Pub Date : 2024-11-07DOI: 10.1016/j.aca.2024.343399
Daniela Oliveira , Pedro Oliveira , Ana Xu , Eduarda Rodrigues , Susana G. Guerreiro , Rafael C. Castro , David S.M. Ribeiro , João L.M. Santos , Ana Margarida L. Piloto
This study introduces a fluorescent immunosensor colour panel with antibody-conjugated quantum dots for detecting CA19-9 in human serum. The immunosensors presented decreasing fluorescence with increasing CA19-9 concentrations, with a linear detection range from 0.01 to 501.87 U mL−1 and detection limits of 1.66 × 10⁻⁴, 2.71 × 10⁻⁴, and 5.45 × 10⁻⁴ U mL−1 for the green-, orange-, and red-emitting conjugates in human serum. These limits are well below the 37 U mL−1 cutoff for early pancreatic cancer risk. The immunosensor panel is simple, sensitive, and specific, offering a visual colour readout for rapid CA19-9 detection, making it ideal for point-of-care applications. The results highlight the potential of the developed conjugates as a sensitive fluorescence colour panel for detecting CA19-9 across a wide range in human serum, both below and above the pancreatic cancer cutoff. With just 200 μL of sample and a single pre-filtration step, the assay delivers results in under 15 min, offering a cost-effective and efficient platform for point-of-care use.
{"title":"Optical immunosensor panel using quantum dot-antibody conjugates for highly sensitive detection of carbohydrate antigen 19–9 (CA19-9)","authors":"Daniela Oliveira , Pedro Oliveira , Ana Xu , Eduarda Rodrigues , Susana G. Guerreiro , Rafael C. Castro , David S.M. Ribeiro , João L.M. Santos , Ana Margarida L. Piloto","doi":"10.1016/j.aca.2024.343399","DOIUrl":"10.1016/j.aca.2024.343399","url":null,"abstract":"<div><div>This study introduces a fluorescent immunosensor colour panel with antibody-conjugated quantum dots for detecting CA19-9 in human serum. The immunosensors presented decreasing fluorescence with increasing CA19-9 concentrations, with a linear detection range from 0.01 to 501.87 U mL<sup>−1</sup> and detection limits of 1.66 × 10⁻⁴, 2.71 × 10⁻⁴, and 5.45 × 10⁻⁴ U mL<sup>−1</sup> for the green-, orange-, and red-emitting conjugates in human serum. These limits are well below the 37 U mL<sup>−1</sup> cutoff for early pancreatic cancer risk. The immunosensor panel is simple, sensitive, and specific, offering a visual colour readout for rapid CA19-9 detection, making it ideal for point-of-care applications. The results highlight the potential of the developed conjugates as a sensitive fluorescence colour panel for detecting CA19-9 across a wide range in human serum, both below and above the pancreatic cancer cutoff. With just 200 μL of sample and a single pre-filtration step, the assay delivers results in under 15 min, offering a cost-effective and efficient platform for point-of-care use.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343399"},"PeriodicalIF":5.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598048","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 : 2024-11-06DOI: 10.1016/j.aca.2024.343408
Zhiying Shao , Kezuo Di , Lijun Ding , Fuheng You , Cunhao Fan , Kun Wang
Background
Heavy metal pollution is a global environmental problem. Self-reduction strategy has garnered attention in adsorption and electrochemical detection of heavy metal ions due to their operational simplicity and elimination of the need for external electrodeposition steps. Therefore, it is crucial to integrate self-reduction-based adsorption with electrochemical detection. Metal-Organic Frameworks (MOFs) have demonstrated successful applications in adsorption and electrochemical detection. Moreover, owing to the presence of organic ligands featuring amino and electron-rich aromatic ring moieties, MOFs possess reducing capabilities towards metal ions.
Results
Herein, 2,4,6-triaminopyrimidine, characterized by its abundance of amino and electron-rich aromatic ring constituents, was selected as the organic ligand for the synthesis of Zn-MOFs, showcasing their efficacy in self-reduction-based adsorption and electrochemical detection of heavy metal ions. The Zn-MOFs exhibited swift uptake of heavy metal ions, boasting a remarkable adsorption capacity (4624 mg/g for Cu(II), 4261 mg/g for Hg(II), and 4874 mg/g for Pb(II)), while also exhibiting low detection limits (0.17 μg/L for Cu(II), 0.25 μg/L for Hg(II), and 0.22 μg/L for Pb(II)) in the electrochemical detection of heavy metal ions.
Significance
In this work, amino-rich Zn-MOFs were prepared for self-reducing adsorption and electrochemical detection of heavy metal ions, providing promising material for the detection and removal of heavy metal ions, offering a new method for the effective elimination and rapid detection of heavy metal ions, and pointing out a promising path for the treatment and monitoring of environmental issues.
