Pub Date : 2024-09-07DOI: 10.1016/j.microc.2024.111601
Leonardo Francisco Rafael Lemes, Frederico Luis Felipe Soares, Noemi Nagata
Due to rising temperatures in recent years, there has been an increase in outbreaks of arboviral diseases like Dengue, chikungunya, Zika, and yellow fever, which are primarily transmitted by two mosquitos. The outbreak has sparked significant concern among the population and prompted countries to heighten their precautions, specially by increasing the use of insects repellents. Regarding the regulatory demands of these products, this study develops a novel analytical method for the determination of DEET, Icaridin, and IR3535 in insect repellents combining excitation-emission matrix (EEM) fluorescence spectroscopy with higher-order multivariate calibration techniques. For this purpose, a dataset comprising 21 samples containing the studied active ingredients was used to construct Parallel Factor Analysis (PARAFAC) and Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) models. As a result, DEET, Icaridin, and IR3535 were quantified with a RMSEP lower than 1.84% for PARAFAC and below 11.30% for MCR-ALS. The EJCR test confirmed the accuracy of the proposed methods, which agreed with the high-performance liquid chromatography reference method at a 95% confidence level. These findings suggest that developing multiway calibration models using EEM proves to be accurate and cost-effective for quality control in repellent-based products.
{"title":"Determination of DEET, Icaridin, and IR3535 in insect repellents using excitation-emission matrix (EEM) fluorescence spectroscopy and multiway calibration","authors":"Leonardo Francisco Rafael Lemes, Frederico Luis Felipe Soares, Noemi Nagata","doi":"10.1016/j.microc.2024.111601","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111601","url":null,"abstract":"Due to rising temperatures in recent years, there has been an increase in outbreaks of arboviral diseases like Dengue, chikungunya, Zika, and yellow fever, which are primarily transmitted by two mosquitos. The outbreak has sparked significant concern among the population and prompted countries to heighten their precautions, specially by increasing the use of insects repellents. Regarding the regulatory demands of these products, this study develops a novel analytical method for the determination of DEET, Icaridin, and IR3535 in insect repellents combining excitation-emission matrix (EEM) fluorescence spectroscopy with higher-order multivariate calibration techniques. For this purpose, a dataset comprising 21 samples containing the studied active ingredients was used to construct Parallel Factor Analysis (PARAFAC) and Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) models. As a result, DEET, Icaridin, and IR3535 were quantified with a RMSEP lower than 1.84% for PARAFAC and below 11.30% for MCR-ALS. The EJCR test confirmed the accuracy of the proposed methods, which agreed with the high-performance liquid chromatography reference method at a 95% confidence level. These findings suggest that developing multiway calibration models using EEM proves to be accurate and cost-effective for quality control in repellent-based products.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212483","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 : 2024-09-07DOI: 10.1016/j.microc.2024.111604
Qian Wang, Yongjiao Ren, Shijie Li, Junping Wang
Multimodal lateral flow immunoassay has displayed the great potential to improve the flexibility and practicality of point-of-care testing. Herein, this study developed a dual-mode photothermal (PT) and surface-enhanced Raman scattering (SERS) immunochromatographic sensor for sensitive detection of aflatoxin B (AFB). The bifunctional waxberry-like core-satellite nanoparticles loaded with 5,5′-Dithiobis (2-nitrobenzoic acid) (DTNB) were prepared and coupled with antibody to form PT@SERS nanoprobes for qualitative and quantitative detection of AFB. The photothermal conversion efficiency and SERS enhancement factor of the nanoprobes were 42.11 % and 1.59 × 10, respectively. Under the optimal conditions, the limit of detection of PT assay was 0.033 ng/mL with a linear range of 0.05–10 ng/mL (R = 0.997); the limit of detection of SERS assay was 0.0073 ng/mL with a linear range of 0.005–10 ng/mL (R = 0.998). The results of the specificity analysis indicated no cross-reactions with the other toxins. The recoveries of the spiked corn and peanut were from 85.39 % to 112.15 % (PT assay) and 80.04 % to 106.57 % (SERS assay), respectively. The assay demonstrated that the developed dual-mode sensor provided a promising option for achieving the rapid detection of AFB.
