Pub Date : 2025-03-26DOI: 10.1016/j.aca.2025.343942
Žiga Tkalec, Štěpán Koudelka, Jana Klánová, Elliott J. Price
Background
Analyte annotation confidence in untargeted liquid chromatography mass-spectrometry (LC-MS) based chemical analysis can be enhanced by leveraging retention time information. For this, the chromatographic characteristics of the analytical system used should be well characterized. In this study, we measured 604 diverse chemical standards to characterize a dual LC setup consisting of pentabromobenzyl (PBr) and type-C silica hydride (SiH) columns operating in reversed-phase (RP) and aqueous normal-phase (ANP) mode, respectively.
Results
ANP and RP separations individually retained 40 % and 64 % of standards in cLogP range from −6.60 to 8.67 and -3.34 to 12.95, respectively. Using both columns, the coverage increased to 79 % of standards with cLogP range from -6.60 to 12.95 (median cLogP = 1.63). Retention selectivity follows the number of basic nitrogen atoms in the molecule on SiH column and polarity (cLogP) on PBr column. Column repeatability and reproducibility were tested in triplicate using a chemically diverse subset of 108 standards. Repeatability of retention times, peak widths and peak areas was 0.3 %,14 %, 4 % for SiH column and 0.2 %, 12 %, 4 % for PBr column. Similarly, reproducibility was 15 %, 34 %, 30 % for SiH column and 9 %, 18 % and 34 % for PBr column. Predictive RT models were developed based on experimental RT data, achieving R2 values of 0.92 and 0.96, with mean absolute errors of 0.29 min and 0.27 min for SiH and PBr columns, respectively.
Significance
As proof of concept, 129 metabolites were annotated in pooled human serum and plasma by matching standard or predicted RT on one or both columns. The RT models and MS2 spectra of standards are openly available, facilitating uptake of this well-characterized chromatographic system to increase confidence in analyte annotation.
{"title":"Dual LC column characterization for mass spectrometry-based small molecule profiling of human plasma and serum","authors":"Žiga Tkalec, Štěpán Koudelka, Jana Klánová, Elliott J. Price","doi":"10.1016/j.aca.2025.343942","DOIUrl":"https://doi.org/10.1016/j.aca.2025.343942","url":null,"abstract":"<h3>Background</h3>Analyte annotation confidence in untargeted liquid chromatography mass-spectrometry (LC-MS) based chemical analysis can be enhanced by leveraging retention time information. For this, the chromatographic characteristics of the analytical system used should be well characterized. In this study, we measured 604 diverse chemical standards to characterize a dual LC setup consisting of pentabromobenzyl (PBr) and type-C silica hydride (SiH) columns operating in reversed-phase (RP) and aqueous normal-phase (ANP) mode, respectively.<h3>Results</h3>ANP and RP separations individually retained 40 % and 64 % of standards in cLogP range from −6.60 to 8.67 and -3.34 to 12.95, respectively. Using both columns, the coverage increased to 79 % of standards with cLogP range from -6.60 to 12.95 (median cLogP = 1.63). Retention selectivity follows the number of basic nitrogen atoms in the molecule on SiH column and polarity (cLogP) on PBr column. Column repeatability and reproducibility were tested in triplicate using a chemically diverse subset of 108 standards. Repeatability of retention times, peak widths and peak areas was 0.3 %,14 %, 4 % for SiH column and 0.2 %, 12 %, 4 % for PBr column. Similarly, reproducibility was 15 %, 34 %, 30 % for SiH column and 9 %, 18 % and 34 % for PBr column. Predictive RT models were developed based on experimental RT data, achieving R<sup>2</sup> values of 0.92 and 0.96, with mean absolute errors of 0.29 min and 0.27 min for SiH and PBr columns, respectively.<h3>Significance</h3>As proof of concept, 129 metabolites were annotated in pooled human serum and plasma by matching standard or predicted RT on one or both columns. The RT models and MS2 spectra of standards are openly available, facilitating uptake of this well-characterized chromatographic system to increase confidence in analyte annotation.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"8 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.aca.2025.343976
Yuhang Lin , Tianshuo Wang , Yuanhao Liu , Lianxi Pu , Mingxuan Jia , Xilong Zhou , Lijun Ding , Weiran Zhu , Kun Wang
Background
Rational engineering of multienzyme system architecture is essential for achieving high-performance multi-enzyme cascade catalysis in sensing applications. In this context, the initiation step of the cascade reaction pathway plays a pivotal role in enhancing catalytic efficiency. CoFe Prussian blue analogue (CoFePBA), a dual-metal organic framework, is an ideal template for multi-enzyme design, leveraging its diverse dual-metal ion functionalities and synergistic effects. Defect engineering approaches enable the fine-tuning of catalytic properties, optimizing electron transfer and promoting reaction intermediates. Therefore, the rational design of the multienzyme system structure is critical for efficient cascade catalysis.
Results
In this study, we utilized deep eutectic solvents (DES) to selectively induce Co defects in CoFePBA (CoFePBA-DES) under mild conditions, providing more active sites and enhancing the Co2+/Co3+ ratio, significantly boosting the initial step of the cascade reaction. This then triggers the three-enzyme cascade reaction system—oxidase (OXD), superoxide dismutase (SOD), and peroxidase (POD)—which facilitates the conversion of products from O2 to O2•- to endogenous H2O2, achieving a two-fold increase in its yield and subsequently to OH• in a sequential reaction, demonstrating excellent multi-enzyme cascade catalytic activity. Utilizing the inhibitory effect of glutathione (GSH) on multi-enzyme cascade catalytic activity, we designed a highly efficient and rapid colorimetric sensor for the sensitive detection of GSH, with a detection range of 0.5–160 μM and a detection limit of 0.15 μM.
