Pub Date : 2024-09-27Epub Date: 2024-08-23DOI: 10.1021/acssensors.4c01029
Michael Kühl, Daniel Aagren Nielsen, Sergey M Borisov
Mapping of O2 with luminescent sensors within intact animals is challenging due to attenuation of excitation and emission light caused by tissue absorption and scattering as well as interfering background fluorescence. Here we show the application of luminescent O2 sensor nanoparticles (∼50-70 nm) composed of the O2 indicator platinum(II) tetra(4-fluoro)phenyltetrabenzoporphyrin (PtTPTBPF) immobilized in poly(methyl methacrylate-co-methacrylic acid) (PMMA-MA). We injected the sensor nanoparticles into the gastrovascular system of intact colony fractions of reef-building tropical corals that harbor photosynthetic microalgae in their tissues. The sensor nanoparticles are excited by red LED light (617 nm) and emit in the near-infrared (780 nm), which enhances the transmission of excitation and emission light through biological materials. This enabled us to map the internal O2 concentration via time-domain luminescence lifetime imaging through the outer tissue layers across several coral polyps in flowing seawater. After injection, nanoparticles dispersed within the coral tissue for several hours. While luminescence intensity imaging showed some local aggregation of sensor particles, lifetime imaging showed a more homogeneous O2 distribution across a larger area of the coral colony. Local stimulation of symbiont photosynthesis in corals induced oxygenation of illuminated tissue areas and formation of lateral O2 gradients toward surrounding respiring tissues, which were dissipated rapidly after the onset of darkness. Such measurements are key to improving our understanding of how corals regulate their internal chemical microenvironment and metabolic activity, and how they are affected by environmental stress such as ocean warming, acidification, and deoxygenation. Our experimental approach can also be adapted for in vivo O2 imaging in other natural systems such as biofilms, plant and animal tissues, as well as in organoids and other cell constructs, where imaging internal O2 conditions are relevant and challenging due to high optical density and background fluorescence.
{"title":"<i>In Vivo</i> Lifetime Imaging of the Internal O<sub>2</sub> Dynamics in Corals with near-Infrared-Emitting Sensor Nanoparticles.","authors":"Michael Kühl, Daniel Aagren Nielsen, Sergey M Borisov","doi":"10.1021/acssensors.4c01029","DOIUrl":"10.1021/acssensors.4c01029","url":null,"abstract":"<p><p>Mapping of O<sub>2</sub> with luminescent sensors within intact animals is challenging due to attenuation of excitation and emission light caused by tissue absorption and scattering as well as interfering background fluorescence. Here we show the application of luminescent O<sub>2</sub> sensor nanoparticles (∼50-70 nm) composed of the O<sub>2</sub> indicator platinum(II) tetra(4-fluoro)phenyltetrabenzoporphyrin (PtTPTBPF) immobilized in poly(methyl methacrylate-<i>co</i>-methacrylic acid) (PMMA-MA). We injected the sensor nanoparticles into the gastrovascular system of intact colony fractions of reef-building tropical corals that harbor photosynthetic microalgae in their tissues. The sensor nanoparticles are excited by red LED light (617 nm) and emit in the near-infrared (780 nm), which enhances the transmission of excitation and emission light through biological materials. This enabled us to map the internal O<sub>2</sub> concentration via time-domain luminescence lifetime imaging through the outer tissue layers across several coral polyps in flowing seawater. After injection, nanoparticles dispersed within the coral tissue for several hours. While luminescence intensity imaging showed some local aggregation of sensor particles, lifetime imaging showed a more homogeneous O<sub>2</sub> distribution across a larger area of the coral colony. Local stimulation of symbiont photosynthesis in corals induced oxygenation of illuminated tissue areas and formation of lateral O<sub>2</sub> gradients toward surrounding respiring tissues, which were dissipated rapidly after the onset of darkness. Such measurements are key to improving our understanding of how corals regulate their internal chemical microenvironment and metabolic activity, and how they are affected by environmental stress such as ocean warming, acidification, and deoxygenation. Our experimental approach can also be adapted for <i>in vivo</i> O<sub>2</sub> imaging in other natural systems such as biofilms, plant and animal tissues, as well as in organoids and other cell constructs, where imaging internal O<sub>2</sub> conditions are relevant and challenging due to high optical density and background fluorescence.</p>","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11443520/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142045953","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}
Pub Date : 2024-09-27Epub Date: 2024-08-15DOI: 10.1021/acssensors.4c01057
Justine Coïs, Marie-Laure Niepon, Manon Wittwer, Hessam Sepasi Tehrani, Philippe Bun, Jean-Maurice Mallet, Vincent Vialou, Blaise Dumat
Fluorescent protein-based pH biosensors enable the tracking of pH changes during protein trafficking and, in particular, exocytosis. The recent development of chemogenetic reporters combining synthetic fluorophores with self-labeling protein tags offers a versatile alternative to fluorescent proteins that combines the diversity of chemical probes and indicators with the selectivity of the genetic encoding. However, this hybrid protein labeling strategy does not avoid common drawbacks of organic fluorophores such as the risk of off-target signal due to unbound molecules. Here, we describe a novel fluorogenic and chemogenetic pH sensor based on a cell-permeable molecular pH indicator called pHluo-Halo-1, whose fluorescence can be locally activated in cells by reaction with HaloTag, ensuring excellent signal selectivity in wash-free imaging experiments. pHluo-Halo-1 was selected out of a series of four fluorogenic molecular rotor structures based on protein chromophore analogues. It displays good pH sensitivity with a pKa of 6.3 well-suited to monitor pH variations during exocytosis and an excellent labeling selectivity in cells. It was applied to follow the secretion of CD63-HaloTag fusion proteins using TIRF microscopy. We anticipate that this strategy based on the combination of a tunable and chemically accessible fluorogenic probe with a well-established protein tag will open new possibilities for the development of versatile alternatives to fluorescent proteins for elucidating the dynamics and regulatory mechanisms of proteins in living cells.