{"title":"A dual-mode immunochromatographic sensor with photothermal and surface-enhanced Raman scattering for sensitive detection of aflatoxin B1","authors":"Qian Wang, Yongjiao Ren, Shijie Li, Junping Wang","doi":"10.1016/j.microc.2024.111604","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111604","url":null,"abstract":"Multimodal lateral flow immunoassay has displayed the great potential to improve the flexibility and practicality of point-of-care testing. Herein, this study developed a dual-mode photothermal (PT) and surface-enhanced Raman scattering (SERS) immunochromatographic sensor for sensitive detection of aflatoxin B (AFB). The bifunctional waxberry-like core-satellite nanoparticles loaded with 5,5′-Dithiobis (2-nitrobenzoic acid) (DTNB) were prepared and coupled with antibody to form PT@SERS nanoprobes for qualitative and quantitative detection of AFB. The photothermal conversion efficiency and SERS enhancement factor of the nanoprobes were 42.11 % and 1.59 × 10, respectively. Under the optimal conditions, the limit of detection of PT assay was 0.033 ng/mL with a linear range of 0.05–10 ng/mL (R = 0.997); the limit of detection of SERS assay was 0.0073 ng/mL with a linear range of 0.005–10 ng/mL (R = 0.998). The results of the specificity analysis indicated no cross-reactions with the other toxins. The recoveries of the spiked corn and peanut were from 85.39 % to 112.15 % (PT assay) and 80.04 % to 106.57 % (SERS assay), respectively. The assay demonstrated that the developed dual-mode sensor provided a promising option for achieving the rapid detection of AFB.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212481","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 : 2024-09-07DOI: 10.1016/j.microc.2024.111569
Lan Ma, Yuanyuan Li, Le Shang, Yulong Ma, Yonggang Sun, Wenxin Ji
Exploration and development of novel chromatographic stationary phases is an effective way to improve the separation efficiency of geometric isomers with similar physicochemical properties. Covalent organic frameworks (COFs) are a new class of porous organic polymers that show a wide range of applications in the field of separation science due to their tunable geometries and functionalities, infinitely extended network structures, and abundant interaction sites. However, the common imine-bonded COFs are poorly resistant to hydrolysis in HPLC. In this work, 2,4,6-trimethyl-1,3,5-triazine (TMT) and 1,3,5-tris (4-formylphenyl) triazine (TFPT) were used as raw materials, a sp carbon-conjugated covalent organic framework (spc-COF) was synthesized through self-assembly monolayer-assisted surface-initiated Schiff-base-mediated hydroxyl-aldehyde condensation reaction, and loaded on the surface of silica substrate with a CN bond to obtain a new segregated material (SiO@spc-COF). SiO@spc-COF was used as a high-performance liquid chromatography (HPLC) packing material for the separation of geometric isomers. Benefitting from its superb in-plane π-conjugation, highly ordered and robust framework structure, high chemical and thermal stability of spc-COF, and the unique hydrophilic covalent triazine groups, hydrophobic benzene rings and other groups that can provide a variety of interactions such as hydrophobicity, π-π stacking, hydrogen bonding and hydrophilicity of the prepared SiO@spc-COF stationary phases, they exhibit excellent molecular shape selectivity and resolution in separating geometrical isomers. These geometric isomers include isomers such as polycyclic aromatic hydrocarbons (PAHs), tocopherols, carotenoids, diethylstilbestrol, 1,4-cyclohexanediol and astaxanthin. Compared to commercial C columns, this column has more flexible selectivity and higher separation performance. In addition, due to the introduction of hydrophobicity, π-π stacking action and hydrophilic triazine components, the SiO@spc-COF stationary phase also has RPLC/HILIC mixed mode characteristics. Baseline separations of monosubstituted benzenes, alkylbenzenes, positional isomers, sulfonamides, benzoic acid, anilines, nucleosides and nucleobases compounds were achieved on SiO@spc-COF packed columns. This successful application highlights the great potential of spc-COF for the separation of geometrical isomers, and provides a way to overcome the stability of common imine-bonded COFs materials in HPLC, as well as to compensate for the shortcomings and deficiencies of a single chromatographic mode in the separation of complex samples. Furthermore, this is the first report of a practical separation of important geometrical isomers using spc-COF materials.
