloromethane, while the remainder of the original GMF substrate is rendered superhydrophobic by reacting with octadecyltrimethoxysilane (OTMS). Following the reassembly of the device, the Cu(I)-catalyzed alkyne–azide cycloaddition (CuAAC)-based assay is performed by introducing A-7-HC in the presence of different concentrations of copper standards. Coupling with smartphone imaging under customized LED irradiation, we showed that the assay sites (discs) are distinct and uniform (free of coffee-ring effect); the achieved limits of detection (9.2 ± 0.8 ppb) for copper are impressive in comparison with traditionally prepared devices (drop-casting reagents on photolithographically patterned GMF/paper). As we have validated the device with the results obtained with atomic absorption spectroscopy of commercial copper diary supplements, this work reveals the potential of combining covalent surface modification with benchtop patterning techniques to create flexible μPADs for performing quantitative colorimetric and fluorometric assays.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22191–22199"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comprehensive and Site-Specific Characterization of Protein N-Glycosylation in AD Samples Reveals Its Potential Roles in Protein Aggregation and Synaptic Dysfunction","authors":"Xing Xu,&nbsp;, ,&nbsp;Haiyan Tan,&nbsp;, ,&nbsp;Kejun Yin,&nbsp;, ,&nbsp;Senhan Xu,&nbsp;, ,&nbsp;Zeyu Wang,&nbsp;, ,&nbsp;Geidy E. Serrano,&nbsp;, ,&nbsp;Thomas G Beach,&nbsp;, ,&nbsp;Xusheng Wang,&nbsp;, ,&nbsp;Junmin Peng*,&nbsp;, and ,&nbsp;Ronghu Wu*,&nbsp;","doi":"10.1021/acs.analchem.5c02455","DOIUrl":"10.1021/acs.analchem.5c02455","url":null,"abstract":"<p >Alzheimer’s disease (AD) is a neurodegenerative disorder characterized by progressive cognitive decline. Emerging evidence strongly suggests that protein glycosylation is strongly related to this disease. However, the extent and functional consequences of site-specific N-glycosylation alterations in AD remain to be further explored. Here, we employed a dendrimer boronic acid (DBA)-based enrichment strategy combined with multiplexed proteomics to systematically analyze protein N-glycosylation in post-mortem human brain tissues. We identified 3,105 N-glycosylation sites on 1,299 glycoproteins from nine AD cases and nine healthy controls, and performed a systematic and site-specific investigation of glycosylation alterations in AD. Glycoproteins involved in cholesterol efflux were upregulated, whereas those associated with chemical synaptic transmission and ion transport were significantly downregulated in AD compared to control brain samples. We observed widespread dysregulation of N-glycosylation across multiple protein domains, particularly in the ConA-like lectins/glucanases and Zn-dependent exopeptidases domains. Notably, we identified 161 N-glycosylation sites located within aggregation-prone regions (APRs), and reduced glycosylation at APRs on plaque-associated glycoproteins may be associated with protein aggregation and plaque formation. Additionally, downregulated N-glycosylation sites were enriched in synaptic membrane proteins, such as Ca²⁺ ion channels, GABA-gated chloride channels, and glutamate receptors, implicating glycosylation loss in synaptic dysfunction. Our findings suggest that the loss of N-glycosylation may contribute to the pathogenesis of AD through impairing synaptic transmission and promoting protein aggregation. This study provides novel insights into glycosylation-dependent mechanisms of neurodegeneration, highlighting N-glycosylation as a potential therapeutic target for AD treatment.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"21873–21882"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.analchem.5c02455","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215958","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CRISPR-Programmed CuO Nanocatalyst Release for Ultrasensitive Detection of Pathogens in Sterile Body Fluids","authors":"Jiayi Xiao,&nbsp;, ,&nbsp;Xiumei Hu,&nbsp;, ,&nbsp;Hanren Chen,&nbsp;, ,&nbsp;Bihong Diao,&nbsp;, ,&nbsp;Xueer Huang,&nbsp;, and ,&nbsp;Lihong Liu*,&nbsp;","doi":"10.1021/acs.analchem.5c05043","DOIUrl":"10.1021/acs.analchem.5c05043","url":null,"abstract":"<p >Treatment of sterile body fluids (SBFs) infections is delayed by conventional methods that require up to 72 h to detect pathogens. Here, we present a CRISPR-associated protein 12a (Cas12a)-programmed nanocatalyst release (CNR) method for culture-free diagnostics. To enhance both sensitivity and coverage, three starter DNA (sDNA)-complementary DNA (cDNA) probe pairs were designed for conserved regions and additional three pairs for variable regions of bacterial 16S or fungal 18S rRNA. Upon target recognition, cDNA undergoes strand displacement, releasing sDNA to activate Cas12a. The activated Cas12a cleaves copper oxide nanoparticle (CuONPs)-loaded magnetic probes, releasing tandem CuONPs. Upon acid dissolution, each CuONP generates Cu²⁺ ions that catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB), producing a visible colorimetric signal. This quadruple signal amplification strategy integrates high-copy rRNA targets, multi-cDNA recognition, Cas12a-mediated continuous release of tandem CuONPs, and Cu²⁺-driven chromogenic amplification. This nucleic acid amplification-free assay detects pathogens at 0.69 CFU mL^–1 in original SBFs samples (after 10-fold centrifugation) within 70 min. In 64 clinical samples, it achieved 100% sensitivity and 100% specificity versus culture. Notably, one culture-negative but clinically confirmed case was correctly identified. Overall, the CNR method offers a rapid, ultrasensitive, and accessible diagnostic solution for resource-limited settings.