{"title":"A Fluorogenic Chemogenetic pH Sensor for Imaging Protein Exocytosis.","authors":"Justine Coïs, Marie-Laure Niepon, Manon Wittwer, Hessam Sepasi Tehrani, Philippe Bun, Jean-Maurice Mallet, Vincent Vialou, Blaise Dumat","doi":"10.1021/acssensors.4c01057","DOIUrl":"10.1021/acssensors.4c01057","url":null,"abstract":"<p><p>Fluorescent protein-based pH biosensors enable the tracking of pH changes during protein trafficking and, in particular, exocytosis. The recent development of chemogenetic reporters combining synthetic fluorophores with self-labeling protein tags offers a versatile alternative to fluorescent proteins that combines the diversity of chemical probes and indicators with the selectivity of the genetic encoding. However, this hybrid protein labeling strategy does not avoid common drawbacks of organic fluorophores such as the risk of off-target signal due to unbound molecules. Here, we describe a novel fluorogenic and chemogenetic pH sensor based on a cell-permeable molecular pH indicator called <b>pHluo-Halo-1</b>, whose fluorescence can be locally activated in cells by reaction with HaloTag, ensuring excellent signal selectivity in wash-free imaging experiments. <b>pHluo-Halo-1</b> was selected out of a series of four fluorogenic molecular rotor structures based on protein chromophore analogues. It displays good pH sensitivity with a p<i>K</i><sub>a</sub> of 6.3 well-suited to monitor pH variations during exocytosis and an excellent labeling selectivity in cells. It was applied to follow the secretion of CD63-HaloTag fusion proteins using TIRF microscopy. We anticipate that this strategy based on the combination of a tunable and chemically accessible fluorogenic probe with a well-established protein tag will open new possibilities for the development of versatile alternatives to fluorescent proteins for elucidating the dynamics and regulatory mechanisms of proteins in living cells.</p>","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141981164","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}
Pub Date : 2024-09-26DOI: 10.1021/acssensors.4c00788
Michele Segantini, Gianluca Marcozzi, Tarek Elrifai, Ekaterina Shabratova, Katja Höflich, Mihaela Deaconeasa, Volker Niemann, Rainer Pietig, Joseph E. McPeak, Jens Anders, Boris Naydenov, Klaus Lips
Electron paramagnetic resonance (EPR) spectroscopy provides information about the physical and chemical properties of materials by detecting paramagnetic states. Conventional EPR measurements are performed in high Q resonator using large electromagnets which limits the available space for operando experiments. Here we present a solution toward a portable EPR sensor based on the combination of the EPR-on-a-Chip (EPRoC) and a single-sided permanent magnet. This device can be placed directly into the sample environment (i.e., catalytic reaction vessels, ultrahigh vacuum deposition chambers, aqueous environments, etc.) to conduct in situ and operando measurements. The EPRoC reported herein is comprised of an array of 14 voltage-controlled oscillator (VCO) coils oscillating at 7 GHz. By using a single grain of crystalline BDPA, EPR measurements at different positions of the magnet with respect to the VCO array were performed. It was possible to create a 2D spatial map of a 1.5 mm × 5 mm region of the magnetic field with 50 μm resolution. This allowed for the determination of the magnetic field intensity and homogeneity, which are found to be 254.69 mT and 700 ppm, respectively. The magnetic field was mapped also along the vertical direction using a thin film a-Si layer. The EPRoC and permanent magnet were combined to form a miniaturized EPR spectrometer to perform experiments on tempol (4-hydroxy-2,2,6,6-teramethylpiperidin-1-oxyl) dissolved in an 80% glycerol and 20% water solution. It was possible to determine the molecular tumbling correlation time and to establish a calibration procedure to quantify the number of spins within the sample.