Significance
Compared to traditional etching techniques, DES-based methods offer superior selectivity, lower toxicity, and better structural preservation of the MOF framework, making them a promising tool for controlled defect engineering. By selectively creating defects, the initial steps of the cascade reaction are activated, resulting in a significant enhancement of catalytic activity. This approach provides a viable pathway for the preparation of high-performance dual-metal catalysts for cascade reaction catalysts and sensing applications.
{"title":"Multi-nanozyme cascade system for boosting colorimetric sensing by selective etching bimetallic MOFs","authors":"Yuhang Lin , Tianshuo Wang , Yuanhao Liu , Lianxi Pu , Mingxuan Jia , Xilong Zhou , Lijun Ding , Weiran Zhu , Kun Wang","doi":"10.1016/j.aca.2025.343976","DOIUrl":"10.1016/j.aca.2025.343976","url":null,"abstract":"<div><h3>Background</h3><div>Rational engineering of multienzyme system architecture is essential for achieving high-performance multi-enzyme cascade catalysis in sensing applications. In this context, the initiation step of the cascade reaction pathway plays a pivotal role in enhancing catalytic efficiency. CoFe Prussian blue analogue (CoFePBA), a dual-metal organic framework, is an ideal template for multi-enzyme design, leveraging its diverse dual-metal ion functionalities and synergistic effects. Defect engineering approaches enable the fine-tuning of catalytic properties, optimizing electron transfer and promoting reaction intermediates. Therefore, the rational design of the multienzyme system structure is critical for efficient cascade catalysis.</div></div><div><h3>Results</h3><div>In this study, we utilized deep eutectic solvents (DES) to selectively induce Co defects in CoFePBA (CoFePBA-DES) under mild conditions, providing more active sites and enhancing the Co<sup>2+</sup>/Co<sup>3+</sup> ratio, significantly boosting the initial step of the cascade reaction. This then triggers the three-enzyme cascade reaction system—oxidase (OXD), superoxide dismutase (SOD), and peroxidase (POD)—which facilitates the conversion of products from O<sub>2</sub> to O<sub>2</sub><sup>•-</sup> to endogenous H<sub>2</sub>O<sub>2</sub>, achieving a two-fold increase in its yield and subsequently to OH<sup>•</sup> in a sequential reaction, demonstrating excellent multi-enzyme cascade catalytic activity. Utilizing the inhibitory effect of glutathione (GSH) on multi-enzyme cascade catalytic activity, we designed a highly efficient and rapid colorimetric sensor for the sensitive detection of GSH, with a detection range of 0.5–160 μM and a detection limit of 0.15 μM.</div></div><div><h3>Significance</h3><div>Compared to traditional etching techniques, DES-based methods offer superior selectivity, lower toxicity, and better structural preservation of the MOF framework, making them a promising tool for controlled defect engineering. By selectively creating defects, the initial steps of the cascade reaction are activated, resulting in a significant enhancement of catalytic activity. This approach provides a viable pathway for the preparation of high-performance dual-metal catalysts for cascade reaction catalysts and sensing applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343976"},"PeriodicalIF":5.7,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.aca.2025.343974
Kittiya Sakdaphetsiri , Thana Thaweeskulchai , Wiwittawin Sukmas , Joseph Wang , Albert Schulte , Nadnudda Rodthongkum
Background
A non-invasive glucose biosensor for multiple biofluids based on platinum nanoparticle (Pt-NP)-modified laser-induced graphene (LIG) electrodes coated with a zein/gelatin/glucose oxidase (GOx) for amperometric detection of glucose is created. The biosensor fabrication is cost-effective and scalable, as it combines simple LIG electrode fabrication with direct Pt-NP electrodeposition and a sequence of drop-and-dry steps for zein and gelatin layer then GOx enzyme. The Pt-NP modification on the LIG electrode functions as an electrocatalyst to enhance the anodic H2O2 signal, which is directly proportional to glucose concentration. The zein layer acts as a diffusion barrier to mitigate potential interferences, while the gelatin film provides amine groups for the glutaraldehyde-mediated immobilization of the GOx enzyme.
Results
The key parameters of LIG were optimized, such as power laser, number of Pt-NP cycles, and zein concentration. In addition, LIG was characterized by Raman spectroscopy, SEM, and cyclic voltammetry (CV) to ensure graphitization and electron transfer performance. The as prepared LIG/Pt-NP/Zein/Gel-GOx glucose biosensor was in anodic H2O2 detection mode and tested for glucose measurements in multiple biofluids including sweat, saliva, and urine. At H2O2 detection potential of +0.4 V, a linear detection range from 0 up to 2 mM glucose was obtained with a limit of detection (LOD) of 0.01 mM, making it feasible for glucose determination in various clinically relevant biofluids. By comparing with the commercial SPE, this LIG-based sensor offered much higher detection sensitivity towards both H2O2 and glucose, making it a superior choice for electrochemical analysis.