{"title":"Preparation of sp2c-COF functionalized silica gel material as chromatographic stationary phases for their high-resolution separation of geometric isomers","authors":"Lan Ma, Yuanyuan Li, Le Shang, Yulong Ma, Yonggang Sun, Wenxin Ji","doi":"10.1016/j.microc.2024.111569","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111569","url":null,"abstract":"Exploration and development of novel chromatographic stationary phases is an effective way to improve the separation efficiency of geometric isomers with similar physicochemical properties. Covalent organic frameworks (COFs) are a new class of porous organic polymers that show a wide range of applications in the field of separation science due to their tunable geometries and functionalities, infinitely extended network structures, and abundant interaction sites. However, the common imine-bonded COFs are poorly resistant to hydrolysis in HPLC. In this work, 2,4,6-trimethyl-1,3,5-triazine (TMT) and 1,3,5-tris (4-formylphenyl) triazine (TFPT) were used as raw materials, a sp carbon-conjugated covalent organic framework (spc-COF) was synthesized through self-assembly monolayer-assisted surface-initiated Schiff-base-mediated hydroxyl-aldehyde condensation reaction, and loaded on the surface of silica substrate with a CN bond to obtain a new segregated material (SiO@spc-COF). SiO@spc-COF was used as a high-performance liquid chromatography (HPLC) packing material for the separation of geometric isomers. Benefitting from its superb in-plane π-conjugation, highly ordered and robust framework structure, high chemical and thermal stability of spc-COF, and the unique hydrophilic covalent triazine groups, hydrophobic benzene rings and other groups that can provide a variety of interactions such as hydrophobicity, π-π stacking, hydrogen bonding and hydrophilicity of the prepared SiO@spc-COF stationary phases, they exhibit excellent molecular shape selectivity and resolution in separating geometrical isomers. These geometric isomers include isomers such as polycyclic aromatic hydrocarbons (PAHs), tocopherols, carotenoids, diethylstilbestrol, 1,4-cyclohexanediol and astaxanthin. Compared to commercial C columns, this column has more flexible selectivity and higher separation performance. In addition, due to the introduction of hydrophobicity, π-π stacking action and hydrophilic triazine components, the SiO@spc-COF stationary phase also has RPLC/HILIC mixed mode characteristics. Baseline separations of monosubstituted benzenes, alkylbenzenes, positional isomers, sulfonamides, benzoic acid, anilines, nucleosides and nucleobases compounds were achieved on SiO@spc-COF packed columns. This successful application highlights the great potential of spc-COF for the separation of geometrical isomers, and provides a way to overcome the stability of common imine-bonded COFs materials in HPLC, as well as to compensate for the shortcomings and deficiencies of a single chromatographic mode in the separation of complex samples. Furthermore, this is the first report of a practical separation of important geometrical isomers using spc-COF materials.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212490","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}
Kynurenic acid (KYNA) is an endogenous tryptophan (Try) metabolite that has anticonvulsant and neuroprotective activities. Many diseases and disorders have been attributed to the kynurenine pathway, including Alzheimer’s disease, amyotrophic lateral sclerosis, Huntington’s disease, AIDS dementia complex, malaria, cancer, depression, and schizophrenia, where tryptophan and kynurenine imbalances have been found. In addition to that, screening of environmental pollutants, especially nitrobenzene (NB) from wastewater discharges, is an essential aspect of governmental and commercial company observation. NB is prolonged exposure causes major harm to human health and environmental disruption. As a result, the