{"title":"Highly Sensitive Hyperpolarized Multiplexed Single-Scan 2D 13C−1H NMR of Complex Mixtures at Natural 13C Abundance","authors":"Wiktor Adamski,Yuliia Horbenko,Benoît Charrier,Aurélie Bernard,Patrick Giraudeau","doi":"10.1021/acs.analchem.6c04662","DOIUrl":"https://doi.org/10.1021/acs.analchem.6c04662","url":null,"abstract":"Abstract Hyperpolarization provides a major sensitivity boost in NMR spectroscopy, and dissolution Dynamic Nuclear Polarization (d-DNP) has emerged as a particularly well-suited approach to analyze complex mixtures at natural 13C abundance. However, it only allows single-scan NMR detection due to the irreversible nature of hyperpolarized magnetization decay in solution. This precludes the acquisition of heteronuclear 2D NMR spectra, which are highly needed to obtain information on the identity and concentration of mixture components. To overcome this issue, ultrafast (UF) 2D NMR has been the method of choice for the last two decades, but it suffers from limited resolution and sensitivity, which restrains its application to 13C-labeled or highly concentrated molecular mixtures. Herein, we propose a new concept coined Selective Multiplexed Acquisition by Sequential Harnessing (SMASH), which when combined with d-DNP allows us to retrieve 13C−1H correlations of small-molecule mixtures at low mM concentrations (in d-DNP juice) and natural 13C abundance. This new method improves the sensitivity of single-scan heteronuclear 2D NMR by a factor of 10 to 20 compared to UF experiments, thus considerably lowering the limit of detection of d-DNP-hyperpolarized 2D NMR experiments. The potential of SMASH NMR is illustrated on d-DNP hyperpolarized metabolite mixtures, showing that it will complement UF 2D NMR methods in the future to reveal the 13C−1H correlations of hyperpolarized small-molecule mixtures at 13C natural abundance.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"39 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209959","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":"Synergistic Vacancy-Mediated Adsorption-Activation Strategy and Spatial Confinement Effect for Enhanced Electrochemiluminescence Sensing of Isocarbophos","authors":"Chenxi Yang,Ying Wang,Xiaojiao Du,Xueling Shan,Wenchang Wang,Haijiao Xie,Ding Jiang","doi":"10.1021/acs.analchem.6c04668","DOIUrl":"https://doi.org/10.1021/acs.analchem.6c04668","url":null,"abstract":"Abstract Exploring advanced strategies to overcome the sluggish activation kinetics of co-reactants and insufficient radical generation is pivotal for boosting electrochemiluminescence (ECL) sensing performance. Herein, an active radical-enriched ECL sensing platform for the ultrasensitive detection of isocarbophos (ICP) was fabricated by utilizing a synergistic vacancy-mediated adsorption-activation strategy coupled with a spatial confinement effect. Specifically, an oxygen-deficient titanium metal−organic framework (D-Ti MOF) was integrated as a robust co-reaction accelerator to trigger the emission of a pyrene-based hydrogen-bonded organic framework (PSA-HOF). Mechanistic studies revealed that abundant oxygen vacancies in D-Ti MOF served as catalytic sites, lowering the activation barrier of peroxydisulfate (K2S2O8) and promoting targeted adsorption and O−O bond cleavage to generate a high flux of sulfate radicals (SO4•−). Meanwhile, the porous MOF architecture imposed nanoscale spatial confinement, enriching reactive intermediates at the electrode interface and reducing diffusional loss. Such a confinement-enabled interfacial microenvironment was further substantiated by kinetic analyses, which revealed that D-Ti MOF promoted S2O82− reduction and redirected the process from predominantly diffusion-controlled behavior toward an adsorption- and confinement-coupled pathway, thereby increasing the local availability and productive utilization of reactive intermediates. Leveraging an isocarbophos-specific split aptamer recognition strategy, the proposed ECL biosensor exhibited a broad linear range (10 fM to 0.1 μM), an ultralow detection limit (8.38 fM), excellent stability, remarkable selectivity and reproducibility, making it highly applicable for practical sample monitoring. This work offers a new perspective for advancing co-reactant-based ECL biosensors and proposes a novel design strategy for ultrasensitive ECL sensing platforms.