{"title":"Compact Electron Paramagnetic Resonance on a Chip Spectrometer Using a Single Sided Permanent Magnet","authors":"Michele Segantini, Gianluca Marcozzi, Tarek Elrifai, Ekaterina Shabratova, Katja Höflich, Mihaela Deaconeasa, Volker Niemann, Rainer Pietig, Joseph E. McPeak, Jens Anders, Boris Naydenov, Klaus Lips","doi":"10.1021/acssensors.4c00788","DOIUrl":"https://doi.org/10.1021/acssensors.4c00788","url":null,"abstract":"Electron paramagnetic resonance (EPR) spectroscopy provides information about the physical and chemical properties of materials by detecting paramagnetic states. Conventional EPR measurements are performed in high <i>Q</i> resonator using large electromagnets which limits the available space for operando experiments. Here we present a solution toward a portable EPR sensor based on the combination of the EPR-on-a-Chip (EPRoC) and a single-sided permanent magnet. This device can be placed directly into the sample environment (i.e., catalytic reaction vessels, ultrahigh vacuum deposition chambers, aqueous environments, etc.) to conduct in situ and operando measurements. The EPRoC reported herein is comprised of an array of 14 voltage-controlled oscillator (VCO) coils oscillating at 7 GHz. By using a single grain of crystalline BDPA, EPR measurements at different positions of the magnet with respect to the VCO array were performed. It was possible to create a 2D spatial map of a 1.5 mm × 5 mm region of the magnetic field with 50 μm resolution. This allowed for the determination of the magnetic field intensity and homogeneity, which are found to be 254.69 mT and 700 ppm, respectively. The magnetic field was mapped also along the vertical direction using a thin film a-Si layer. The EPRoC and permanent magnet were combined to form a miniaturized EPR spectrometer to perform experiments on tempol (4-hydroxy-2,2,6,6-teramethylpiperidin-1-oxyl) dissolved in an 80% glycerol and 20% water solution. It was possible to determine the molecular tumbling correlation time and to establish a calibration procedure to quantify the number of spins within the sample.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325721","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}
Pub Date : 2024-09-25DOI: 10.1021/acssensors.4c01467
Minhui Liang, Li Liang, Mahnoush Tayebi, Jianwei Zhong, Ye Ai
Droplet microfluidic systems have emerged as indispensable and advanced tools in contemporary biological science. A prominent example is the droplet digital polymerase chain reaction (ddPCR), which plays a pivotal role in next-generation sequencing and the detection of rare nucleic acids or mutations. However, existing optical detection configurations are bulky, intricate, and costly, and require meticulous optical alignment to optimize fluorescence sensing. Herein, we propose a lab-in-fiber optofluidic system (LiFO), which provides a stable and compact footprint, self-alignment, and enhanced optical coupling for high-accuracy ddPCR. Moreover, LiFO could expand its capabilities for multiangle-scattering light collection in which we collect focused forward-scattering light (fFSL) to enable real-time droplet counting and size monitoring. To accomplish these attributes, LiFO incorporates optical fibers, along with fabricated PDMS grooves, for a self-aligned optical setup to implement simultaneous fluorescence and scattering detection. Furthermore, LiFO harnesses the concept of flowing droplets functioning as microlenses, which allows us to collect and translate fFSL signals into droplet size information. We have demonstrated the effectiveness of LiFO in ddPCR applications, illustrating its capacity to enhance the accuracy and precision of DNA quantification. Notably, LiFO exhibits improved linearity in the measurement of serial DNA dilutions, reflected by an increase in R2 from 0.956 to 0.997. These results demonstrate the potential of LiFO to serve as a valuable tool across a wide spectrum of droplet microfluidic platforms, offering opportunities for advancement in practical applications.