{"title":"Amino-enriched Zn-MOFs with self-reduction for energy-free simultaneous removal and electrochemical detection of heavy metal ions in the aquatic environment","authors":"Zhiying Shao , Kezuo Di , Lijun Ding , Fuheng You , Cunhao Fan , Kun Wang","doi":"10.1016/j.aca.2024.343408","DOIUrl":"10.1016/j.aca.2024.343408","url":null,"abstract":"<div><h3>Background</h3><div>Heavy metal pollution is a global environmental problem. Self-reduction strategy has garnered attention in adsorption and electrochemical detection of heavy metal ions due to their operational simplicity and elimination of the need for external electrodeposition steps. Therefore, it is crucial to integrate self-reduction-based adsorption with electrochemical detection. Metal-Organic Frameworks (MOFs) have demonstrated successful applications in adsorption and electrochemical detection. Moreover, owing to the presence of organic ligands featuring amino and electron-rich aromatic ring moieties, MOFs possess reducing capabilities towards metal ions.</div></div><div><h3>Results</h3><div>Herein, 2,4,6-triaminopyrimidine, characterized by its abundance of amino and electron-rich aromatic ring constituents, was selected as the organic ligand for the synthesis of Zn-MOFs, showcasing their efficacy in self-reduction-based adsorption and electrochemical detection of heavy metal ions. The Zn-MOFs exhibited swift uptake of heavy metal ions, boasting a remarkable adsorption capacity (4624 mg/g for Cu(II), 4261 mg/g for Hg(II), and 4874 mg/g for Pb(II)), while also exhibiting low detection limits (0.17 μg/L for Cu(II), 0.25 μg/L for Hg(II), and 0.22 μg/L for Pb(II)) in the electrochemical detection of heavy metal ions.</div></div><div><h3>Significance</h3><div>In this work, amino-rich Zn-MOFs were prepared for self-reducing adsorption and electrochemical detection of heavy metal ions, providing promising material for the detection and removal of heavy metal ions, offering a new method for the effective elimination and rapid detection of heavy metal ions, and pointing out a promising path for the treatment and monitoring of environmental issues.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343408"},"PeriodicalIF":5.7,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594347","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 : 2024-11-06DOI: 10.1016/j.aca.2024.343409
Jiawei Zhou , Lili Zhao , Yuee Zhong , Peipei Li , Xiaohua Zhu , Shu Huang , Youyu Zhang , Meiling Liu
Human immunoglobulin (HIgG) has gained recognition as a crucial biomarker diagnosing and treating various diseases, particularly in identifying elevated serum levels in conditions like measles and pneumococcal disease. Traditional detection methods, however, are often hindered by inefficiencies, high costs, and potential inaccuracies, underscoring the urgent need for more sensitive, efficient, accurate, and self-calibration methods for HIgG. Here, a novel ZnIn2S4/SnO2 composites was synthesized, featuring uniformly dispersed SnO2 nanoparticles on the flower-like ZnIn2S4 structure, resulting in a type II heterojunction that promotes the separation and transfer of photogenerated carriers. Under optimized conditions, this composite demonstrated remarkable photocurrent enhancements 52 and 195 times greater than that of the individual ZnIn2S4 or SnO2, respectively. A novel dual-mode biosensing platform was subsequently developed, employing the ZnIn2S4/SnO2 composites as both as the photoelectrochemical (PEC) signal generator and antibody carrier. This system utilizes multifunctional CuO NPs with ascorbic acid oxidase-like properties, serving as a secondary antibody label. Upon specific binding to HIgG, a notable decrease in the PEC response occurs due to the catalytic activity of CuO NPs and the antigen-antibody interactions. The introduction of o-phenylenediamine (OPD) further enhances detection by facilitating the formation of a fluorescent substance DHAA. This dual-signal approach yielded excellent linear correlations between both PEC and fluorescence signals and HIgG concentration, achieving low detection limits of 22.5 pg/mL or 8.6 pg/mL. These two signals originated from the same PEC electrode with continuous detection in the absence and presence of OPD, simplifying experimental procedures and enhancing the reliability of detection. The non-toxic, chemically stable ZnIn2S4/SnO2 composites ensures reliable and sensitive detection through photocurrent output after incubation with biomolecules. The integration of nanozyme catalysis, biospecific reactions, and in situ fluorescent products generation promise high selectivity across diverse immunosensing applications.
{"title":"Dual-mode detection of human immunoglobulin via copper oxide nanozyme catalysis fluorescent species generation and photoelectrochemical alteration in ZnIn2S4/SnO2-based system","authors":"Jiawei Zhou , Lili Zhao , Yuee Zhong , Peipei Li , Xiaohua Zhu , Shu Huang , Youyu Zhang , Meiling Liu","doi":"10.1016/j.aca.2024.343409","DOIUrl":"10.1016/j.aca.2024.343409","url":null,"abstract":"<div><div>Human immunoglobulin (HIgG) has gained recognition as a crucial biomarker diagnosing and treating various diseases, particularly in identifying elevated serum levels in conditions like measles and pneumococcal disease. Traditional detection methods, however, are often hindered by inefficiencies, high costs, and potential inaccuracies, underscoring the urgent need for more sensitive, efficient, accurate, and self-calibration methods for HIgG. Here, a novel ZnIn<sub>2</sub>S<sub>4</sub>/SnO<sub>2</sub> composites was synthesized, featuring uniformly dispersed SnO<sub>2</sub> nanoparticles on the flower-like ZnIn<sub>2</sub>S<sub>4</sub> structure, resulting in a type II heterojunction that promotes the separation and transfer of photogenerated carriers. Under optimized conditions, this composite demonstrated remarkable photocurrent enhancements 52 and 195 times greater than that of the individual ZnIn<sub>2</sub>S<sub>4</sub> or SnO<sub>2</sub>, respectively. A novel dual-mode biosensing platform was subsequently developed, employing the ZnIn<sub>2</sub>S<sub>4</sub>/SnO<sub>2</sub> composites as both as the photoelectrochemical (PEC) signal generator and antibody carrier. This system utilizes multifunctional CuO NPs with ascorbic acid oxidase-like properties, serving as a secondary antibody label. Upon specific binding to HIgG, a notable decrease in the PEC response occurs due to the catalytic activity of CuO NPs and the antigen-antibody interactions. The introduction of <em>o</em>-phenylenediamine (OPD) further enhances detection by facilitating the formation of a fluorescent substance DHAA. This dual-signal approach yielded excellent linear correlations between both PEC and fluorescence signals and HIgG concentration, achieving low detection limits of 22.5 pg/mL or 8.6 pg/mL. These two signals originated from the same PEC electrode with continuous detection in the absence and presence of OPD, simplifying experimental procedures and enhancing the reliability of detection. The non-toxic, chemically stable ZnIn<sub>2</sub>S<sub>4</sub>/SnO<sub>2</sub> composites ensures reliable and sensitive detection through photocurrent output after incubation with biomolecules. The integration of nanozyme catalysis, biospecific reactions, and in situ fluorescent products generation promise high selectivity across diverse immunosensing applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343409"},"PeriodicalIF":5.7,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594350","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 : 2024-11-06DOI: 10.1016/j.aca.2024.343400
Abi Legesse, Negussie Megersa, Bhagwan Singh Chandravanshi
Background
The widespread use of pesticides for the protection of fruits has resulted in the presence of pesticide residue levels beyond their limit in fruits. This ensures their transfer to processed products, such as juices, posing a threat to human health. Therefore, an efficient and selective method is required for monitoring pesticide residues in fruit juices. Hence, an effervescence-assisted dispersive liquid-liquid microextraction based on surface floating organic droplets was developed for the simultaneous extraction of five pesticide residues of different classes. An environmentally green low-density organic solvent, 1-undecanol, was used as extraction solvent.
