ACS Measurement Science Au最新文献

{"title":"Unraveling the Impact of Polyethylenimine-Coated Gold Nanoparticle Size on the Efficiency of Sandwich-Style Electrochemical Immunosensors","authors":"Thitirat Putnin,&nbsp;Supakeit Chanarsa,&nbsp;Patrawadee Yaiwong,&nbsp;Aroonsri Ngamaroonchote,&nbsp;Noppadol Aroonyadet,&nbsp;Jaroon Jakmunee,&nbsp;Suwussa Bamrungsap,&nbsp;Rawiwan Laocharoensuk and Kontad Ounnunkad*,&nbsp;","doi":"10.1021/acsmeasuresciau.4c0007510.1021/acsmeasuresciau.4c00075","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00075https://doi.org/10.1021/acsmeasuresciau.4c00075","url":null,"abstract":"<p >Sometimes, smaller size is not always better, and looking for nanomaterials that offer better device performance requires consideration of their properties at the first stage. In this study, the effects of the size of polyethylenimine-capped AuNPs (PEI-AuNPs) and proteins on the immunosensor performances, namely, sensitivity and limit of detection, are examined. The size-effect investigation of PEI-AuNPs involves their modification on the surface of disposable screen-printed carbon electrodes to support primary antibodies and their ability to load secondary antibodies and redox probes to perform amplification in the immunosensor. The correlation of the average size, electrochemical activities, protein size, and device property of PEI-AuNPs is investigated. The synthesized PEI-AuNPs with different average diameters ranging from 4.7 to 44.9 nm are employed for the investigation. When the sensor surface forms a sandwich architecture, the detection employs the current response of Ag⁺ ions on the PEI-AuNPs bioconjugate, which greatly increases by increasing the protein concentration. In addition, the best electrochemical signal of PEI-AuNPs or their antibody complexes with a unique AuNPs’ average size allows superior signal amplification. The effect of using different sizes of target proteins on their devices is not significantly observed. Although in general small-sized nanomaterials offer high active surface areas, which can improve the electrode surface, reactivity, and device performance, we observe that the medium size of PEI-AuNPs (16.3 nm) gives the best sensitivity and detection limit of this sensor type. Therefore, the finding is useful for considering and optimizing their sizes for tunable voltammetric properties and acquiring a superior sensor.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"96–108 96–108"},"PeriodicalIF":4.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling the Impact of Polyethylenimine-Coated Gold Nanoparticle Size on the Efficiency of Sandwich-Style Electrochemical Immunosensors.","authors":"Thitirat Putnin, Supakeit Chanarsa, Patrawadee Yaiwong, Aroonsri Ngamaroonchote, Noppadol Aroonyadet, Jaroon Jakmunee, Suwussa Bamrungsap, Rawiwan Laocharoensuk, Kontad Ounnunkad","doi":"10.1021/acsmeasuresciau.4c00075","DOIUrl":"10.1021/acsmeasuresciau.4c00075","url":null,"abstract":"<p><p>Sometimes, smaller size is not always better, and looking for nanomaterials that offer better device performance requires consideration of their properties at the first stage. In this study, the effects of the size of polyethylenimine-capped AuNPs (PEI-AuNPs) and proteins on the immunosensor performances, namely, sensitivity and limit of detection, are examined. The size-effect investigation of PEI-AuNPs involves their modification on the surface of disposable screen-printed carbon electrodes to support primary antibodies and their ability to load secondary antibodies and redox probes to perform amplification in the immunosensor. The correlation of the average size, electrochemical activities, protein size, and device property of PEI-AuNPs is investigated. The synthesized PEI-AuNPs with different average diameters ranging from 4.7 to 44.9 nm are employed for the investigation. When the sensor surface forms a sandwich architecture, the detection employs the current response of Ag⁺ ions on the PEI-AuNPs bioconjugate, which greatly increases by increasing the protein concentration. In addition, the best electrochemical signal of PEI-AuNPs or their antibody complexes with a unique AuNPs' average size allows superior signal amplification. The effect of using different sizes of target proteins on their devices is not significantly observed. Although in general small-sized nanomaterials offer high active surface areas, which can improve the electrode surface, reactivity, and device performance, we observe that the medium size of PEI-AuNPs (16.3 nm) gives the best sensitivity and detection limit of this sensor type. Therefore, the finding is useful for considering and optimizing their sizes for tunable voltammetric properties and acquiring a superior sensor.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"96-108"},"PeriodicalIF":4.