development of innovative sensors capable of detecting KYNA and NB traces in blood serum and water, respectively, is important. This work proposes an innovative electrochemical clinical and environmental based sensor for KYNA and NB detection and that is based on a graphitic carbon nitride (GCN)-conducting oligomer composite fabricated glassy carbon (GC) electrode. Melamine was directly pyrolyzed to yield the GCN used in this study. The prepared exfoliated GCN (E-GCN) has a sheet-like structure, demonstrated by the scanning electron microscopy (SEM) image and the Energy-dispersive X-ray analysis (EDAX) analysis confirmed the elemental composition. The potentiodynamic technique was used to create the E-GCN composite with oligo 3-amino-5-mercapto-1,2,4-triazole (AMTa). E-GCN-oligomer composites were successfully formed, as evidenced by additional analysis of the developed composites performed utilizing SEM, X-ray diffraction spectroscopy (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FT-IR) and X-ray photoelectron spectroscopy (XPS) techniques. The electrochemical impedance spectroscopy (EIS) studies demonstrate that the electron transfer reaction was easier at the GC/E-GCN-oligo AMTa electrode than it was at the bare GC, GC/GCN, and GC/oligo AMTa electrodes. The electrocatalytic activity of GCN, oligo AMTa, and GCN-oligo AMTa fabricatedelectrodes regardingthe oxidation of KYNA and reduction of NB was investigated further. Contrasting the E-GCN-oligo AMTa modified electrode to the bare GC, E-GCN, and oligo AMTa modified electrodes, it was discovered that the latter two exhibited lower electrocatalytic activity towards the oxidation of KYNA and reduction of NB. The enhanced electrocatalytic activity of KYNA and NB at the fabricatedE-GCN-oligo AMTa electrode was ascribed to its improved conductivity, greater electroactive surface area, and faster electron transfer rate. Then the developed bio and environmental sensors identified KYNA and NB within a range of 1 nM to 0.5 mM KYNA and 80 nM to 1 mM NB, with limits of detection of 1.8 × 10 M and 3.7 10 M, respectively. The suggested approach was implemented to use by analyzing KYNA in human blood serum and NB in lake water samples.
犬尿氨酸（Kynurenic acid，KYNA）是一种内源性色氨酸（Try）代谢物，具有抗惊厥和神经保护活性。许多疾病和失调都与犬尿氨酸途径有关，包括阿尔茨海默病、肌萎缩性脊髓侧索硬化症、亨廷顿氏病、艾滋病痴呆综合症、疟疾、癌症、抑郁症和精神分裂症，在这些疾病和失调中都发现了色氨酸和犬尿氨酸的失衡。此外，筛查环境污染物，尤其是废水排放中的硝基苯（NB），是政府和商业公司观察的一个重要方面。长期接触硝基苯会对人体健康和环境造成严重危害。因此，开发能够分别检测血清和水中 KYNA 和 NB 痕量的创新传感器非常重要。本研究提出了一种用于检测 KYNA 和 NB 的创新型临床和环境电化学传感器，该传感器基于石墨氮化碳（GCN）-导电低聚物复合材料制成的玻璃碳（GC）电极。本研究中使用的氮化石墨是直接热解三聚氰胺得到的。扫描电子显微镜（SEM）图像显示，制备的剥离 GCN（E-GCN）具有片状结构，能量色散 X 射线分析（EDAX）证实了其元素组成。利用电位动力学技术制造了 E-GCN 与 3-氨基-5-巯基-1,2,4-三唑（AMTa）寡聚体的复合材料。利用扫描电子显微镜（SEM）、X 射线衍射光谱（XRD）、衰减全反射-傅立叶变换红外光谱（ATR-FT-IR）和 X 射线光电子能谱（XPS）技术对所开发的复合材料进行了补充分析，证明 E-GCN-oligomer 复合材料已成功形成。电化学阻抗谱（EIS）研究表明，与裸 GC、GC/GCN 和 GC/oligo AMTa 电极相比，GC/E-GCN-oligo AMTa 电极更容易发生电子转移反应。进一步研究了 GCN、低聚 AMTa 和 GCN-oligo AMTa 制成的电极对 KYNA 氧化和 NB 还原的电催化活性。将 E-GCN-oligo AMTa 改性电极与裸 GC、E-GCN 和寡 AMTa 改性电极进行对比，发现后两者对 KYNA 氧化和 NB 还原的电催化活性较低。在 E-GCN-oligo AMTa 制成的电极上，KYNA 和 NB 的电催化活性得到了增强，这归因于它具有更好的导电性、更大的电活性表面积和更快的电子传递速率。然后，所开发的生物和环境传感器可在 1 nM 至 0.5 mM KYNA 和 80 nM 至 1 mM NB 的范围内识别 KYNA 和 NB，检测限分别为 1.8 × 10 M 和 3.7 10 M。所建议的方法通过分析人体血清中的 KYNA 和湖水样本中的 NB 实现了应用。
{"title":"Novel electrochemical platforms for the detection of both clinical disorder biomarker and environmental pollutants using graphitic carbon nitride-conducting oligomer composites","authors":"Veeramani Mangala Gowri, K. Hemkumar, Jeerawan Khumphon, Theelada Panleam, Sirikanjana Thongmee","doi":"10.1016/j.microc.2024.111555","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111555","url":null,"abstract":"Kynurenic acid (KYNA) is an endogenous tryptophan (Try) metabolite that has anticonvulsant and neuroprotective activities. Many diseases and disorders have been attributed to the kynurenine pathway, including Alzheimer’s disease, amyotrophic lateral