Results
The developed method was optimized and validated for quantitative extraction of multiclass pesticide residues at trace levels from fruit juice samples, including apple, pineapple, guava and orange samples. The method showed good linearity in the range of 0.8–300 ng mL−1 for all pesticide residues with a regression coefficient ranging from 0.9979 to 0.9997 under the optimized conditions. The LOD and LOQ of the method ranged between 0.03 and 0.16 ng mL−1 and 0.11–0.52 ng mL−1, respectively, indicating the high sensitivity of the proposed method. Repeatability and reproducibility, in terms of %RSD, were obtained in the range of 1.16–5.50 % and 3.12–7.72 %, respectively.
Significance
The developed method exhibited acceptable mean recoveries (%R) in the range of 73.77–113.34 % with %RSDs (n = 3) ranging from 1.25 to 7.74 % for all the analytes studied. Therefore, the developed method can be used as a selective, sensitive and efficient extraction method for the extraction of multiclass pesticides from fruit juice samples.
背景为保护水果而广泛使用杀虫剂，导致水果中的杀虫剂残留水平超过了其极限。这确保了它们转移到果汁等加工产品中，对人类健康构成威胁。因此，需要一种高效且具有选择性的方法来监测果汁中的农药残留。因此，本研究开发了一种基于浮动有机液滴固化的泡腾法辅助分散液液微萃取方法，用于同时萃取五种不同类别的农药残留。萃取溶剂为绿色环保的低密度有机溶剂 1-十一醇。(94)结果所建立的方法对果汁样品（包括苹果、菠萝、番石榴和橙子样品）中痕量多类农药残留的定量萃取进行了优化和验证。在优化条件下，所有农药残留在 0.8 至 300 ng mL-1 范围内线性关系良好，回归系数为 0.9979 至 0.9997。方法的检出限和定量限分别为0.03～0.16 ng mL-1 和0.11～0.52 ng mL-1，表明该方法的灵敏度较高。方法的重复性和重现性分别为1.16%～5.50%和3.12%～7.72%。(101) 重要意义所建立的方法在 73.77-113.34% 的平均回收率（%R）和 1.25-7.74% 的%RSD（n=3）范围内对所有研究的分析物均显示了可接受的平均回收率（%R）。因此，所建立的方法可作为一种选择性强、灵敏度高且高效的萃取方法用于果汁样品中多类农药的萃取。(52)
{"title":"Effervescence-assisted dispersive liquid-liquid microextraction for the extraction and preconcentration of pesticide residues in fruit juice samples","authors":"Abi Legesse, Negussie Megersa, Bhagwan Singh Chandravanshi","doi":"10.1016/j.aca.2024.343400","DOIUrl":"10.1016/j.aca.2024.343400","url":null,"abstract":"<div><h3>Background</h3><div>The widespread use of pesticides for the protection of fruits has resulted in the presence of pesticide residue levels beyond their limit in fruits. This ensures their transfer to processed products, such as juices, posing a threat to human health. Therefore, an efficient and selective method is required for monitoring pesticide residues in fruit juices. Hence, an effervescence-assisted dispersive liquid-liquid microextraction based on surface floating organic droplets was developed for the simultaneous extraction of five pesticide residues of different classes. An environmentally green low-density organic solvent, 1-undecanol, was used as extraction solvent.</div></div><div><h3>Results</h3><div>The developed method was optimized and validated for quantitative extraction of multiclass pesticide residues at trace levels from fruit juice samples, including apple, pineapple, guava and orange samples. The method showed good linearity in the range of 0.8–300 ng mL<sup>−1</sup> for all pesticide residues with a regression coefficient ranging from 0.9979 to 0.9997 under the optimized conditions. The LOD and LOQ of the method ranged between 0.03 and 0.16 ng mL<sup>−1</sup> and 0.11–0.52 ng mL<sup>−1</sup>, respectively, indicating the high sensitivity of the proposed method. Repeatability and reproducibility, in terms of %RSD, were obtained in the range of 1.16–5.50 % and 3.12–7.72 %, respectively.</div></div><div><h3>Significance</h3><div>The developed method exhibited acceptable mean recoveries (%R) in the range of 73.77–113.34 % with %RSDs (n = 3) ranging from 1.25 to 7.74 % for all the analytes studied. Therefore, the developed method can be used as a selective, sensitive and efficient extraction method for the extraction of multiclass pesticides from fruit juice samples.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343400"},"PeriodicalIF":5.7,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594349","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 : 2024-11-05DOI: 10.1016/j.aca.2024.343397
Yueran Ren , Bingqian Zhou , Minghui Yu , Yangyang Xue , Weijun Kong , Rui Yang
Background
Cancer has become one of the main causes of death globally. The level of tumor markers in serum is correlated with the occurrence of cancer. Carcinoembryonic antigen (CEA) is the most commonly utilized tumor marker for cancer detection. Recently, various analytical technologies have been reported to detect biomarkers. However, developing a simple, sensitive, and noninvasive approach for CEA detection remains challenging in cancer diagnosis. Consequently, there is an urgent need for researchers to carry out innovative approaches for CEA detection.