{"title":"Lab-In-Fiber Optofluidic Device for Droplet Digital Polymerase Chain Reaction (DdPCR) with Real-Time Monitoring","authors":"Minhui Liang, Li Liang, Mahnoush Tayebi, Jianwei Zhong, Ye Ai","doi":"10.1021/acssensors.4c01467","DOIUrl":"https://doi.org/10.1021/acssensors.4c01467","url":null,"abstract":"Droplet microfluidic systems have emerged as indispensable and advanced tools in contemporary biological science. A prominent example is the droplet digital polymerase chain reaction (ddPCR), which plays a pivotal role in next-generation sequencing and the detection of rare nucleic acids or mutations. However, existing optical detection configurations are bulky, intricate, and costly, and require meticulous optical alignment to optimize fluorescence sensing. Herein, we propose a lab-in-fiber optofluidic system (LiFO), which provides a stable and compact footprint, self-alignment, and enhanced optical coupling for high-accuracy ddPCR. Moreover, LiFO could expand its capabilities for multiangle-scattering light collection in which we collect focused forward-scattering light (fFSL) to enable real-time droplet counting and size monitoring. To accomplish these attributes, LiFO incorporates optical fibers, along with fabricated PDMS grooves, for a self-aligned optical setup to implement simultaneous fluorescence and scattering detection. Furthermore, LiFO harnesses the concept of flowing droplets functioning as microlenses, which allows us to collect and translate fFSL signals into droplet size information. We have demonstrated the effectiveness of LiFO in ddPCR applications, illustrating its capacity to enhance the accuracy and precision of DNA quantification. Notably, LiFO exhibits improved linearity in the measurement of serial DNA dilutions, reflected by an increase in <i>R</i><sup>2</sup> from 0.956 to 0.997. These results demonstrate the potential of LiFO to serve as a valuable tool across a wide spectrum of droplet microfluidic platforms, offering opportunities for advancement in practical applications.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321016","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}
Pub Date : 2024-09-25DOI: 10.1021/acssensors.4c01763
Changyu Tian, Seyoung Shin, Youngwook Cho, Youngho Song, Soo-Yeon Cho
Optical nanosensors, including single-walled carbon nanotubes (SWCNTs), provide real-time spatiotemporal reporting at the single-molecule level within a nanometer-scale area. However, their superior sensitivity also makes them susceptible to slight environmental influences such as reference analytes in media, external fluid flow, and mechanical modulations. Consequently, they often fail to achieve the optimal limit of detection (LOD) and frequently convey misinformation spatiotemporally. To address this challenge, we developed a single-pixel mapping technique for optical nanosensor arrays that operates with high spatiotemporal precision using machine learning. We systematically measured the spatial sensing images of various analyte concentrations below the LOD by using a near-infrared (nIR) fluorescent SWCNT nanosensor array. For dopamine (DA) as an example analyte, we extracted single-pixel level sensing features such as entropy, the Laplacian operator, and neighboring values under noise levels. We then trained the artificial intelligence (AI) model to accurately identify specific reaction pixels of the nanosensor array, even below the LOD region. Additionally, our method can distinguish subtle noise caused by fluid in the media or mechanical modulation of the array substrate. As a result, our approach significantly improved the detection sensitivity of the nanosensor array, achieving a 13-fold increase over the original LOD and halving the detection time of the reporter pixels, with F1 scores exceeding 0.9. This method not only lowers the LOD of optical nanosensors but also isolates sensor responses specific to the analyte, providing accurate spatiotemporal information to the user, even in noisy conditions. It can be universally applied to various optical nanosensor materials and analytes, maximizing the sensitivity and accuracy of the nanosensors used in diagnostics and analysis.
{"title":"High Spatiotemporal Precision Mapping of Optical Nanosensor Array Using Machine Learning","authors":"Changyu Tian, Seyoung Shin, Youngwook Cho, Youngho Song, Soo-Yeon Cho","doi":"10.1021/acssensors.4c01763","DOIUrl":"https://doi.org/10.1021/acssensors.4c01763","url":null,"abstract":"Optical nanosensors, including single-walled carbon nanotubes (SWCNTs), provide real-time spatiotemporal reporting at the single-molecule level within a nanometer-scale area. However, their superior sensitivity also makes them susceptible to slight environmental influences such as reference analytes in media, external fluid flow, and mechanical modulations. Consequently, they often fail to achieve the optimal limit of detection (LOD) and frequently convey misinformation spatiotemporally. To address this challenge, we developed a single-pixel mapping technique for optical nanosensor arrays that operates with high spatiotemporal precision using machine learning. We systematically measured the spatial sensing images of various analyte concentrations below the LOD by using a near-infrared (nIR) fluorescent SWCNT nanosensor array. For dopamine (DA) as an example analyte, we extracted single-pixel level sensing features such as entropy, the Laplacian operator, and neighboring values under noise levels. We then trained the artificial intelligence (AI) model to accurately identify specific reaction pixels of the nanosensor array, even below the LOD region. Additionally, our method can distinguish subtle noise caused by fluid in the media or mechanical modulation of the array substrate. As a result, our approach significantly improved the detection sensitivity of the nanosensor array, achieving a 13-fold increase over the original LOD and halving the detection time of the reporter pixels, with F1 scores exceeding 0.9. This method not only lowers the LOD of optical nanosensors but also isolates sensor responses specific to the analyte, providing accurate spatiotemporal information to the user, even in noisy conditions. It can be universally applied to various optical nanosensor materials and analytes, maximizing the sensitivity and accuracy of the nanosensors used in diagnostics and analysis.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317514","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}
Disease diagnosis of Helicobacter pylori (Hp) through human exhaled breath analysis has attracted considerable attention. However, conventional methods, such as carbon 13 (13C) breath test and infrared spectrometers, are facing the challenge of achieving portability and reliability synchronously. Herein, we report a portable and hand-held Hp analyzer using a bimetallic PtRu@SnO2-based gas sensor for the prediagnosis of Hp infection, which is based on detecting ammonia (NH3) as a potential biomarker in exhaled breath. Owing to the surface functionalization through highly catalytically active bimetallic PtRu nanoparticles (NPs) prepared by a photochemical reduction strategy, the PtRu@SnO2-based sensor exhibits high sensitivity and selectivity toward trace-level (200 ppb) NH3 even at high-humidity surroundings (80% RH). Consequently, the designed portable and hand-held Hp analyzer makes the accurate determination of NH3 at 800 ppb in exhaled breath. The tuning of energy band structure and electrical characteristics and the catalytic modulation of NH3 oxidation by PtRu NPs are proposed to be the reasons behind the enhanced NH3 gas-sensing performance, as confirmed by in situ analysis using an online MKS MultiGas 2030 FTIR gas analyzer. This work paves the way for the prediagnosis of Hp infection using a metal oxide gas sensor.