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22427–22435"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"pH-Modulated Nanogaps in Self-Assembling Gold Nanoparticle Metasurface","authors":"Xiwang Hou,&nbsp;, ,&nbsp;Tianhao Chen,&nbsp;, ,&nbsp;Minggang Zhao*,&nbsp;, and ,&nbsp;Ye Ma*,&nbsp;","doi":"10.1021/acs.analchem.5c04330","DOIUrl":"10.1021/acs.analchem.5c04330","url":null,"abstract":"<p >The development of tunable metamaterials has attracted increasing attention. However, achieving real-time modulation of the optical properties remains a significant challenge. Stimuli-responsive polymers with their rapid response characteristics offer new opportunities for applications in optical modulation and sensing. Here, we propose a novel approach for controlling interparticle spacing and pH sensing by constructing a plasmonic metasurface via self-assembly of nanoparticles (NPs) at the liquid–liquid interface. Variations in the surface plasmon resonance peak position and reflectance in the reflection spectrum indicate changes in the interparticle spacing within the metasurface. Furthermore, pH variations in the aqueous phase modulate the intensity of the Raman characteristic peaks in surface-enhanced Raman scattering spectra. We demonstrate that AuNPs modified with poly(4-vinylpyridine) (P4VP) exhibit reversible pH-responsive behavior. The pH-induced coupling and decoupling of plasmonic modes enable tunable interparticle distances from 14 to 2.2 nm and linear pH sensing over a broad range of pH 3 to 11. The sensing performance has also been validated in practical samples.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22211–22218"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantifying and Utilizing Electroosmotic Flow for Mechanical Measurements with the Scanning Ion Conductance Microscope.","authors":"Johannes Rheinlaender,Tilman E Schäffer","doi":"10.1021/acs.analchem.5c03186","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03186","url":null,"abstract":"The scanning ion conductance microscope (SICM) is an emerging imaging technique for the investigation of delicate samples on the nanometer scale in liquid environments using ion current through a glass nanopipette. In recent years, the SICM has been increasingly applied to mechanical measurements, typically using a microfluidic flow in the nanopipette induced by hydrostatic pressure. Here, we introduce the use of electroosmotic flow (EOF) in mechanical SICM measurements. We show that the EOF in small SICM nanopipettes is comparable to the flow induced by commonly applied hydrostatic pressures. We quantify the electroosmotic mobility, which is a central parameter of EOF but strongly depends on experimental conditions, by measuring the streaming current independent of nanopipette geometry. Using decane microdroplets, we show that both EOF and hydrostatic pressure can be used to mechanically probe elastic samples on the nanometer scale. We then develop a numerical model to quantify the stiffness and the Young's modulus of elastic samples using EOF. Finally, we use EOF to map the Young's modulus of living cells, which gives similar results to the hydrostatic pressure method. We thereby demonstrate that EOF can be used to quantitatively probe sample stiffness with the SICM.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"47 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Plasma–Microdroplet Fusion for Online Post-Column Epoxidation: Toward Deep Lipidomics on Unmodified Mass Spectrometers","authors":"Niraj K. Panday,&nbsp;, ,&nbsp;Alexander J. Grooms,&nbsp;, ,&nbsp;Santosh R. Acharya,&nbsp;, and ,&nbsp;Abraham K. Badu-Tawiah*,&nbsp;","doi":"10.1021/acs.analchem.5c02269","DOIUrl":"10.1021/acs.analchem.5c02269","url":null,"abstract":"<p >The ability to characterize closely related lipids is clinically important, requiring the development of analytical tools to differentiate species responsible for metabolic disorders from those needed for metabolic homeostasis. Herein, we report a new liquid chromatographic (LC) method that utilizes online microdroplet-based epoxidation reactions during electrospray to enable C═C bond localization on conventional tandem mass spectrometry (MS/MS). Through a coaxial spray mechanism, charged microdroplets derived from the LC column and containing the lipid analyte were fused with nonthermal plasma, which facilitated (i) positive ion mode detection of various lipid classes and (ii) instantaneous C═C bond epoxidation via reaction with reactive oxygen species in the nonthermal plasma. Consequently, conventional low-energy MS/MS based on collision-induced dissociation was effective in characterizing the positional isomers of various lipids. Our ability to modify electrosprayed microdroplets post-column allowed independent optimization of the LC mobile phase, which in turn enabled both polar and nonpolar lipids to be separated on a C12 reverse-phase column. A data-dependent acquisition (DDA) method was created to enable the automated characterization of epoxide products in a 17-component lipid mixture. The DDA method was applied to characterize new triacylglycerol previously not detected in extra virgin olive oil.