Result
In this work, copper ferrite nanoparticles (CuFe2O4 NPs) with excellent dispersity and fascinating magnetism have been successfully synthesized. To get CuFe2O4@ABEI-GNPs, ABEI-gold NPs (ABEI-GNPs) were generated on the surface of CuFe2O4 NPs by using N-(4-Aminobutyl)-N-ethylisoluminol (ABEI) as a mild reduction reagent to reduce chloroauric acid tetrahydrate (HAuCl4·4H2O). The CuFe2O4@ABEI-GNPs exhibited a superior chemiluminescence (CL) performance compared with CuFe2O4@ABEI NPs, which was attributed to the synergistic catalysis effects of CuFe2O4 NPs and GNPs. Interestingly, two unique CL emission peaks were observed in the kinetic curve of CuFe2O4@ABEI-GNPs. Furthermore, it was found that the kinetic curve could be regulated by the pH of hydrogen peroxide (H2O2) and a possible CL mechanism was proposed. Owing to the favorable CL properties of CuFe2O4@ABEI-GNPs, a label-free differential immunosensor was fabricated for CEA monitoring using the intensity difference between CL-1 and CL-2. The developed immunosensor exhibited a wide linear range from 0.1 to 5000 pg/mL, and a low detection limit of 0.05 pg/mL.
Significance and novelty
The immunosensor was capable of determining CEA in real samples with simple operation, high accuracy, and good sensitivity. This study introduces a novel approach for developing CL functionalized materials, which have broad application potential in bioassays. The proposed differential method could serve as a novel tool for determining CEA in the diagnosis of clinical cancer.
{"title":"Label-free differential chemiluminescent immunosensor based on magnetic nanoparticles CuFe2O4@ABEI-GNPs with dual catalytic sites","authors":"Yueran Ren , Bingqian Zhou , Minghui Yu , Yangyang Xue , Weijun Kong , Rui Yang","doi":"10.1016/j.aca.2024.343397","DOIUrl":"10.1016/j.aca.2024.343397","url":null,"abstract":"<div><h3>Background</h3><div>Cancer has become one of the main causes of death globally. The level of tumor markers in serum is correlated with the occurrence of cancer. Carcinoembryonic antigen (CEA) is the most commonly utilized tumor marker for cancer detection. Recently, various analytical technologies have been reported to detect biomarkers. However, developing a simple, sensitive, and noninvasive approach for CEA detection remains challenging in cancer diagnosis. Consequently, there is an urgent need for researchers to carry out innovative approaches for CEA detection.</div></div><div><h3>Result</h3><div>In this work, copper ferrite nanoparticles (CuFe<sub>2</sub>O<sub>4</sub> NPs) with excellent dispersity and fascinating magnetism have been successfully synthesized. To get CuFe<sub>2</sub>O<sub>4</sub>@ABEI-GNPs, ABEI-gold NPs (ABEI-GNPs) were generated on the surface of CuFe<sub>2</sub>O<sub>4</sub> NPs by using N-(4-Aminobutyl)-N-ethylisoluminol (ABEI) as a mild reduction reagent to reduce chloroauric acid tetrahydrate (HAuCl<sub>4</sub>·4H<sub>2</sub>O). The CuFe<sub>2</sub>O<sub>4</sub>@ABEI-GNPs exhibited a superior chemiluminescence (CL) performance compared with CuFe<sub>2</sub>O<sub>4</sub>@ABEI NPs, which was attributed to the synergistic catalysis effects of CuFe<sub>2</sub>O<sub>4</sub> NPs and GNPs. Interestingly, two unique CL emission peaks were observed in the kinetic curve of CuFe<sub>2</sub>O<sub>4</sub>@ABEI-GNPs. Furthermore, it was found that the kinetic curve could be regulated by the pH of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and a possible CL mechanism was proposed. Owing to the favorable CL properties of CuFe<sub>2</sub>O<sub>4</sub>@ABEI-GNPs, a label-free differential immunosensor was fabricated for CEA monitoring using the intensity difference between CL-1 and CL-2. The developed immunosensor exhibited a wide linear range from 0.1 to 5000 pg/mL, and a low detection limit of 0.05 pg/mL.</div></div><div><h3>Significance and novelty</h3><div>The immunosensor was capable of determining CEA in real samples with simple operation, high accuracy, and good sensitivity. This study introduces a novel approach for developing CL functionalized materials, which have broad application potential in bioassays. The proposed differential method could serve as a novel tool for determining CEA in the diagnosis of clinical cancer.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343397"},"PeriodicalIF":5.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588494","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}
Chemiluminescence (CL) analysis, characterized by its simple instrumentation, high signal-to-noise ratio, wide linear range, and minimal background interference, has garnered increasing attention from researchers. Nanomaterials (NMs) have been explored to enhance CL intensity. Notably, sub-1 nanometer scale NMs are considered to hold significant untapped potential due to their size effects. The application of these sub-1 nanometer NMs in enhancing CL is anticipated to yield favorable results. Additionally, the low water solubility and bioavailability of quercetin glycosides lead to their presence in bodily fluids at only trace levels, highlighting the urgent need for efficient and rapid detection methods.