通过人体呼出气体分析诊断幽门螺旋杆菌(Hp)疾病已引起广泛关注。然而,碳 13(13C)呼气测试和红外光谱仪等传统方法在实现便携性和可靠性同步方面面临挑战。在此,我们报告了一种使用基于双金属 PtRu@SnO2 的气体传感器的便携式手持 Hp 分析仪,该分析仪以检测呼出气体中的潜在生物标记物氨(NH3)为基础,用于 Hp 感染的预诊断。由于通过光化学还原策略制备的高催化活性双金属铂钌纳米粒子(NPs)进行了表面功能化,即使在高湿度环境(80% RH)下,基于铂钌@二氧化锰的传感器也能对痕量(200 ppb)NH3表现出高灵敏度和高选择性。因此,所设计的便携式和手持式 Hp 分析仪能准确测定呼出气体中 800 ppb 的 NH3。通过使用在线 MKS MultiGas 2030 傅立叶变换红外气体分析仪进行现场分析,证实了 PtRu NPs 能带结构和电学特性的调整以及对 NH3 氧化的催化调制是 NH3 气体传感性能增强的原因。这项工作为利用金属氧化物气体传感器对 Hp 感染进行预先诊断铺平了道路。
{"title":"Portable and Hand-Held Ammonia Gas Sensor Enables Noninvasive Prediagnosis of Helicobacter pylori Infection.","authors":"Hanlin Wu,Dan Li,Ji Liu,Xueqin Gong,Tong Wang,Liupeng Zhao,Tianshuang Wang,Xu Yan,Fangmeng Liu,Peng Sun,Geyu Lu","doi":"10.1021/acssensors.4c01609","DOIUrl":"https://doi.org/10.1021/acssensors.4c01609","url":null,"abstract":"Disease diagnosis of Helicobacter pylori (Hp) through human exhaled breath analysis has attracted considerable attention. However, conventional methods, such as carbon 13 (13C) breath test and infrared spectrometers, are facing the challenge of achieving portability and reliability synchronously. Herein, we report a portable and hand-held Hp analyzer using a bimetallic PtRu@SnO2-based gas sensor for the prediagnosis of Hp infection, which is based on detecting ammonia (NH3) as a potential biomarker in exhaled breath. Owing to the surface functionalization through highly catalytically active bimetallic PtRu nanoparticles (NPs) prepared by a photochemical reduction strategy, the PtRu@SnO2-based sensor exhibits high sensitivity and selectivity toward trace-level (200 ppb) NH3 even at high-humidity surroundings (80% RH). Consequently, the designed portable and hand-held Hp analyzer makes the accurate determination of NH3 at 800 ppb in exhaled breath. The tuning of energy band structure and electrical characteristics and the catalytic modulation of NH3 oxidation by PtRu NPs are proposed to be the reasons behind the enhanced NH3 gas-sensing performance, as confirmed by in situ analysis using an online MKS MultiGas 2030 FTIR gas analyzer. This work paves the way for the prediagnosis of Hp infection using a metal oxide gas sensor.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325142","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}
Pub Date : 2024-09-25DOI: 10.1021/acssensors.4c00848
Gregory S. McCarty, Carl J. Meunier, Leslie A. Sombers
Carbon–fiber microelectrodes are proven and powerful sensors for electroanalytical measurements in a variety of environments, including complex systems such as the brain. They are used to detect and quantify a range of biological molecules, including neuropeptides, which are of broad interest for understanding physiological function. The enkephalins (met- and leu-) are endogenous opioid peptides that are involved in both pain and motivated behavior. Each is comprised of only five amino acids including tyrosine, an electroactive species. Electroanalytical measurements targeting tyrosine can reveal the dynamics of endogenous enkephalin transients in live tissue. However, when using electrochemistry in a biological system, selectivity is always a concern. Many larger neuropeptides also contain tyrosine. As such, they could generate a redox signature similar to that of the enkephalins, potentially confounding the measurement. In this work, three distinctly sized dioxythiophene monomers were mixed with Nafion and electrodeposited onto cylindrical carbon–fiber microelectrodes to form composite polymer films that allow for the tunable, size-based exclusion of larger molecules. The dioxythiophene monomers 3,4-ethylenedioxythiophene (EDOT), 3,4-propylenedioxythiophene (ProDOT), and 3,4-(2′,2′-diethylpropylene) dioxythiophene (ProDOT-Et2) were used to create nanostructured pores of increasing size. The dioxythiophene/Nafion modified electrodes were characterized in the voltammetric detection of dopamine, a classic small molecule neurotransmitter, and a series of tyrosine containing neuropeptides of increasing size: met-enkephalin (M-ENK; 5 residues), oxytocin (OXY; 9 residues), neurotensin (NT; 13 residues), and neuropeptide Y (NPY; 36 residues). The modified electrodes exhibited enhanced selectivity for smaller peptide species over larger peptides in a manner consistent with the size of the dioxythiophene monomer incorporated into the polymeric film, allowing for tunability in terms of size-based selective detection.