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11843508/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143483920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Challenges in PFAS Postdegradation Analysis: Insights from the PFAS-CTAB Model System","authors":"Chanaka Navarathna*,&nbsp;Ransford Appianin Boateng and Long Luo*,&nbsp;","doi":"10.1021/acsmeasuresciau.4c0008310.1021/acsmeasuresciau.4c00083","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00083https://doi.org/10.1021/acsmeasuresciau.4c00083","url":null,"abstract":"<p >Per- and polyfluoroalkyl substances (PFAS) are synthetic chemicals widely used for their oil and water-repellent properties. Their environmental persistence and potential health risks have raised significant concerns. As PFAS degrades through remediation or natural processes, they form complex mixtures of the original chemicals, transformation byproducts, and degradation additives. Analyzing PFAS after degradation presents analytical challenges due to possible chemical and physical interactions, including ion pairing, micelle formation, and complexation. These factors can significantly impact the precision and accuracy of PFAS measurements, yet they are often overlooked in PFAS degradation studies. In this work, we demonstrate that with the addition of ppb-level cetyltrimethylammonium bromide (CTAB), a cationic surfactant used in PFAS plasma-based degradation, the PFAS calibration curve linearity, sensitivity, and reproducibility are severely compromised. Isotopically labeled internal standards cannot fully correct these issues. Furthermore, the standard EPA methods 537.1, 533, and 1633 could not accurately recover PFAS concentrations in the PFAS and CTAB mixtures, with severe matrix effects observed for longer-chain and nitrogen-containing PFAS. Among these methods, Method 1633 is currently the most suitable option for postdegradation analysis. Method 1633 showed the lowest CTAB interference because this method used another weak ion pair additive, formic acid or acetic acid (in commercial lab analysis), to acidify the sample before LC–MS/MS analysis and added an isotopically labeled internal standard. For future PFAS degradation studies, we recommend systematically evaluating the matrix effect on the PFAS quantification using a recovery matrix to validate the analytical methods before use.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"135–144 135–144"},"PeriodicalIF":4.6,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00083","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435879","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Insights into HRP-Catalyzed Oxidation of the Near-Infrared Fluorescent Dye Sulfo-cyanine 7.","authors":"Gabriela Manrique, Jérémie Gottraux, Simon Matoori","doi":"10.1021/acsmeasuresciau.4c00080","DOIUrl":"10.1021/acsmeasuresciau.4c00080","url":null,"abstract":"<p><p>Horseradish peroxidase (HRP) is a widely used enzyme that oxidizes a range of substrates in the presence of its co-substrate hydrogen peroxide (H₂O₂). In the past, we identified sulfo-cyanine 7 (S7) as a novel near-infrared substrate of HRP, which loses its fluorescence upon enzymatic oxidation in a hydrogen peroxide-dependent manner. However, the catalytic mechanism and the chemical structure of the oxidation products were not well understood. In this study, we investigate the catalytic mechanism of S7 oxidation by HRP and identify two radical products formed during the reaction. Our results point to the formation of non-near-infrared fluorescent species, and the regeneration of S7. These results strongly point to a disproportionation reaction that was described for other HRP substrates, namely the structurally related ABTS (2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonic acid)).</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"130-134"},"PeriodicalIF":4.6,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11843493/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143484200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Challenges in PFAS Postdegradation Analysis: Insights from the PFAS-CTAB Model System.","authors":"Chanaka Navarathna, Ransford Appianin Boateng, Long Luo","doi":"10.1021/acsmeasuresciau.4c00083","DOIUrl":"10.1021/acsmeasuresciau.4c00083","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFAS) are synthetic chemicals widely used for their oil and water-repellent properties. Their environmental persistence and potential health risks have raised significant concerns. As PFAS degrades through remediation or natural processes, they form complex mixtures of the original chemicals, transformation byproducts, and degradation additives. Analyzing PFAS after degradation presents analytical challenges due to possible chemical and physical interactions, including ion pairing, micelle formation, and complexation. These