Results
In this work, phosphomolybdic acid (PMA) was incorporated into CuO to synthesize sub-1 nanometer CuO-PMA nanosheets (SNSs) using a cluster-core co-assembly strategy. Conformational and structural characterization confirmed the successful synthesis of these nanosheets. The CuO-PMA SNSs were employed to enhance the CL emission of the luminol-H2O2 system, resulting in an increase of over 1000 times. The catalytic properties of CuO-PMA SNSs significantly facilitated the decomposition of H2O2, leading to an enhanced production of reactive oxygen species, which in turn induced the CL enhancement. Given that the antioxidant effect of quercetin would consume the reactive oxygen species generated during the catalysis, a decrease in CL intensity was anticipated. A CL sensor for quercetin detection was developed based on the CuO-PMA SNSs-luminol-H2O2 system, demonstrating a strong linear relationship (R2 = 0.9969) and a low detection limit of 0.31 nM.
Significance
This research provides a strategy to enhance the CL intensity of the luminol-H2O2 system by using CuO-PMA SNSs, offering a highly sensitive assay for detecting quercetin concentrations. The method is characterized as a simple and cost-effective analytical strategy making CL analysis very attractive for chemical analysts.
{"title":"Enhanced chemiluminescence with sub-1 nanometer CuO-PMA nanosheets for the sensitive detection of quercetin","authors":"Kuangjun Li , Chunxia Huang , Tianyou Chen, Suxing Jiao, Jing Wu","doi":"10.1016/j.aca.2024.343395","DOIUrl":"10.1016/j.aca.2024.343395","url":null,"abstract":"<div><h3>Background</h3><div>Chemiluminescence (CL) analysis, characterized by its simple instrumentation, high signal-to-noise ratio, wide linear range, and minimal background interference, has garnered increasing attention from researchers. Nanomaterials (NMs) have been explored to enhance CL intensity. Notably, sub-1 nanometer scale NMs are considered to hold significant untapped potential due to their size effects. The application of these sub-1 nanometer NMs in enhancing CL is anticipated to yield favorable results. Additionally, the low water solubility and bioavailability of quercetin glycosides lead to their presence in bodily fluids at only trace levels, highlighting the urgent need for efficient and rapid detection methods.</div></div><div><h3>Results</h3><div>In this work, phosphomolybdic acid (PMA) was incorporated into CuO to synthesize sub-1 nanometer CuO-PMA nanosheets (SNSs) using a cluster-core co-assembly strategy. Conformational and structural characterization confirmed the successful synthesis of these nanosheets. The CuO-PMA SNSs were employed to enhance the CL emission of the luminol-H<sub>2</sub>O<sub>2</sub> system, resulting in an increase of over 1000 times. The catalytic properties of CuO-PMA SNSs significantly facilitated the decomposition of H<sub>2</sub>O<sub>2</sub>, leading to an enhanced production of reactive oxygen species, which in turn induced the CL enhancement. Given that the antioxidant effect of quercetin would consume the reactive oxygen species generated during the catalysis, a decrease in CL intensity was anticipated. A CL sensor for quercetin detection was developed based on the CuO-PMA SNSs-luminol-H<sub>2</sub>O<sub>2</sub> system, demonstrating a strong linear relationship (R<sup>2</sup> = 0.9969) and a low detection limit of 0.31 nM.</div></div><div><h3>Significance</h3><div>This research provides a strategy to enhance the CL intensity of the luminol-H<sub>2</sub>O<sub>2</sub> system by using CuO-PMA SNSs, offering a highly sensitive assay for detecting quercetin concentrations. The method is characterized as a simple and cost-effective analytical strategy making CL analysis very attractive for chemical analysts.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343395"},"PeriodicalIF":5.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580353","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 : 2024-11-05DOI: 10.1016/j.aca.2024.343398
Zhiguang Suo , Tao Lu , Jiahui Liu , Jiayi Li , Li Wang , Yong Liu , Min Wei
Background
Aflatoxin B1 (AFB1) is a widely distributed toxic contaminant in food and poses a serious threat to public health. Therefore, an accurate, simple, cost-effective and on-site assay method is needed for sensitive detection of AFB1. Aptamer shows great potential in the construction of biosensor due to its high specificity and affinity. Multimodal biosensor based on aptamer is highly suitable for the analysis of AFB1 under complex conditions. And the detection results in different modes can be verified with each other, which greatly improves the accuracy of AFB1 detection.