sclerosis, Huntington’s disease, AIDS dementia complex, malaria, cancer, depression, and schizophrenia, where tryptophan and kynurenine imbalances have been found. In addition to that, screening of environmental pollutants, especially nitrobenzene (NB) from wastewater discharges, is an essential aspect of governmental and commercial company observation. NB is prolonged exposure causes major harm to human health and environmental disruption. As a result, the development of innovative sensors capable of detecting KYNA and NB traces in blood serum and water, respectively, is important. This work proposes an innovative electrochemical clinical and environmental based sensor for KYNA and NB detection and that is based on a graphitic carbon nitride (GCN)-conducting oligomer composite fabricated glassy carbon (GC) electrode. Melamine was directly pyrolyzed to yield the GCN used in this study. The prepared exfoliated GCN (E-GCN) has a sheet-like structure, demonstrated by the scanning electron microscopy (SEM) image and the Energy-dispersive X-ray analysis (EDAX) analysis confirmed the elemental composition. The potentiodynamic technique was used to create the E-GCN composite with oligo 3-amino-5-mercapto-1,2,4-triazole (AMTa). E-GCN-oligomer composites were successfully formed, as evidenced by additional analysis of the developed composites performed utilizing SEM, X-ray diffraction spectroscopy (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FT-IR) and X-ray photoelectron spectroscopy (XPS) techniques. The electrochemical impedance spectroscopy (EIS) studies demonstrate that the electron transfer reaction was easier at the GC/E-GCN-oligo AMTa electrode than it was at the bare GC, GC/GCN, and GC/oligo AMTa electrodes. The electrocatalytic activity of GCN, oligo AMTa, and GCN-oligo AMTa fabricatedelectrodes regardingthe oxidation of KYNA and reduction of NB was investigated further. Contrasting the E-GCN-oligo AMTa modified electrode to the bare GC, E-GCN, and oligo AMTa modified electrodes, it was discovered that the latter two exhibited lower electrocatalytic activity towards the oxidation of KYNA and reduction of NB. The enhanced electrocatalytic activity of KYNA and NB at the fabricatedE-GCN-oligo AMTa electrode was ascribed to its improved conductivity, greater electroactive surface area, and faster electron transfer rate. Then the developed bio and environmental sensors identified KYNA and NB within a range of 1 nM to 0.5 mM KYNA and 80 nM to 1 mM NB, with limits of detection of 1.8 × 10 M and 3.7 10 M, respectively. The suggested approach was implemented to use by analyzing KYNA in human blood serum and NB in lake water samples.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212503","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}
Imazalil is an imidazole fungicide that controls fruit diseases by inhibiting ergosterol synthesis but has resulted in residues in food. There is a need to develop rapid immunoassays suitable for food safety monitoring and primary screening of large samples. The development of high-performance antibodies represents a pivotal front-end process in the establishment of immuno-rapid assays for harmful small molecules. This study innovatively adopted a hapten preparation strategy by introducing a quaternary ammonium cationic arm to enhance specific immune responses without exposing the common fragment imidazole ring. Theoretical chemistry techniques, including electrostatic potential, lipophilic potential, molecular structure superposition, and frontier molecular orbital energy gap-based molecular softness, were used to analyze the structural features of the quaternary ammonium cationic hapten IMZ-A. The results showed that IMZ-A retained imazalil’s microelectronic and macroscopic three-dimensional spatial superposition structures and showed increased softness for higher bioreactivity. The obtained imazalil monoclonal antibody demonstrates high specificity and sensitivity, with an IC of 1.96 ng mL. A colloidal gold immunochromatographic assay was developed, detecting imazalil residues in fruit samples within 7 min, with a qLOD of 0.57–2.05 ng mL and an IC of 3.67–12.41 ng mL in citrus, apple, and banana samples. This work offers a convenient and highly sensitive immunoassay for large-scale detection of trace imazalil residues. More significantly, it provides a novel and general design idea for hapten, namely, introducing cations into hapten molecules to improve their specific immune potential.