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"21853–21862"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Deep Learning-Enhanced Dual-Component Gas Sensor Based on Wavelength Modulation Spectroscopy","authors":"Huidi Zhang,&nbsp;, ,&nbsp;Xiaonan Zhang,&nbsp;, ,&nbsp;Jun Tang,&nbsp;, ,&nbsp;Yaohan Li,&nbsp;, ,&nbsp;Zhirong Zhang,&nbsp;, and ,&nbsp;Sheng Zhou*,&nbsp;","doi":"10.1021/acs.analchem.5c03438","DOIUrl":"10.1021/acs.analchem.5c03438","url":null,"abstract":"<p >Considering the challenge of qualitative and quantitative detection for gas mixtures caused by spectral overlap, a deep learning-enhanced dual-component gas sensor based on wavelength modulation spectroscopy (WMS) with the 2<i>f</i>/1<i>f</i> signals is proposed, achieving simultaneous detection of exhaled carbon dioxide (CO₂) and methane (CH₄) concentrations using a single laser. A convolutional neural network (CNN)-based concentration prediction model (CPM) is introduced to address the cross-interference caused by the spectral overlap between gas molecules and to predict the concentration of each gas component accurately. Unlike traditional methods that collect a large number of labeled data from time-consuming experiments, a generative adversarial network (GAN) is used for the data augmentation of 2<i>f</i>/1<i>f</i> spectral signals, effectively addressing the issue of scarce experimental data for model training. The predicted concentrations are linearly fitted against the standard concentrations with high determination coefficients, demonstrating the strong feasibility and reliability of the proposed gas sensor. Allan deviation analysis indicates minimum detection limits of 17.34 ppm for CO₂ and 3.52 ppb for CH₄ at integration times of 112 and 159 s, respectively. Critically, the successful measurement of exhaled CO₂ and CH₄ concentrations using this sensor demonstrates its excellent performance in practical applications. This is a successful attempt to apply deep learning-enhanced WMS to dual-component gas detection in human breath, which provides guidance for simultaneous measurement of multicomponent gases and further paves the way for breath diagnosis.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22032–22040"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"All-Optical Electrochemiluminescence by Light Downconversion at BiVO4 Photoanodes","authors":"Xiaodan Gou,&nbsp;, ,&nbsp;Changlin Zhou,&nbsp;, ,&nbsp;Jun-Jie Zhu*,&nbsp;, ,&nbsp;Gabriel Loget*,&nbsp;, and ,&nbsp;Neso Sojic*,&nbsp;","doi":"10.1021/acs.analchem.5c03936","DOIUrl":"10.1021/acs.analchem.5c03936","url":null,"abstract":"<p >Electrochemiluminescence (ECL) is a powerful analytical technique. However, the necessity of an external power supply limits its use for portable sensing devices. Herein, we report a new sensing scheme based on an all-optical ECL (AO-ECL), which addresses this issue by emitting light without external electrical devices but through light excitation (λ_exc). In AO-ECL, the photovoltage generated by the semiconductor simultaneously drives the anodic ECL reaction (producing photons at λ_AO-ECL) and a cathodic charge transfer. While this approach significantly reduces the complexity of ECL instrumentation, current materials for such systems often suffer from relatively complex fabrication methods and all existing AO-ECL systems are upconversion systems (e.g., λ_exc &gt; λ_AO-ECL). Here, we report for the first time an AO-ECL downconversion process (e.g., λ_exc &lt; λ_AO-ECL) based on a bismuth vanadate (BiVO₄) electrode with the model luminol–H₂O₂ system. Because BiVO₄ has a wide absorption below 500 nm, the ECL emission spectrum further red-shifts to 510 nm. The strong responsiveness toward H₂O₂ of the BiVO₄ AO-ECL system enables a significant shift on ECL onset potential from +0.3 V to −0.3 V (vs Ag/AgCl). A nearly 2.6-fold enhancement in ECL intensity was achieved at 0.4 V and the distinct ECL signal is observed even without applied bias. Moreover, the platform enabled cadmium ion (Cd²⁺) detection, with the AO-ECL intensity rising 2.2-fold. The simplicity of BiVO₄ electrode fabrication combined with its cost-effectiveness positions this downconversion AO-ECL system as a potential candidate for the development of portable bioanalytical sensors and wireless bioimaging applications.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22108–22115"},"PeriodicalIF":6.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}