Results
Herein, accurate detection of AFB1 was achieved through the development of a multi-mode biosensor integrating electrochemistry, glucosemeter and smartphone-based colorimetric quantification. Streptavidin-Cu3(PO4)2 hybrid nanoflowers (SA-Cu3(PO4)2 HNFs) were synthesised and then conjugated with biotinylated invertase as a signal probe. The electrochemical signal was achieved via intrinsic redox activity. Simultaneously, sucrose could be converted to glucose by the action of invertase, which can cause changes in the glucosemeter signal as well as in the colour of urine glucose test strips. The glucosemeter could complete the signal response in 7 s, and the urine glucose test strips could complete the colour development in 30 s. The detection range of AFB1 by this system in electrochemical mode is 0.001–100 ng/mL, and in glucosemeter mode and smartphone mode is 0.01–50 ng/mL. The limits of detection were 0.49 pg/mL in electrochemistry mode, 5.4 pg/mL in glucosemeter mode and 3.7 pg/mL in smartphone mode.
Significance
The successful construction of this multi-mode biosensor demonstrates the advantages of multifunctional nanomaterials and mobile technology. Rapid and accurate detection of AFB1 is achieved through the integration of electrochemistry, glucosemeter and smartphone-based colorimetric quantification. And this biosensor provides a novel detection platform that combines sensitivity, accuracy, affordability and portability for rapid on-site food safety screening.
{"title":"Electrochemistry–glucosemeter–smartphone integrated multi-mode biosensor for accurate detection of aflatoxin B1","authors":"Zhiguang Suo , Tao Lu , Jiahui Liu , Jiayi Li , Li Wang , Yong Liu , Min Wei","doi":"10.1016/j.aca.2024.343398","DOIUrl":"10.1016/j.aca.2024.343398","url":null,"abstract":"<div><h3>Background</h3><div>Aflatoxin B1 (AFB1) is a widely distributed toxic contaminant in food and poses a serious threat to public health. Therefore, an accurate, simple, cost-effective and on-site assay method is needed for sensitive detection of AFB1. Aptamer shows great potential in the construction of biosensor due to its high specificity and affinity. Multimodal biosensor based on aptamer is highly suitable for the analysis of AFB1 under complex conditions. And the detection results in different modes can be verified with each other, which greatly improves the accuracy of AFB1 detection.</div></div><div><h3>Results</h3><div>Herein, accurate detection of AFB1 was achieved through the development of a multi-mode biosensor integrating electrochemistry, glucosemeter and smartphone-based colorimetric quantification. Streptavidin-Cu<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> hybrid nanoflowers (SA-Cu<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> HNFs) were synthesised and then conjugated with biotinylated invertase as a signal probe. The electrochemical signal was achieved via intrinsic redox activity. Simultaneously, sucrose could be converted to glucose by the action of invertase, which can cause changes in the glucosemeter signal as well as in the colour of urine glucose test strips. The glucosemeter could complete the signal response in 7 s, and the urine glucose test strips could complete the colour development in 30 s. The detection range of AFB1 by this system in electrochemical mode is 0.001–100 ng/mL, and in glucosemeter mode and smartphone mode is 0.01–50 ng/mL. The limits of detection were 0.49 pg/mL in electrochemistry mode, 5.4 pg/mL in glucosemeter mode and 3.7 pg/mL in smartphone mode.</div></div><div><h3>Significance</h3><div>The successful construction of this multi-mode biosensor demonstrates the advantages of multifunctional nanomaterials and mobile technology. Rapid and accurate detection of AFB1 is achieved through the integration of electrochemistry, glucosemeter and smartphone-based colorimetric quantification. And this biosensor provides a novel detection platform that combines sensitivity, accuracy, affordability and portability for rapid on-site food safety screening.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343398"},"PeriodicalIF":5.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588317","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 : 2024-11-05DOI: 10.1016/j.aca.2024.343386
Zhuowei Fu , Yiwen Yang , Zhifeng Li , Yanbo Zeng , Hailong Wang , Yifeng Han , Qiukai Tang , Lei Li
Background
C-reactive protein (CRP), one of the classic biomarkers of inflammation, is closely related to infectious inflammation, cardiovascular disease, cancer, and other diseases. Therefore, timely and accurate detection of CRP in human blood is crucial for the discovery, diagnosis, and treatment of the aforementioned diseases. Herein, a novel label-free NIR fluorescence aptasensor with a large Stokes shift based on an AIEE anthracene derivative B and a molybdenum disulfide (MoS2) platform was developed and used for the high sensitivity and specificity detection of CRP.
Results
Compound B could emit near-infrared (NIR) fluorescence with a large Stokes shift (190 nm). Notably, this compound could bind with the aptamer of CRP (CRP-Apt) through electrostatic attraction to form a B/CRP-Apt complex, generating an aggregation-induced emission enhancement effect and enhancing the fluorescent intensity of B. B/CRP-Apt could be adsorbed on the surface of MoS2 with the addition of MoS2 to its solution, and the fluorescence of Compound B was quenched. CRP was then added to the above solution. CRP-Apt had a substantially higher affinity for CRP than MoS2. Therefore, B/CRP-Apt detached from the surface of MoS2 and bound to CRP, thereby restoring the fluorescence of B. Experimental results showed a good linear relationship between the fluorescent recovery intensity of B and the concentration of CRP in the concentration range of 0.3–70 ng mL−1, with a limit of detection as low as 0.1 ng mL−1.
Significance and novelty
The aptasensor integrates the advantages of high sensitivity of NIR fluorescence, high specificity of aptamers, good water-solubility and AIEE effect of Compound B. And it could be applied to the determination of CRP in human serum samples, while most of the reported methods can only determine CRP in spiked human serum samples.