factors can significantly impact the precision and accuracy of PFAS measurements, yet they are often overlooked in PFAS degradation studies. In this work, we demonstrate that with the addition of ppb-level cetyltrimethylammonium bromide (CTAB), a cationic surfactant used in PFAS plasma-based degradation, the PFAS calibration curve linearity, sensitivity, and reproducibility are severely compromised. Isotopically labeled internal standards cannot fully correct these issues. Furthermore, the standard EPA methods 537.1, 533, and 1633 could not accurately recover PFAS concentrations in the PFAS and CTAB mixtures, with severe matrix effects observed for longer-chain and nitrogen-containing PFAS. Among these methods, Method 1633 is currently the most suitable option for postdegradation analysis. Method 1633 showed the lowest CTAB interference because this method used another weak ion pair additive, formic acid or acetic acid (in commercial lab analysis), to acidify the sample before LC-MS/MS analysis and added an isotopically labeled internal standard. For future PFAS degradation studies, we recommend systematically evaluating the matrix effect on the PFAS quantification using a recovery matrix to validate the analytical methods before use.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"135-144"},"PeriodicalIF":4.6,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11843502/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143484161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Insights into HRP-Catalyzed Oxidation of the Near-Infrared Fluorescent Dye Sulfo-cyanine 7","authors":"Gabriela Manrique,&nbsp;Jérémie Gottraux and Simon Matoori*,&nbsp;","doi":"10.1021/acsmeasuresciau.4c0008010.1021/acsmeasuresciau.4c00080","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00080https://doi.org/10.1021/acsmeasuresciau.4c00080","url":null,"abstract":"<p >Horseradish peroxidase (HRP) is a widely used enzyme that oxidizes a range of substrates in the presence of its co-substrate hydrogen peroxide (H₂O₂). In the past, we identified sulfo-cyanine 7 (S7) as a novel near-infrared substrate of HRP, which loses its fluorescence upon enzymatic oxidation in a hydrogen peroxide-dependent manner. However, the catalytic mechanism and the chemical structure of the oxidation products were not well understood. In this study, we investigate the catalytic mechanism of S7 oxidation by HRP and identify two radical products formed during the reaction. Our results point to the formation of non-near-infrared fluorescent species, and the regeneration of S7. These results strongly point to a disproportionation reaction that was described for other HRP substrates, namely the structurally related ABTS (2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonic acid)).</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"130–134 130–134"},"PeriodicalIF":4.6,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00080","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143436378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single-Cell Analysis with Spatiotemporal Control of Local pH.","authors":"Kelsey Cremin, Gabriel N Meloni, Orkun S Soyer, Patrick R Unwin","doi":"10.1021/acsmeasuresciau.4c00079","DOIUrl":"10.1021/acsmeasuresciau.4c00079","url":null,"abstract":"<p><p>This work presents an experimental platform combining scanning ion conductance microscopy (SICM) with confocal laser scanning microscopy (CLSM), using intra- and extracellular pH indicator dyes to study the impact of acid delivery on individual HeLa cells within a population. The proton gradient generated by the SICM delivery is highly confined by the action of the media buffer, making the challenge local. Temporal and spatial aspects of the delivery are modeled by simulations, allowing for pH gradients across individual cells, even within a group, to be calculated. We find a strong dependency between the intracellular pH and the extracellular pH gradient imposed by local acid delivery. Postdelivery intracellular pH recovery depends on the extent of the acid challenge, with cells exposed to lower pH not returning to basal intracellular pH values after the extracellular pH recovers. This is a unique method for concentration-gradient challenge studies of cell populations that will have broad applications in cell biology. SICM can be used to deliver different chemicals and enables a wide range of local conditions to be applied across a cell population, for which the effects can be investigated at the single-cell level.