Significance
This LIG/Pt-NPs/Zein/Gel-GOx offers a practical and high sensitivity approach to glucose measurement with a wide linearity for multiple biofluids. Given the straightforward and easily scalable process, this high-performance, LIG-based glucose biosensor presents a compelling alternative over commercial screen-printed electrode. Highlighted the novelty using zein as a protective layer to reduce interferences. Owing to the simplicity of fabrication with high potential for up-scaling, this high analytical performance biosensor might be an alternative tool for multiplex glucose biosensors in point-of-care applications.
{"title":"Laser-induced graphene electrode modified by platinum nanoparticle/zein/gelatin/glucose oxidase for non-invasive glucose sensor in multiple biofluids","authors":"Kittiya Sakdaphetsiri , Thana Thaweeskulchai , Wiwittawin Sukmas , Joseph Wang , Albert Schulte , Nadnudda Rodthongkum","doi":"10.1016/j.aca.2025.343974","DOIUrl":"10.1016/j.aca.2025.343974","url":null,"abstract":"<div><h3>Background</h3><div>A non-invasive glucose biosensor for multiple biofluids based on platinum nanoparticle (Pt-NP)-modified laser-induced graphene (LIG) electrodes coated with a zein/gelatin/glucose oxidase (GOx) for amperometric detection of glucose is created. The biosensor fabrication is cost-effective and scalable, as it combines simple LIG electrode fabrication with direct Pt-NP electrodeposition and a sequence of drop-and-dry steps for zein and gelatin layer then GOx enzyme. The Pt-NP modification on the LIG electrode functions as an electrocatalyst to enhance the anodic H<sub>2</sub>O<sub>2</sub> signal, which is directly proportional to glucose concentration. The zein layer acts as a diffusion barrier to mitigate potential interferences, while the gelatin film provides amine groups for the glutaraldehyde-mediated immobilization of the GOx enzyme.</div></div><div><h3>Results</h3><div>The key parameters of LIG were optimized, such as power laser, number of Pt-NP cycles, and zein concentration. In addition, LIG was characterized by Raman spectroscopy, SEM, and cyclic voltammetry (CV) to ensure graphitization and electron transfer performance. The as prepared LIG/Pt-NP/Zein/Gel-GOx glucose biosensor was in anodic H<sub>2</sub>O<sub>2</sub> detection mode and tested for glucose measurements in multiple biofluids including sweat, saliva, and urine. At H<sub>2</sub>O<sub>2</sub> detection potential of +0.4 V, a linear detection range from 0 up to 2 mM glucose was obtained with a limit of detection (LOD) of 0.01 mM, making it feasible for glucose determination in various clinically relevant biofluids. By comparing with the commercial SPE, this LIG-based sensor offered much higher detection sensitivity towards both H<sub>2</sub>O<sub>2</sub> and glucose, making it a superior choice for electrochemical analysis.</div></div><div><h3>Significance</h3><div>This LIG/Pt-NPs/Zein/Gel-GOx offers a practical and high sensitivity approach to glucose measurement with a wide linearity for multiple biofluids. Given the straightforward and easily scalable process, this high-performance, LIG-based glucose biosensor presents a compelling alternative over commercial screen-printed electrode. Highlighted the novelty using zein as a protective layer to reduce interferences. Owing to the simplicity of fabrication with high potential for up-scaling, this high analytical performance biosensor might be an alternative tool for multiplex glucose biosensors in point-of-care applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343974"},"PeriodicalIF":5.7,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703470","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.aca.2025.343972
Xingchi Liu , Xinchen Qiu , Zhang Pan , Jing Chen , Shanshan Li , Jingmeng Cheng
Background
Escherichia coli (E. coli) is one of the most common pathogens in water and foods, and it poses a significant threat to global public health, particularly in low- and middle-income countries. However, most of the state-of-art detection method for E. coli bacteria sensing needs fluorescence staining or pre-immobilizations or specific biomaker as labels before tests, making the detection process a time costing and labor intensitive work. Thus, it is desirable to develop a label-free and no-immobilization detection method for the sensitive detection of E. coli or other pathogens. Results: In this work, we developed a sensitive method for E. coli detection without any labels or pre-immobilizations. Here the source AC signal provides ACEK effects to trap bacteria onto the electrode surface. As the source AC signal is cut off, the enriched bacteria would release from sensor electrodes. Then, a significant interfacial capacitance change along with particle releasing is observed by applying a measurement AC signal. The DEP capture of E. coli bacteria at different AC frequencies and voltages are experimentally investigated to optimize the performance of capacitive sensors. To note, the total area of our sensitive unit can be as large as 2 mm × 2 mm with the geometry design of isomotive DEP. Capacitive sensing tests of river water collected from local river and tap water with several control groups are performed to show its reliability as a biosensing approach for the sensitive detection of E. coli. Significance: The most significant advantage of this method is that we do not need to pre-immobilize any probes (antigens, or antibodies, etc.) or take incubation onto the sensor electrode before taking capacitance measurement. Moreover, the straight forward operation is pre-immobilization free, and therefore it meets the requirements of on-site bacteria detection for pathogen detection in water quality monitoring or food safety.