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"11 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209328","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":"Synergistic Integration of Water-Stable 2D Perovskite Heterojunctions and Self-Priming DNA Walkers for Sensitive Photoelectrochemical Biosensing","authors":"Chaomin Gao,Haihan Yu,Shenguang Ge,Jinghua Yu","doi":"10.1021/acs.analchem.6c05016","DOIUrl":"https://doi.org/10.1021/acs.analchem.6c05016","url":null,"abstract":"Abstract Two-dimensional Ruddlesden−Popper (2D RP) perovskites hold immense promise as light-harvesting photoactive materials for photoelectrochemical (PEC) bioanalysis, yet their poor aqueous durability and suboptimal charge-carrier dynamics severely restrict PEC sensing implementation. Herein, we report a dual-functional strategy that simultaneously addresses both challenges through the in-situ construction of a Z-scheme heterojunction, (BA)2PbI4−Pb(OH)2 (BA = butylammonium), via Lewis base vapor diffusion. The Pb(OH)2 barrier formed during synthesis acts as a robust protective shield that preserves the perovskite’s structural integrity, while the intimate Z-scheme heterointerface constructed in the heterojunction remains functional and continues to accelerate spatial charge separation even after three years of immersion in ultrapure water, as corroborated by electron paramagnetic resonance spectroscopy, photo-assisted Kelvin probe force microscopy, and density functional theory calculations. To further amplify the PEC signal, we engineer a circular DNA scaffold-supported tripedal DNA walker powered by self-priming polymerization, eliminating the requirement for exogenous primers in traditional polymerase-driven DNA nanomachines. Target-triggered autonomous walking of the tripedal DNA nanomachine continuously disassembles surface-tethered hairpin tracks, drastically mitigating interfacial steric hindrance and yielding prominent photocurrent enhancement. Synergizing the ultra-stable Z-scheme RP perovskite photoelectrode with the primer-free DNA walker, the integrated PEC sensing platform achieves ultrasensitive quantification of acetamiprid with a wide linear range spanning 10−13 to 10−6 M. This work establishes a new paradigm for rationally designing aqueous-stable perovskites and coupling them with intelligent molecular devices, paving the way for high-performance PEC sensing platforms.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"64 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210006","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}
Javier López-Asanza,Edward Zamudio,Angela Molina,Gastón A. Crespo,María Cuartero,Eduardo Laborda
{"title":"When Two Interfaces Meet: A Unified Theory for Thin-Membrane Voltammetric Ion Selective Electrodes","authors":"Javier López-Asanza,Edward Zamudio,Angela Molina,Gastón A. Crespo,María Cuartero,Eduardo Laborda","doi":"10.1021/acs.analchem.6c03127","DOIUrl":"https://doi.org/10.1021/acs.analchem.6c03127","url":null,"abstract":"Abstract Voltammetric solid-contact ion-selective electrodes (SC-ISEs) exhibit electrochemical responses that arise from the coupling of heterogeneous electron transfer at the electrode−membrane interface with ion transfer at the membrane−sample boundary. In this work, a novel theoretical framework is developed for voltammetric SC-ISEs based on thin membranes, capturing the intrinsic consequences of coupling two polarized interfaces in series under markedly different mass-transport conditions in the membrane and solution phases. The theory describes the current/charge−potential−time responses and the corresponding interfacial potentials and dynamic ion and redox-species concentrations, accounting for the effects of membrane and solution composition, membrane thickness, and experimental timescale. Besides, the theory enables quantitative analysis of experimental voltammetric outcomes. A systematic classification of cyclic voltammetry (CV) responses is obtained in terms of three dimensionless parameters that quantify ion availability in the sample solution relative to the confined membrane. Simple relationships for peak positions and practical diagnostic criteria based on CV shape and scan-rate dependence are derived to verify thin-membrane conditions and the absence of kinetic or ohmic limitations, identifying indeed whether charge compensation proceeds via ion release or uptake.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"626 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209963","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}