{"title":"Novel cation-based hapten design strategy and development of a monoclonal antibody-based immunochromatographic assay strip for highly specific detection of imazalil: Theoretical chemical insights","authors":"Tong Wang, Yongyi Zhang, Zhizhou Ling, Ying He, Jinyi Yang, Yuanxin Tian, Yu Wang, Hong Wang, Zhenlin Xu, Yuanming Sun, Yudong Shen","doi":"10.1016/j.microc.2024.111576","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111576","url":null,"abstract":"Imazalil is an imidazole fungicide that controls fruit diseases by inhibiting ergosterol synthesis but has resulted in residues in food. There is a need to develop rapid immunoassays suitable for food safety monitoring and primary screening of large samples. The development of high-performance antibodies represents a pivotal front-end process in the establishment of immuno-rapid assays for harmful small molecules. This study innovatively adopted a hapten preparation strategy by introducing a quaternary ammonium cationic arm to enhance specific immune responses without exposing the common fragment imidazole ring. Theoretical chemistry techniques, including electrostatic potential, lipophilic potential, molecular structure superposition, and frontier molecular orbital energy gap-based molecular softness, were used to analyze the structural features of the quaternary ammonium cationic hapten IMZ-A. The results showed that IMZ-A retained imazalil’s microelectronic and macroscopic three-dimensional spatial superposition structures and showed increased softness for higher bioreactivity. The obtained imazalil monoclonal antibody demonstrates high specificity and sensitivity, with an IC of 1.96 ng mL. A colloidal gold immunochromatographic assay was developed, detecting imazalil residues in fruit samples within 7 min, with a qLOD of 0.57–2.05 ng mL and an IC of 3.67–12.41 ng mL in citrus, apple, and banana samples. This work offers a convenient and highly sensitive immunoassay for large-scale detection of trace imazalil residues. More significantly, it provides a novel and general design idea for hapten, namely, introducing cations into hapten molecules to improve their specific immune potential.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212500","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 : 2024-09-06DOI: 10.1016/j.microc.2024.111550
D. Castro-Reigía, I. García, S. Sanllorente, L.A. Sarabia, M.C. Ortiz
This paper deals with the application of near infrared spectroscopy (NIR) in a classification problem involving multiple classes in order to differentiate contaminated olives. A total of 452 samples, ripe and unripe, were treated with five different agrochemicals reproducing the traditional fumigation process in the olive tree. The main objective was to differentiate through a classification if the samples were or were not treated, but also, which chemical was used for each olive. Firstly, Partial Least Squares-Discriminant Analysis (PLS-DA) was performed to differentiate between untreated and treated samples. Then, two novel chemometric approaches, a classification one and a modelling one, were applied for ripe and unripe olives, achieving good results and determining with which chemical were the olives sprinkled with. For the classification of the samples in the six different classes (untreated olives, or treated with one of the five agrochemicals), an Automatic Hierarchical