{"title":"Label-free detection of E. coli by alternating current electrokinetic capacitive sensors","authors":"Xingchi Liu , Xinchen Qiu , Zhang Pan , Jing Chen , Shanshan Li , Jingmeng Cheng","doi":"10.1016/j.aca.2025.343972","DOIUrl":"10.1016/j.aca.2025.343972","url":null,"abstract":"<div><h3>Background</h3><div>Escherichia coli (<em>E. coli</em>) is one of the most common pathogens in water and foods, and it poses a significant threat to global public health, particularly in low- and middle-income countries. However, most of the state-of-art detection method for E. coli bacteria sensing needs fluorescence staining or pre-immobilizations or specific biomaker as labels before tests, making the detection process a time costing and labor intensitive work. Thus, it is desirable to develop a label-free and no-immobilization detection method for the sensitive detection of <em>E. coli</em> or other pathogens. <u>Results</u>: In this work, we developed a sensitive method for <em>E. coli</em> detection without any labels or pre-immobilizations. Here the source AC signal provides ACEK effects to trap bacteria onto the electrode surface. As the source AC signal is cut off, the enriched bacteria would release from sensor electrodes. Then, a significant interfacial capacitance change along with particle releasing is observed by applying a measurement AC signal. The DEP capture of <em>E. coli</em> bacteria at different AC frequencies and voltages are experimentally investigated to optimize the performance of capacitive sensors. To note, the total area of our sensitive unit can be as large as 2 mm × 2 mm with the geometry design of isomotive DEP. Capacitive sensing tests of river water collected from local river and tap water with several control groups are performed to show its reliability as a biosensing approach for the sensitive detection of <em>E. coli</em>. <u>Significance:</u> The most significant advantage of this method is that we do not need to pre-immobilize any probes (antigens, or antibodies, etc.) or take incubation onto the sensor electrode before taking capacitance measurement. Moreover, the straight forward operation is pre-immobilization free, and therefore it meets the requirements of on-site bacteria detection for pathogen detection in water quality monitoring or food safety.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1354 ","pages":"Article 343972"},"PeriodicalIF":5.7,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1016/j.aca.2025.343958
Qihui Wang, Ju Yang, Siqi Yang, Jiagen Li, Congdi Chen, Jiexue Wang, Zhihui Xiong, Kang Sun, Guowei Deng
Background
Residues of moxifloxacin (MFX) and copper ions (Cu2+) can have detrimental health effects on humans. Thus, it is essential to develop a sensitive method for the detection of MFX and Cu2+. Fluorescence analysis is a potent technique, offering simplicity, speed, and efficiency. However, analytical results from single-emission fluorescence methods can be affected by environmental factors, probe inhomogeneity, and light-source intensity. Therefore, there is a need to design a novel dual-emission ratiometric fluorescence probe for the determination of MFX and Cu2+ to address these challenges and enhance the accuracy and sensitivity of the measurements.
Results
A novel dual emission ratiometric-based fluorescence probe (B/G probe) was constructed by N-doped carbon dots and coumarin derivatives. The B/G probe exhibited two fluorescence emission peaks at 442 nm and 513 nm when excited at 336 nm. The inner-filter effect played a significant role in the quenching characteristics of MFX. Additionally, Cu2+ ions were found to have a strong affinity for MFX. Consequently, this fluorescence probe was developed to detect MFX initially and subsequently Cu2+ ions. The detection limit (DL) was 17.5 nM and 32.5 nM for MFX and Cu2+ ions, respectively. The B/G probe had better selectivity and anti-interference capability. Satisfactory recovery rate indicated that the B/G prob had good accuracy for detection of MFX and Cu2+ ions.
Significance
This study represents the inaugural application of N-doped carbon dots and coumarin derivatives to construct a novel dual emission ratiometric-based fluorescence probe, demonstrating a marked advancement in innovation. This approach has significantly enhanced the sensitivity for the determination of MFX and Cu2+ ions. Compared with fluorescence probe of single signal, this method provides an effective strategy for detection MFX and Cu2+ with good accuracy, good selectivity, rapid detection and lower DL.
{"title":"Dual emission ratiometric fluorescence probe based on N-doped carbon dots and coumarin derivatives for determination of moxifloxacin and copper ion","authors":"Qihui Wang, Ju Yang, Siqi Yang, Jiagen Li, Congdi Chen, Jiexue Wang, Zhihui Xiong, Kang Sun, Guowei Deng","doi":"10.1016/j.aca.2025.343958","DOIUrl":"10.1016/j.aca.2025.343958","url":null,"abstract":"<div><h3>Background</h3><div>Residues of moxifloxacin (MFX) and copper ions (Cu<sup>2+</sup>) can have detrimental health effects on humans. Thus, it is essential to develop a sensitive method for the detection of MFX and Cu<sup>2+</sup>. Fluorescence analysis is a potent technique, offering simplicity, speed, and efficiency. However, analytical results from single-emission fluorescence methods can be affected by environmental factors, probe inhomogeneity, and light-source intensity. Therefore, there is a need to design a novel dual-emission ratiometric fluorescence probe for the determination of MFX and Cu<sup>2+</sup> to address these challenges and enhance the accuracy and sensitivity of the measurements.</div></div><div><h3>Results</h3><div>A novel dual emission ratiometric-based fluorescence probe (B/G probe) was constructed by N-doped carbon dots and coumarin derivatives. The B/G probe exhibited two fluorescence emission peaks at 442 nm and 513 nm when excited at 336 nm. The inner-filter effect played a significant role in the quenching characteristics of MFX. Additionally, Cu<sup>2+</sup> ions were found to have a strong affinity for MFX. Consequently, this fluorescence probe was developed to detect MFX initially and subsequently Cu<sup>2+</sup> ions. The detection limit (DL) was 17.5 nM and 32.5 nM for MFX and Cu<sup>2+</sup> ions, respectively. The B/G probe had better selectivity and anti-interference capability. Satisfactory recovery rate indicated that the B/G prob had good accuracy for detection of MFX and Cu<sup>2+</sup> ions.</div></div><div><h3>Significance</h3><div>This study represents the inaugural application of N-doped carbon dots and coumarin derivatives to construct a novel dual emission ratiometric-based fluorescence probe, demonstrating a marked advancement in innovation. This approach has significantly enhanced the sensitivity for the determination of MFX and Cu<sup>2+</sup> ions. Compared with fluorescence probe of single signal, this method provides an effective strategy for detection MFX and Cu<sup>2+</sup> with good accuracy, good selectivity, rapid detection and lower DL.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343958"},"PeriodicalIF":5.7,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Embryonic Nanog is recognized as a crucial controller of pluripotency. In the progression of cancer and the formation of metastasis, cancer cells with stem cell-like characteristics frequently express Nanog. Precisely identifying the Nanog antigen poses a significant challenge due to its low abundance in biofluids. The precise detection of the Nanog antigen originating from cancer cells has attracted growing interest for its potential uses in diagnostics and prognostics.