{"title":"Dioxythiophene/Nafion Polymer Composite Membranes for Tunable Size-Based Selectivity in the Voltammetric Detection of Small Neuropeptides","authors":"Gregory S. McCarty, Carl J. Meunier, Leslie A. Sombers","doi":"10.1021/acssensors.4c00848","DOIUrl":"https://doi.org/10.1021/acssensors.4c00848","url":null,"abstract":"Carbon–fiber microelectrodes are proven and powerful sensors for electroanalytical measurements in a variety of environments, including complex systems such as the brain. They are used to detect and quantify a range of biological molecules, including neuropeptides, which are of broad interest for understanding physiological function. The enkephalins (met- and leu-) are endogenous opioid peptides that are involved in both pain and motivated behavior. Each is comprised of only five amino acids including tyrosine, an electroactive species. Electroanalytical measurements targeting tyrosine can reveal the dynamics of endogenous enkephalin transients in live tissue. However, when using electrochemistry in a biological system, selectivity is always a concern. Many larger neuropeptides also contain tyrosine. As such, they could generate a redox signature similar to that of the enkephalins, potentially confounding the measurement. In this work, three distinctly sized dioxythiophene monomers were mixed with Nafion and electrodeposited onto cylindrical carbon–fiber microelectrodes to form composite polymer films that allow for the tunable, size-based exclusion of larger molecules. The dioxythiophene monomers 3,4-ethylenedioxythiophene (EDOT), 3,4-propylenedioxythiophene (ProDOT), and 3,4-(2′,2′-diethylpropylene) dioxythiophene (ProDOT-Et<sub>2</sub>) were used to create nanostructured pores of increasing size. The dioxythiophene/Nafion modified electrodes were characterized in the voltammetric detection of dopamine, a classic small molecule neurotransmitter, and a series of tyrosine containing neuropeptides of increasing size: met-enkephalin (M-ENK; 5 residues), oxytocin (OXY; 9 residues), neurotensin (NT; 13 residues), and neuropeptide Y (NPY; 36 residues). The modified electrodes exhibited enhanced selectivity for smaller peptide species over larger peptides in a manner consistent with the size of the dioxythiophene monomer incorporated into the polymeric film, allowing for tunability in terms of size-based selective detection.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317516","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}
Pub Date : 2024-09-25DOI: 10.1021/acssensors.4c01403
Jiang Liu,Chenhua Han,Jiawang Chen,Liwen Nan,Yulin Si
The development of all-solid-state precise pH electrodes holds significant importance in various fields, particularly in marine scientific research. To achieve this goal, we proposed a novel fabrication technique for an all-solid-state ruthenium oxide (Ti/RuOx) pH electrode. We thin-coated the RuCl3 precursor solution on a titanium wire substrate using a heat gun repeatedly and then calcined it in a mixture of Li2CO3 and Na2O2 at 400 °C to obtain a ruthenium oxide (RuOx) film. This RuOx film was subjected to acid treatment with dilute nitric acid, and a polytetrafluoroethylene heat shrink tube was wrapped around the non-RuOx film area. Finally, the RuOx film was fully immersed in a pH 4.00 buffer solution, finalizing the electrode preparation. The RuOx film exhibits a dense and regular conical morphology. The Ti/RuOx electrode demonstrates a good near-Nernstian response slope (e.g., -59.04 mV/pH at 25 °C), high linearity (e.g., R2 = 0.9999), rapid response (<1 s), low hysteresis (<3 mV), excellent reversibility, and good repeatability in the pH range of 2.00-10.00. After full hydration, the Ti/RuOx electrode shows a potential drift of 8.5 mV and a drift rate of approximately 0.27 mV/day over a period of 25 days, indicating good long-term stability. Furthermore, the Ti/RuOx electrode exhibits robust resistance against interference from various ions and low-concentration redox substances, ensuring a long storage life (at least 280 days), and high measurement accuracy (e.g., ± 0.02 pH units) for diverse water samples, including seawater, freshwater, and tap water. This study has evaluated the potential of the Ti/RuOx electrode as a reliable and accurate tool for pH measurements in marine scientific applications.