Shui Qin Chai,Xin Hou,Jiu Mao Zhao,Wan Lin Sun,Shu Chen Pei,Yun Ying Cheng,Wen Yi Lv,Chun Mei Li
{"title":"AND-Gated Intramolecular Confined CHA Converts Forked DNA Probes into Brushlike Assemblies for Tumor-Cell Imaging","authors":"Shui Qin Chai,Xin Hou,Jiu Mao Zhao,Wan Lin Sun,Shu Chen Pei,Yun Ying Cheng,Wen Yi Lv,Chun Mei Li","doi":"10.1021/acs.analchem.6c05499","DOIUrl":"https://doi.org/10.1021/acs.analchem.6c05499","url":null,"abstract":"Abstract Sensitive and selective imaging of low-abundance intracellular biomarkers is important for cellular analysis and disease-related biomarker evaluation, but it is often hampered by insufficient sensitivity and false-positive signals from single-target analysis. Herein, we developed a dual-locked forked DNA fluorescent probe (DL-forked probe) that integrated intramolecular confined catalytic hairpin assembly (intra-CHA) with AND-logic gating. The probe facilitated cellular uptake in the tested tumor cells via the AS1411 aptamer, without transfection reagents. APE1 and miRNA-21, two biomarkers overexpressed in tumor cells, served as the dual inputs. APE1 first cleaved the AP site in H2 to expose a toehold for miRNA-21, which then triggered a rapid intra-CHA cycle, converting the forked structure into brushlike DNA assemblies with fluorescence recovery. The spatial confinement effect restricted the reactants within ∼13 nm, with the geometric local concentration approximately 9.2 × 103-fold higher than the nominal concentration of the free-CHA system, thereby drastically accelerating reaction kinetics. The DL-forked probe exhibited a detection limit of 29 pM for miRNA-21 and 7.0 × 10−3 U/mL for APE1, with outstanding selectivity. In live-cell imaging, the probe generated 2.2-fold stronger fluorescence than the free-CHA control and produced distinct fluorescence responses among the tested tumor cells (MDA-MB-231, MCF-7, A549) and normal AML12 cells, with signal enhancements of 14.7- to 33.0-fold. These results agreed well with the independent reference methods of ELISA and RT-qPCR. This AND-gated, confinement-accelerated CHA platform provides a potential strategy for dual-biomarker-gated intracellular imaging and warrants further evaluation in clinically relevant models.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"11 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210009","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}
Chang Zhang,Hao Wang,Yingying Zhu,Haifeng Dong,Huiting Lu
{"title":"Structural Encoding-decoupled Universal Recognition\u0000Enables Amplification-free Multiplex miRNA Detection","authors":"Chang Zhang,Hao Wang,Yingying Zhu,Haifeng Dong,Huiting Lu","doi":"10.1021/acs.analchem.6c03760","DOIUrl":"https://doi.org/10.1021/acs.analchem.6c03760","url":null,"abstract":"Abstract Accurate multiplex analysis of microRNAs (miRNAs) remains constrained by enzymatic amplification, spectral crosstalk, and instrumental complexity. Herein, we report a conceptually distinct PhC-SQ platform that integrates photonic crystal (PhC) structural encoding with S9.6-mediated universal recognition for amplification-free multiplex miRNA detection. PhC microspheres act as structural color barcodes for target encoding, while quantum dots (QDs) enriched at the microsphere interface serve as fluorescent reporters. Target miRNAs hybridize with surface-bound DNA probes to form DNA/RNA duplexes, which are recognized by the S9.6 antibody. Subsequent biotin–streptavidin assembly recruits QDs, enabling interfacial fluorescence enrichment and enhanced sensitivity without enzymatic amplification. By decoupling encoding from readout, the platform eliminates spectral crosstalk and enables accurate multiplexing. A dual-mode readout, combining confocal quantification with direct UV visualization, further supports point-of-care applicability. Validation in cellular samples shows good agreement with RT-PCR. Overall, this work establishes a structural encoding-universal recognition-interfacial signal enrichment strategy for robust and field-deployable multiplex miRNA detection.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"16 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210014","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}