Results
In this study, a novel fluorescence strategy utilizing green carbon dots was developed for the highly sensitive and specific detection of Nanog. This approach involved the use of fluoro-immunosensors based on magnetic nanoparticles (MNPs) and antibodies targeting the cancer Stem Cells (CSCs) biomarker, Nanog. In this study, the targeted Nanog was magnetically separated following its reaction with green carbon dots and magnetic nanoparticles, both conjugated with anti-nanog antibodies. The findings show a clear increase in fluorescence with the rising concentration of Nanog antigen in the sample. The linear range for Nanog, measured under optimal experimental conditions, was found to be 5.0 × 10 −11 g/L to 1.0 × 10 −9 g/L. The detection limit (LOD) was calculated to be 1.0 × 10 −11 g/L.
Significance
This study introduces a fluoro-immunosensor employing magnetic nanoparticles (MNPs) and high quantum efficiency green-emitting carbon dots. This represents the first use of these carbon dots in this type of sensor. The biosensor has demonstrated effective detection of Nanog in biological samples. This developed biosensor, which is both convenient and highly sensitive, presents a significant opportunity for quantifying Nanog in biological research and clinical applications.
{"title":"Green emitting carbon dots-immunosensor on magnetic nanoparticles for detection of Nanog antigen as a cancer stem cell biomarker","authors":"Fatemeh Mehrabi , Morteza Hosseini , Niloufar Sadeghi , Javad Mohammadi , Mohammad reza Ganjali , Bijan Ranjbar","doi":"10.1016/j.aca.2025.343960","DOIUrl":"10.1016/j.aca.2025.343960","url":null,"abstract":"<div><h3>Background</h3><div>Embryonic Nanog is recognized as a crucial controller of pluripotency. In the progression of cancer and the formation of metastasis, cancer cells with stem cell-like characteristics frequently express Nanog. Precisely identifying the Nanog antigen poses a significant challenge due to its low abundance in biofluids. The precise detection of the Nanog antigen originating from cancer cells has attracted growing interest for its potential uses in diagnostics and prognostics.</div></div><div><h3>Results</h3><div>In this study, a novel fluorescence strategy utilizing green carbon dots was developed for the highly sensitive and specific detection of Nanog. This approach involved the use of fluoro-immunosensors based on magnetic nanoparticles (MNPs) and antibodies targeting the cancer Stem Cells (CSCs) biomarker, Nanog. In this study, the targeted Nanog was magnetically separated following its reaction with green carbon dots and magnetic nanoparticles, both conjugated with anti-nanog antibodies. The findings show a clear increase in fluorescence with the rising concentration of Nanog antigen in the sample. The linear range for Nanog, measured under optimal experimental conditions, was found to be 5.0 × 10 <sup>−11</sup> g/L to 1.0 × 10 <sup>−9</sup> g/L. The detection limit (LOD) was calculated to be 1.0 × 10 <sup>−11</sup> g/L.</div></div><div><h3>Significance</h3><div>This study introduces a fluoro-immunosensor employing magnetic nanoparticles (MNPs) and high quantum efficiency green-emitting carbon dots. This represents the first use of these carbon dots in this type of sensor. The biosensor has demonstrated effective detection of Nanog in biological samples. This developed biosensor, which is both convenient and highly sensitive, presents a significant opportunity for quantifying Nanog in biological research and clinical applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343960"},"PeriodicalIF":5.7,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-22DOI: 10.1016/j.aca.2025.343947
Evangelos Kalampokis, Theodora Nikou, Stavros Beteinakis, Maria Halabalaki
Background
The relationship between diet, human health, and disease prevention is well-established, with food bioactive compounds (FBs) widely recognized for their beneficial effects. Metabolism is key in transforming precursor FBs molecules and facilitating their circulation in the human body. Urine has proven to be a valuable biofluid for monitoring dietary exposure. However, the low concentrations of FBs metabolites, their chemical variability, and the lack of appropriate reference standards present challenges in metabolite identification. To address these challenges, developing urine preparation methods for scalable metabolite isolation and unambiguous structure elucidation could significantly improve the coverage and accurate annotation of urine metabolites.