{"title":"An All-Solid-State Ti/RuOx pH Electrode Prepared Based on the Thermal Oxidation Method.","authors":"Jiang Liu,Chenhua Han,Jiawang Chen,Liwen Nan,Yulin Si","doi":"10.1021/acssensors.4c01403","DOIUrl":"https://doi.org/10.1021/acssensors.4c01403","url":null,"abstract":"The development of all-solid-state precise pH electrodes holds significant importance in various fields, particularly in marine scientific research. To achieve this goal, we proposed a novel fabrication technique for an all-solid-state ruthenium oxide (Ti/RuOx) pH electrode. We thin-coated the RuCl3 precursor solution on a titanium wire substrate using a heat gun repeatedly and then calcined it in a mixture of Li2CO3 and Na2O2 at 400 °C to obtain a ruthenium oxide (RuOx) film. This RuOx film was subjected to acid treatment with dilute nitric acid, and a polytetrafluoroethylene heat shrink tube was wrapped around the non-RuOx film area. Finally, the RuOx film was fully immersed in a pH 4.00 buffer solution, finalizing the electrode preparation. The RuOx film exhibits a dense and regular conical morphology. The Ti/RuOx electrode demonstrates a good near-Nernstian response slope (e.g., -59.04 mV/pH at 25 °C), high linearity (e.g., R2 = 0.9999), rapid response (<1 s), low hysteresis (<3 mV), excellent reversibility, and good repeatability in the pH range of 2.00-10.00. After full hydration, the Ti/RuOx electrode shows a potential drift of 8.5 mV and a drift rate of approximately 0.27 mV/day over a period of 25 days, indicating good long-term stability. Furthermore, the Ti/RuOx electrode exhibits robust resistance against interference from various ions and low-concentration redox substances, ensuring a long storage life (at least 280 days), and high measurement accuracy (e.g., ± 0.02 pH units) for diverse water samples, including seawater, freshwater, and tap water. This study has evaluated the potential of the Ti/RuOx electrode as a reliable and accurate tool for pH measurements in marine scientific applications.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325105","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}
Pub Date : 2024-09-24DOI: 10.1021/acssensors.4c01599
Yeong Jae Kim, Seonyong Lee, Sungkyun Choi, Tae Hoon Eom, Sung Hwan Cho, Sohyeon Park, Sung Hyuk Park, Jae Young Kim, Jaehyun Kim, Gi Baek Nam, Jung-El Ryu, Seon Ju Park, Soo Min Lee, Gun-Do Lee, Jihyun Kim, Ho Won Jang
Hydrogen (H2) is a promising alternative energy source for Net-zero, but the risk of explosion requires accurate and rapid detection systems. As the use of H2 energy expands, sensors require high performance in a variety of properties. Palladium (Pd) is an attractive material for H2 detection due to its high H2 affinity and catalytic properties. However, poor stability caused by volume changes and reliability due to environmental sensitivity remain obstacles. This study proposes a micropatterned thin film of PdAu with optimized composition (Pd0.62Au0.38) as a chemoresistive sensor to overcome these issues. At room temperature, the sensor has a wide detection range of 0.0002% to 5% and a fast response time of 9.5 s. Significantly, the sensor exhibits excellent durability for repeated operation (>35 h) in 5% H2 and resistance to humidity and carbon monoxide. We also report a negative resistivity change in PdAu, which is opposite to that of Pd. Density functional theory (DFT) calculations were performed to investigate the resistance change. DFT analysis revealed that H2 penetrates specific interstitial sites, causing partial lattice compression. The lattice compression causes a decrease in electrical resistance. This work is expected to contribute to the development of high-performance H2 sensors using Pd-based alloys.