{"title":"Detection of C-reactive protein using a label-free NIR fluorescent aptasensor with a large Stokes shift based on an AIEE anthracene derivative","authors":"Zhuowei Fu , Yiwen Yang , Zhifeng Li , Yanbo Zeng , Hailong Wang , Yifeng Han , Qiukai Tang , Lei Li","doi":"10.1016/j.aca.2024.343386","DOIUrl":"10.1016/j.aca.2024.343386","url":null,"abstract":"<div><h3>Background</h3><div>C-reactive protein (CRP), one of the classic biomarkers of inflammation, is closely related to infectious inflammation, cardiovascular disease, cancer, and other diseases. Therefore, timely and accurate detection of CRP in human blood is crucial for the discovery, diagnosis, and treatment of the aforementioned diseases. Herein, a novel label-free NIR fluorescence aptasensor with a large Stokes shift based on an AIEE anthracene derivative B and a molybdenum disulfide (MoS<sub>2</sub>) platform was developed and used for the high sensitivity and specificity detection of CRP.</div></div><div><h3>Results</h3><div>Compound B could emit near-infrared (NIR) fluorescence with a large Stokes shift (190 nm). Notably, this compound could bind with the aptamer of CRP (CRP-Apt) through electrostatic attraction to form a B/CRP-Apt complex, generating an aggregation-induced emission enhancement effect and enhancing the fluorescent intensity of B. B/CRP-Apt could be adsorbed on the surface of MoS<sub>2</sub> with the addition of MoS<sub>2</sub> to its solution, and the fluorescence of Compound B was quenched. CRP was then added to the above solution. CRP-Apt had a substantially higher affinity for CRP than MoS<sub>2</sub>. Therefore, B/CRP-Apt detached from the surface of MoS<sub>2</sub> and bound to CRP, thereby restoring the fluorescence of B. Experimental results showed a good linear relationship between the fluorescent recovery intensity of B and the concentration of CRP in the concentration range of 0.3–70 ng mL<sup>−1</sup>, with a limit of detection as low as 0.1 ng mL<sup>−1</sup>.</div></div><div><h3>Significance and novelty</h3><div>The aptasensor integrates the advantages of high sensitivity of NIR fluorescence, high specificity of aptamers, good water-solubility and AIEE effect of Compound B. And it could be applied to the determination of CRP in human serum samples, while most of the reported methods can only determine CRP in spiked human serum samples.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343386"},"PeriodicalIF":5.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580089","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}
Spectrophotometers are ubiquitous in chemical and biological science; however, their precision limits are under-appreciated. Rules-of-thumb and IUPAC referenced guidance restricting absorbance ranges to minimize uncertainty are based on historically important instruments which are no longer as widely used. Advances over the last half-century changed most “raw” data from absorbance and transmittance values directly produced in analog electronics to digitized intensities. The latter are rarely provided in favour of digitally transformed derived data. Assessment of spectrophotometer limitations using digitized intensities would be straightforward with mean-variance analysis. However, in their absence, derived data evaluated at scale allows efficient characterisation of modern spectrophotometers.
Results
This study analyses signals when I and I0 are not available and only absorbance or transmittance are obtained. Current IUPAC referenced guidance indicates that absorbance should be limited between 0.1 and 1.0 a.u. with optimal performance (minimum relative standard deviation (RSD)) at 0.43 a.u. or 0.86 a.u. depending on the type of limiting noise. We characterised noise in UV–Vis spectrophotometers using three methods and report optimality spectra for the first time. We found the instruments were not Poisson optimal and best RSDs were sometimes above 1.0 a.u. We could find no evidence justifying guidance restricting absorbance to between 0.1 and 1.0 a.u. Measured RSD and light intensity are more important than absorbance values for assuring good quality measurements. However, estimating light intensity is a difficult inverse problem when I and I0 are not available, and the tested commercial instruments did not provide these.
Significance
Based on this work, classical theories are insufficient to describe spectrophotometers accurately. Furthermore, we urge IUPAC to modernise the references in its Gold Book and press instrument makers to improve data transparency. These steps are crucial to use spectrophotometers optimally.
{"title":"Raw data and noise in spectrophotometry","authors":"Bruna Falgueras Vallbona , Ardiana Kajtazi , Golnaz Shahtahmassebi , Quentin S. Hanley","doi":"10.1016/j.aca.2024.343393","DOIUrl":"10.1016/j.aca.2024.343393","url":null,"abstract":"<div><h3>Background</h3><div>Spectrophotometers are ubiquitous in chemical and biological science; however, their precision limits are under-appreciated. Rules-of-thumb and IUPAC referenced guidance restricting absorbance ranges to minimize uncertainty are based on historically important instruments which are no longer as widely used. Advances over the last half-century changed most “raw” data from absorbance and transmittance values directly produced in analog electronics to digitized intensities. The latter are rarely provided in favour of digitally transformed derived data. Assessment of spectrophotometer limitations using digitized intensities would be straightforward with mean-variance analysis. However, in their absence, derived data evaluated at scale allows efficient characterisation of modern spectrophotometers.</div></div><div><h3>Results</h3><div>This study analyses signals when <em>I</em> and <em>I</em><sub><em>0</em></sub> are not available and only absorbance or transmittance are obtained. Current IUPAC referenced guidance indicates that absorbance should be limited between 0.1 and 1.0 a.u. with optimal performance (minimum relative standard deviation (RSD)) at 0.43 a.u. or 0.86 a.u. depending on the type of limiting noise. We characterised noise in UV–Vis spectrophotometers using three methods and report optimality spectra for the first time. We found the instruments were not Poisson optimal and best RSDs were sometimes above 1.0 a.u. We could find no evidence justifying guidance restricting absorbance to between 0.1 and 1.0 a.u. Measured RSD and light intensity are more important than absorbance values for assuring good quality measurements. However, estimating light intensity is a difficult inverse problem when <em>I</em> and <em>I</em><sub>0</sub> are not available, and the tested commercial instruments did not provide these.</div></div><div><h3>Significance</h3><div>Based on this work, classical theories are insufficient to describe spectrophotometers accurately. Furthermore, we urge IUPAC to modernise the references in its Gold Book and press instrument makers to improve data transparency. These steps are crucial to use spectrophotometers optimally.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343393"},"PeriodicalIF":5.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580102","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}
With the rapid development of industrialization, the excessive emission of S2− have become increasingly serious, leading to a surge in the content of S2− in nature. Rapid and accurate detection of S2− contamination in natural adaptogens is crucial for food safety. Annually, discarded eggshell waste, rich in organic and inorganic materials, poses environmental risks if landfilled. Utilizing waste eggshell membrane biomass for S2− detection is cost-effective, yet designing biochar materials for sensors requires balancing catalytic enhancement and anti-interference capabilities. Improving the catalytic performance of biochar for colorimetric S2− detection without metal ion interference presents a challenging issue.