Results
Urine samples were collected from a healthy volunteer after hydroxytyrosol (HT) supplementation. Traditional urine pretreatment protocols, such as liquid-liquid extraction (LLE) and solid-phase extraction (SPE), were tested alongside enrichment methods using resins (XAD-4, XAD-7, ion-exchange). Extracts were analyzed in parallel using HPLC-DAD/ELSD, UPLC-HRMS, and NMR to assess profiles and annotate metabolites. Methods were evaluated based on extraction yield, metabolite chemical and biochemical diversity, metabolite coverage, selectivity, as well as cost, ease and time. The most promising protocols were further tested on a larger scale. Among the methods evaluated, XAD-7 resin and LLE (Urine/EtOAc 1:3) showed the best performance. Furthermore, detailed identification of metabolites (endogenous and exogenous) per protocol was performed using LC-HRMS/MS and NMR. Additionally, investigation of each protocol performance in respect to the biochemical pathway in which metabolites are implicated was assessed.
Significance
The suggested workflow is compatible with both profiling and isolation set-ups and could provide essential insights into urine metabolome and FBs biotransformation. It ensures confident identification and high coverage of metabolites, providing more complete and accurate interpretation of metabolism studies' results and, therefore, valuable input in profiling approaches towards the role of diet on human health.
{"title":"Multiscale workflow for the profiling and identification of urinary food bioactives metabolites Part I: Optimizing urine extraction","authors":"Evangelos Kalampokis, Theodora Nikou, Stavros Beteinakis, Maria Halabalaki","doi":"10.1016/j.aca.2025.343947","DOIUrl":"10.1016/j.aca.2025.343947","url":null,"abstract":"<div><h3>Background</h3><div>The relationship between diet, human health, and disease prevention is well-established, with food bioactive compounds (FBs) widely recognized for their beneficial effects. Metabolism is key in transforming precursor FBs molecules and facilitating their circulation in the human body. Urine has proven to be a valuable biofluid for monitoring dietary exposure. However, the low concentrations of FBs metabolites, their chemical variability, and the lack of appropriate reference standards present challenges in metabolite identification. To address these challenges, developing urine preparation methods for scalable metabolite isolation and unambiguous structure elucidation could significantly improve the coverage and accurate annotation of urine metabolites.</div></div><div><h3>Results</h3><div>Urine samples were collected from a healthy volunteer after hydroxytyrosol (HT) supplementation. Traditional urine pretreatment protocols, such as liquid-liquid extraction (LLE) and solid-phase extraction (SPE), were tested alongside enrichment methods using resins (XAD-4, XAD-7, ion-exchange). Extracts were analyzed in parallel using HPLC-DAD/ELSD, UPLC-HRMS, and NMR to assess profiles and annotate metabolites. Methods were evaluated based on extraction yield, metabolite chemical and biochemical diversity, metabolite coverage, selectivity, as well as cost, ease and time. The most promising protocols were further tested on a larger scale. Among the methods evaluated, XAD-7 resin and LLE (Urine/EtOAc 1:3) showed the best performance. Furthermore, detailed identification of metabolites (endogenous and exogenous) per protocol was performed using LC-HRMS/MS and NMR. Additionally, investigation of each protocol performance in respect to the biochemical pathway in which metabolites are implicated was assessed.</div></div><div><h3>Significance</h3><div>The suggested workflow is compatible with both profiling and isolation set-ups and could provide essential insights into urine metabolome and FBs biotransformation. It ensures confident identification and high coverage of metabolites, providing more complete and accurate interpretation of metabolism studies' results and, therefore, valuable input in profiling approaches towards the role of diet on human health.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343947"},"PeriodicalIF":5.7,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675273","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-22DOI: 10.1016/j.aca.2025.343959
Xing Zhong , Hezheng Zhan , Xiao Wang , Min Zhang , Shoushan Wang , Meili Zhang , Faliang Cheng , Peng Liu
Background
Surface-enhanced Raman spectroscopy (SERS) substrates have undergone extensive development over the years, yet the challenge of significantly enhancing their sensitivity persists. Most existing substrates face considerable difficulties in obtaining the strongest electromagnetic coupling to maximize SERS signal intensity, i.e., it is hard to achieve optimal structural parameters such as the gap width and particle size, and to fabricate surfaces that are free from contamination such as surfactants. Therefore, there is a pressing need for a substrate optimization approach that allows for in-situ monitoring and real-time dynamic adjustments to precisely achieve the ideal substrate characteristics for superior performance.
Results
In this study, a highly sensitive porous copper-gold (Cu–Au) SERS substrate was fabricated using the galvanic replacement reaction (GRR), coupled with in-situ SERS monitoring to optimize substrate preparation. The Cu–Au nanoparticles formed and grew on sacrificial templates while noble metal ions were reduced by the sacrificial metal during GRR. The substrate preparation process revealed that the optimal preparation time was 200 ± 20 s. The SERS performance with crystal violet (CV) as a probe molecule demonstrated the substrate's remarkable sensitivity with detecting concentrations as low as 10−16 M, which surpasses most literature reports. The optimized SERS substrate was further tested for detecting malachite green (MG), yielding an ultra-high enhancement factor (EF) of 8.96 × 1014. The entire optimization process did not involve the addition of aggregation or surfactant agents, ensuring a clean substrate surface.
Significance and novelty
This study is a further proof of the significance of the in-situ optimization of SERS substrates via GRR which allows real-time adjustment of nanoparticle size and gap width to enhance sensitivity. This approach has enabled us to develop substrates with exceptional sensitivity and reproducibility. These significant contributions may open up new avenues for the facile fabrication of ultrasensitive SERS substrates.