{"title":"Highly Durable Chemoresistive Micropatterned PdAu Hydrogen Sensors: Performance and Mechanism.","authors":"Yeong Jae Kim, Seonyong Lee, Sungkyun Choi, Tae Hoon Eom, Sung Hwan Cho, Sohyeon Park, Sung Hyuk Park, Jae Young Kim, Jaehyun Kim, Gi Baek Nam, Jung-El Ryu, Seon Ju Park, Soo Min Lee, Gun-Do Lee, Jihyun Kim, Ho Won Jang","doi":"10.1021/acssensors.4c01599","DOIUrl":"10.1021/acssensors.4c01599","url":null,"abstract":"<p><p>Hydrogen (H<sub>2</sub>) is a promising alternative energy source for Net-zero, but the risk of explosion requires accurate and rapid detection systems. As the use of H<sub>2</sub> energy expands, sensors require high performance in a variety of properties. Palladium (Pd) is an attractive material for H<sub>2</sub> detection due to its high H<sub>2</sub> affinity and catalytic properties. However, poor stability caused by volume changes and reliability due to environmental sensitivity remain obstacles. This study proposes a micropatterned thin film of PdAu with optimized composition (Pd<sub>0.62</sub>Au<sub>0.38</sub>) as a chemoresistive sensor to overcome these issues. At room temperature, the sensor has a wide detection range of 0.0002% to 5% and a fast response time of 9.5 s. Significantly, the sensor exhibits excellent durability for repeated operation (>35 h) in 5% H<sub>2</sub> and resistance to humidity and carbon monoxide. We also report a negative resistivity change in PdAu, which is opposite to that of Pd. Density functional theory (DFT) calculations were performed to investigate the resistance change. DFT analysis revealed that H<sub>2</sub> penetrates specific interstitial sites, causing partial lattice compression. The lattice compression causes a decrease in electrical resistance. This work is expected to contribute to the development of high-performance H<sub>2</sub> sensors using Pd-based alloys.</p>","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.2,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306531","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}
MXene-based conductive hydrogels hold significant promise as epidermal sensors, yet their susceptibility to oxidation represents a formidable limitation. This study addresses this challenge by incorporating MXene into a tannic acid (TA) cross-linked silk fibroin matrix. The resulting conductive hydrogel (denoted as e-dive) exhibits favorable characteristics such as adjustable mechanical properties, self-healing capabilities (both mechanically and electrically), and strong underwater adhesion. The existence of a percolation network of MXene within the nanocomposites guarantees good electrical conductivity. Importantly, the surface interaction of MXene nanosheets with the hydrophobic moiety from TA substantially reduced moisture and oxygen interactions with MXene, thereby effectively mitigating MXene oxidation within hydrogel matrices. This preservation of the electrical characteristics ensures prolonged functional stability. Furthermore, the e-dive demonstrates inherent antibacterial properties, making it suitable for use in underwater environments where bacterial contamination is a concern. The utilization of this advanced e-dive system extends to the correction of diving postures and the facilitation of underwater healthcare and security alerts. Our study presents a robust methodology for enhancing the stability of MXene-based conductive hydrogel electronics, thereby expanding their scope of potential applications.
{"title":"Tannic Acid-Enabled Antioxidant and Stretchable MXene/Silk Strain Sensors for Diving Training Healthcare","authors":"Xiao-Xue Wang, Chen-Yu Wang, Meng Yin, Ke-Zheng Chen, Sheng-Lin Qiao","doi":"10.1021/acssensors.4c01091","DOIUrl":"https://doi.org/10.1021/acssensors.4c01091","url":null,"abstract":"MXene-based conductive hydrogels hold significant promise as epidermal sensors, yet their susceptibility to oxidation represents a formidable limitation. This study addresses this challenge by incorporating MXene into a tannic acid (TA) cross-linked silk fibroin matrix. The resulting conductive hydrogel (denoted as <b>e-dive</b>) exhibits favorable characteristics such as adjustable mechanical properties, self-healing capabilities (both mechanically and electrically), and strong underwater adhesion. The existence of a percolation network of MXene within the nanocomposites guarantees good electrical conductivity. Importantly, the surface interaction of MXene nanosheets with the hydrophobic moiety from TA substantially reduced moisture and oxygen interactions with MXene, thereby effectively mitigating MXene oxidation within hydrogel matrices. This preservation of the electrical characteristics ensures prolonged functional stability. Furthermore, the <b>e-dive</b> demonstrates inherent antibacterial properties, making it suitable for use in underwater environments where bacterial contamination is a concern. The utilization of this advanced <b>e-dive</b> system extends to the correction of diving postures and the facilitation of underwater healthcare and security alerts. Our study presents a robust methodology for enhancing the stability of MXene-based conductive hydrogel electronics, thereby expanding their scope of potential applications.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":null,"pages":null},"PeriodicalIF":8.9,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313907","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}