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"120-129"},"PeriodicalIF":4.6,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11843512/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143483622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single-Cell Analysis with Spatiotemporal Control of Local pH","authors":"Kelsey Cremin,&nbsp;Gabriel N. Meloni,&nbsp;Orkun S. Soyer* and Patrick R. Unwin*,&nbsp;","doi":"10.1021/acsmeasuresciau.4c0007910.1021/acsmeasuresciau.4c00079","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00079https://doi.org/10.1021/acsmeasuresciau.4c00079","url":null,"abstract":"<p >This work presents an experimental platform combining scanning ion conductance microscopy (SICM) with confocal laser scanning microscopy (CLSM), using intra- and extracellular pH indicator dyes to study the impact of acid delivery on individual HeLa cells within a population. The proton gradient generated by the SICM delivery is highly confined by the action of the media buffer, making the challenge local. Temporal and spatial aspects of the delivery are modeled by simulations, allowing for pH gradients across individual cells, even within a group, to be calculated. We find a strong dependency between the intracellular pH and the extracellular pH gradient imposed by local acid delivery. Postdelivery intracellular pH recovery depends on the extent of the acid challenge, with cells exposed to lower pH not returning to basal intracellular pH values after the extracellular pH recovers. This is a unique method for concentration-gradient challenge studies of cell populations that will have broad applications in cell biology. SICM can be used to deliver different chemicals and enables a wide range of local conditions to be applied across a cell population, for which the effects can be investigated at the single-cell level.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"120–129 120–129"},"PeriodicalIF":4.6,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00079","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143436295","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coupled Thermogravimetric Analysis-Potentiometric Titration for Complex Analysis of Poly(vinyl chloride) Thermal Stability","authors":"Jonáš Uřičář*,&nbsp;Anežka Chodounská,&nbsp;Václava Benešová,&nbsp;Jiří Brožek and Radka Kalousková,&nbsp;","doi":"10.1021/acsmeasuresciau.4c0009010.1021/acsmeasuresciau.4c00090","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00090https://doi.org/10.1021/acsmeasuresciau.4c00090","url":null,"abstract":"<p >Degradation of poly(vinyl chloride) is a widely discussed topic, and its thermal stability is one of its most important properties. This work uses coupled thermogravimetric analysis-potentiometric titration for simultaneous analysis of sample weight loss and quantification of released hydrogen chloride. The thermal stability point of highly plasticized samples cannot be determined from thermogravimetric measurement alone, as the weight loss derivative change is not clearly visible. This problem is solved by the presented method, which was applied to both unplasticized and plasticized samples. The obtained data can be used to identify the thermal stability point and separate the mass loss caused by the released hydrochloric acid and by other compounds. Such data can be used in the future for determination of more precise parameters for degradation kinetics models.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"70–73 70–73"},"PeriodicalIF":4.6,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00090","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143436101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coupled Thermogravimetric Analysis-Potentiometric Titration for Complex Analysis of Poly(vinyl chloride) Thermal Stability.","authors":"Jonáš Uřičář, Anežka Chodounská, Václava Benešová, Jiří Brožek, Radka Kalousková","doi":"10.1021/acsmeasuresciau.4c00090","DOIUrl":"10.1021/acsmeasuresciau.4c00090","url":null,"abstract":"<p><p>Degradation of poly(vinyl chloride) is a widely discussed topic, and its thermal stability is one of its most important properties. This work uses coupled thermogravimetric analysis-potentiometric titration for simultaneous analysis of sample weight loss and quantification of released hydrogen chloride. The thermal stability point of highly plasticized samples cannot be determined from thermogravimetric measurement alone, as the weight loss derivative change is not clearly visible. This problem is solved by the presented method, which was applied to both unplasticized and plasticized samples. The obtained data can be used to identify the thermal stability point and separate the mass loss caused by the released hydrochloric acid and by other compounds. Such data can be used in the future for determination of more precise parameters for degradation kinetics models.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 1","pages":"70-73"},"PeriodicalIF":4.6,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11843494/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143484195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}