{"title":"In-situ galvanic replacement reaction assisted preparation of porous Cu–Au composites as highly sensitive SERS substrates","authors":"Xing Zhong , Hezheng Zhan , Xiao Wang , Min Zhang , Shoushan Wang , Meili Zhang , Faliang Cheng , Peng Liu","doi":"10.1016/j.aca.2025.343959","DOIUrl":"10.1016/j.aca.2025.343959","url":null,"abstract":"<div><h3>Background</h3><div>Surface-enhanced Raman spectroscopy (SERS) substrates have undergone extensive development over the years, yet the challenge of significantly enhancing their sensitivity persists. Most existing substrates face considerable difficulties in obtaining the strongest electromagnetic coupling to maximize SERS signal intensity, i.e., it is hard to achieve optimal structural parameters such as the gap width and particle size, and to fabricate surfaces that are free from contamination such as surfactants. Therefore, there is a pressing need for a substrate optimization approach that allows for in-situ monitoring and real-time dynamic adjustments to precisely achieve the ideal substrate characteristics for superior performance.</div></div><div><h3>Results</h3><div>In this study, a highly sensitive porous copper-gold (Cu–Au) SERS substrate was fabricated using the galvanic replacement reaction (GRR), coupled with in-situ SERS monitoring to optimize substrate preparation. The Cu–Au nanoparticles formed and grew on sacrificial templates while noble metal ions were reduced by the sacrificial metal during GRR. The substrate preparation process revealed that the optimal preparation time was 200 ± 20 s. The SERS performance with crystal violet (CV) as a probe molecule demonstrated the substrate's remarkable sensitivity with detecting concentrations as low as 10<sup>−16</sup> M, which surpasses most literature reports. The optimized SERS substrate was further tested for detecting malachite green (MG), yielding an ultra-high enhancement factor (EF) of 8.96 × 10<sup>14</sup>. The entire optimization process did not involve the addition of aggregation or surfactant agents, ensuring a clean substrate surface.</div></div><div><h3>Significance and novelty</h3><div>This study is a further proof of the significance of the in-situ optimization of SERS substrates via GRR which allows real-time adjustment of nanoparticle size and gap width to enhance sensitivity. This approach has enabled us to develop substrates with exceptional sensitivity and reproducibility. These significant contributions may open up new avenues for the facile fabrication of ultrasensitive SERS substrates.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343959"},"PeriodicalIF":5.7,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-22DOI: 10.1016/j.aca.2025.343940
Kuan-Wen Liu , Pei-Yu Sie , Hsi-Ying Chen , Fong-I Ho , Po-Sheng Huang , Pin Chieh Wu , Mei-Yi Liao
Background
Surface-enhanced Raman scattering (SERS) is a powerful analytical technique that utilizes localized electromagnetic fields to amplify molecular vibrational signatures. The effectiveness of SERS substrates relies on the presence of “hot spots,” where electromagnetic fields are highly concentrated. However, the fabrication of metal nanotemplates with optimal hot spot structures is often restricted by the continuous shell formation inherent in conventional synthesis methods, which limits the reproducibility and sensitivity of SERS-based analyses. This study addresses the significant challenge of developing a reliable method for creating SERS substrates with a high density of hot spots.
Results
We developed two-dimensional/three-dimensional (2D/3D) AuAg nanoplates by controlling pore formation within silver templates. This method enabled the selective deposition of gold and silver atoms at high-energy defect sites. The resulting 3D AuAg nanoplates displayed distinctive island-like structures with optimized gap spacings in nanogranule assembly, which led to significant shifts in surface plasmon resonance (SPR). The SERS performance of these 3D AuAg nanoplates, characterized by in-plane absorption, was enhanced, achieving a detection limit of 0.008 ppm for 4-nitrothiophenol, with enhancement factors 2 to 4 times greater than those of conventional nanocube and nanosphere structures. Additionally, functionalization with NTP:4-mercaptophenylboronic acid (MPBA) in a 1:3 ratio demonstrated excellent biocompatibility (>80 % cell viability) and effective cancer-targeting imaging capabilities in both SERS and dark-field microscopy. These findings highlight the crucial role of template morphology in enhancing electromagnetic fields, leading to improved SERS sensitivity for chemical and biological sensing.
Significance
This study conclusively demonstrates the importance of template morphology in optimizing SERS performance. It emphasizes the potential of 2D/3D AuAg nanoplates for advanced chemical sensing and biological diagnostics. The developed methodology provides a viable approach for creating highly sensitive and specific SERS probes, thereby advancing the field of analytical chemistry.