Results
We first modified biochar (EBc) derived from waste eggshell membranes using a combination of thiourea and ZnS nanoparticles, fabricating ZnS-decorated, S–N co-doped biochar (ZnS-SN-EBc) nanozymes, which were applied for the colorimetric assay detection of S2− contamination. The addition of thiourea significantly increases the proportion of pyridinic-N in biochar, enhancing the peroxidase-like activity of the nanozyme. The growth of ZnS nanoparticles on the biochar not only enhances the catalytic performance by increasing the S content but also reduces the content of oxidized S, thereby improving resistance to interference. The detection range for S2− was expanded from 0.1 to 45 μM for EBc to 0.05–225 μM for ZnS-SN-EBc, and the limit of detection improved to 0.0397 μM. Additionally, ZnS-SN-EBc significantly enhanced metal ion interference resistance. S2− detection in five types of adaptogenic herbs verified the accuracy and practicality of the colorimetric assay, with recovery rates comparable to national standards.
Significance
We innovatively repurposed waste eggshell membranes to develop a selective and catalytic peroxidase-like nanozyme, ZnS-decorated S–N co-doped biochar (ZnS-SN-EBc). The developed colorimetric assay utilizing ZnS-SN-EBc demonstrates significant potential for the detection of sulfur ions in adaptogenic herbs, thus contributing to both waste resource utilization and the advancement of food safety detection technologies.
{"title":"High sensitive and discriminating colorimetric assay for S2− overload in adaptogenic herbs utilizing ZnS nanoparticle-enhanced S, N-doped eggshell membrane-derived biochar","authors":"Dapeng Xu , Yanning Zheng , Bimei Xie , Youquan Zhang , Zhangfa Tong , Jianhua Sun , Lixia Sun , Guangzhi Zhou , Dankui Liao","doi":"10.1016/j.aca.2024.343391","DOIUrl":"10.1016/j.aca.2024.343391","url":null,"abstract":"<div><h3>Background</h3><div>With the rapid development of industrialization, the excessive emission of S<sup>2−</sup> have become increasingly serious, leading to a surge in the content of S<sup>2−</sup> in nature. Rapid and accurate detection of S<sup>2−</sup> contamination in natural adaptogens is crucial for food safety. Annually, discarded eggshell waste, rich in organic and inorganic materials, poses environmental risks if landfilled. Utilizing waste eggshell membrane biomass for S<sup>2−</sup> detection is cost-effective, yet designing biochar materials for sensors requires balancing catalytic enhancement and anti-interference capabilities. Improving the catalytic performance of biochar for colorimetric S<sup>2−</sup> detection without metal ion interference presents a challenging issue.</div></div><div><h3>Results</h3><div>We first modified biochar (EBc) derived from waste eggshell membranes using a combination of thiourea and ZnS nanoparticles, fabricating ZnS-decorated, S–N co-doped biochar (ZnS-SN-EBc) nanozymes, which were applied for the colorimetric assay detection of S<sup>2−</sup> contamination. The addition of thiourea significantly increases the proportion of pyridinic-N in biochar, enhancing the peroxidase-like activity of the nanozyme. The growth of ZnS nanoparticles on the biochar not only enhances the catalytic performance by increasing the S content but also reduces the content of oxidized S, thereby improving resistance to interference. The detection range for S<sup>2−</sup> was expanded from 0.1 to 45 μM for EBc to 0.05–225 μM for ZnS-SN-EBc, and the limit of detection improved to 0.0397 μM. Additionally, ZnS-SN-EBc significantly enhanced metal ion interference resistance. S<sup>2−</sup> detection in five types of adaptogenic herbs verified the accuracy and practicality of the colorimetric assay, with recovery rates comparable to national standards.</div></div><div><h3>Significance</h3><div>We innovatively repurposed waste eggshell membranes to develop a selective and catalytic peroxidase-like nanozyme, ZnS-decorated S–N co-doped biochar (ZnS-SN-EBc). The developed colorimetric assay utilizing ZnS-SN-EBc demonstrates significant potential for the detection of sulfur ions in adaptogenic herbs, thus contributing to both waste resource utilization and the advancement of food safety detection technologies.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1333 ","pages":"Article 343391"},"PeriodicalIF":5.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580100","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号