{"title":"Enhanced SERS performance through defect-guided growth of 2D/3D AuAg nanoplates for chemical sensing and cellular imaging applications","authors":"Kuan-Wen Liu , Pei-Yu Sie , Hsi-Ying Chen , Fong-I Ho , Po-Sheng Huang , Pin Chieh Wu , Mei-Yi Liao","doi":"10.1016/j.aca.2025.343940","DOIUrl":"10.1016/j.aca.2025.343940","url":null,"abstract":"<div><h3>Background</h3><div>Surface-enhanced Raman scattering (SERS) is a powerful analytical technique that utilizes localized electromagnetic fields to amplify molecular vibrational signatures. The effectiveness of SERS substrates relies on the presence of “hot spots,” where electromagnetic fields are highly concentrated. However, the fabrication of metal nanotemplates with optimal hot spot structures is often restricted by the continuous shell formation inherent in conventional synthesis methods, which limits the reproducibility and sensitivity of SERS-based analyses. This study addresses the significant challenge of developing a reliable method for creating SERS substrates with a high density of hot spots.</div></div><div><h3>Results</h3><div>We developed two-dimensional/three-dimensional (2D/3D) AuAg nanoplates by controlling pore formation within silver templates. This method enabled the selective deposition of gold and silver atoms at high-energy defect sites. The resulting 3D AuAg nanoplates displayed distinctive island-like structures with optimized gap spacings in nanogranule assembly, which led to significant shifts in surface plasmon resonance (SPR). The SERS performance of these 3D AuAg nanoplates, characterized by in-plane absorption, was enhanced, achieving a detection limit of 0.008 ppm for 4-nitrothiophenol, with enhancement factors 2 to 4 times greater than those of conventional nanocube and nanosphere structures. Additionally, functionalization with NTP:4-mercaptophenylboronic acid (MPBA) in a 1:3 ratio demonstrated excellent biocompatibility (>80 % cell viability) and effective cancer-targeting imaging capabilities in both SERS and dark-field microscopy. These findings highlight the crucial role of template morphology in enhancing electromagnetic fields, leading to improved SERS sensitivity for chemical and biological sensing.</div></div><div><h3>Significance</h3><div>This study conclusively demonstrates the importance of template morphology in optimizing SERS performance. It emphasizes the potential of 2D/3D AuAg nanoplates for advanced chemical sensing and biological diagnostics. The developed methodology provides a viable approach for creating highly sensitive and specific SERS probes, thereby advancing the field of analytical chemistry.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343940"},"PeriodicalIF":5.7,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-22DOI: 10.1016/j.aca.2025.343970
Yichi Zhang , Junsheng Wang , Yuezhu Wang , Xiaotong Xu , Bingchen Liang , Qing Yu , Yinchun Li , Chenyang Wang , Xiaoming Xue
Background
As the issue of heavy metal pollution has become increasingly prominent, the electrochemical detection of trace heavy metal ions in the marine environment has emerged as a significant and commonly utilized method. The detection of heavy metal ions has been a gradual replacement of traditional methods with electrochemical detection. However, the temperature and pH of seawater vary with time and location, leading to biases in the detection results of conventional ion-selective membrane sensors that only focus on the relationship between concentration and voltage.
Results
This paper treats an experimental and modeling study to predict the electrochemical performance of ion-selective membrane sensors under varying temperatures and pH. By investigating the relationship between the working electrode response potential, pH, temperature, and cadmium ion concentration, a multivariate self-calibration model including pH, T, and the logarithm of cadmium ion concentration as independent variables was constructed. The determination coefficient R2 of the model was 0.9997, indicating a good fit. Automatic correction of electrochemical sensor minimizes the impact of temperature and pH, ensuring accurate readings of cadmium ion concentration during long-term monitoring. In addition, the recovery rates of Cd(II) concentration measurements were 113 % (coexisting with Na(I)) and 121 % (coexisting with Cu(II)), indicating good resistance to interference. Accuracy tests showed recovery rates ranging from 98 % to 121 %, demonstrating the good accuracy.
Significance
Therefore, the ion-selective membrane sensors can reduce the interference of temperature and pH on the measurement of heavy metal ion concentrations through the multivariate self-calibration model. This study provides a reliable detection method for addressing the issue of heavy metal pollution in water bodies and has a broad application prospect.
{"title":"Application of multi-variable calibration model of electrochemical sensor in high-accuracy long-term monitoring of cadmium ions","authors":"Yichi Zhang , Junsheng Wang , Yuezhu Wang , Xiaotong Xu , Bingchen Liang , Qing Yu , Yinchun Li , Chenyang Wang , Xiaoming Xue","doi":"10.1016/j.aca.2025.343970","DOIUrl":"10.1016/j.aca.2025.343970","url":null,"abstract":"<div><h3>Background</h3><div>As the issue of heavy metal pollution has become increasingly prominent, the electrochemical detection of trace heavy metal ions in the marine environment has emerged as a significant and commonly utilized method. The detection of heavy metal ions has been a gradual replacement of traditional methods with electrochemical detection. However, the temperature and pH of seawater vary with time and location, leading to biases in the detection results of conventional ion-selective membrane sensors that only focus on the relationship between concentration and voltage.</div></div><div><h3>Results</h3><div>This paper treats an experimental and modeling study to predict the electrochemical performance of ion-selective membrane sensors under varying temperatures and pH. By investigating the relationship between the working electrode response potential, pH, temperature, and cadmium ion concentration, a multivariate self-calibration model including pH, T, and the logarithm of cadmium ion concentration as independent variables was constructed. The determination coefficient R<sup>2</sup> of the model was 0.9997, indicating a good fit. Automatic correction of electrochemical sensor minimizes the impact of temperature and pH, ensuring accurate readings of cadmium ion concentration during long-term monitoring. In addition, the recovery rates of Cd(II) concentration measurements were 113 % (coexisting with Na(I)) and 121 % (coexisting with Cu(II)), indicating good resistance to interference. Accuracy tests showed recovery rates ranging from 98 % to 121 %, demonstrating the good accuracy.</div></div><div><h3>Significance</h3><div>Therefore, the ion-selective membrane sensors can reduce the interference of temperature and pH on the measurement of heavy metal ion concentrations through the multivariate self-calibration model. This study provides a reliable detection method for addressing the issue of heavy metal pollution in water bodies and has a broad application prospect.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1353 ","pages":"Article 343970"},"PeriodicalIF":5.7,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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