Model Builder (AHIMBU) was used, applying sequential binary PLS-DAs. Nevertheless, for the modelling approach, a compliant model, PLS2-CM, also based on PLS, was used with two different codifications for the classes: i) the classic and well-known One Versus All (OVA), and ii) the Error Correction Output Code (ECOC) optimal matrix. The final global results were evaluated using the Diagonal Modified Confusion Entropy (DMCEN) index, which ranges between 0 and 1, and is very sensitive to changes in the sensitivity–specificity matrices (note that the lower the DMCEN, the better the classification is). The best DMCEN value in prediction for unripe olives, 0.4898, was obtained for the PLS2-CM-ECOC, while 0.6937 and 0.7705 DMCEN values were obtained for AHIMBU and PLS2-CM-OVA, respectively. For the case of the ripe samples, the DMCEN values in prediction were better than the ones for the unripe olives: 0.6016, 0.5051, and 0.4166, for AHIMBU, PLS2-CM-OVA and PLS2-CM-ECOC, respectively. In every case, the best DMCEN has been obtained with the PLS2-CM-ECOC procedure.
{"title":"Differentiating five agrochemicals used in the treatment of intact olives by means of NIR spectroscopy, discriminant analysis and compliant class models","authors":"D. Castro-Reigía, I. García, S. Sanllorente, L.A. Sarabia, M.C. Ortiz","doi":"10.1016/j.microc.2024.111550","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111550","url":null,"abstract":"This paper deals with the application of near infrared spectroscopy (NIR) in a classification problem involving multiple classes in order to differentiate contaminated olives. A total of 452 samples, ripe and unripe, were treated with five different agrochemicals reproducing the traditional fumigation process in the olive tree. The main objective was to differentiate through a classification if the samples were or were not treated, but also, which chemical was used for each olive. Firstly, Partial Least Squares-Discriminant Analysis (PLS-DA) was performed to differentiate between untreated and treated samples. Then, two novel chemometric approaches, a classification one and a modelling one, were applied for ripe and unripe olives, achieving good results and determining with which chemical were the olives sprinkled with. For the classification of the samples in the six different classes (untreated olives, or treated with one of the five agrochemicals), an Automatic Hierarchical Model Builder (AHIMBU) was used, applying sequential binary PLS-DAs. Nevertheless, for the modelling approach, a compliant model, PLS2-CM, also based on PLS, was used with two different codifications for the classes: i) the classic and well-known One Versus All (OVA), and ii) the Error Correction Output Code (ECOC) optimal matrix. The final global results were evaluated using the Diagonal Modified Confusion Entropy (DMCEN) index, which ranges between 0 and 1, and is very sensitive to changes in the sensitivity–specificity matrices (note that the lower the DMCEN, the better the classification is). The best DMCEN value in prediction for unripe olives, 0.4898, was obtained for the PLS2-CM-ECOC, while 0.6937 and 0.7705 DMCEN values were obtained for AHIMBU and PLS2-CM-OVA, respectively. For the case of the ripe samples, the DMCEN values in prediction were better than the ones for the unripe olives: 0.6016, 0.5051, and 0.4166, for AHIMBU, PLS2-CM-OVA and PLS2-CM-ECOC, respectively. In every case, the best DMCEN has been obtained with the PLS2-CM-ECOC procedure.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212504","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 : 2024-09-06DOI: 10.1016/j.microc.2024.111593
Marwa R. El-Zahry
Herein, the current study describes a simple and low-cost electrochemical platform for simultaneous estimation of diclofenac sodium (DCF) and posaconazole (POS) that is proved to be effective treatment of fungal mycetoma. Molybdenum-doped graphene oxide nanorods anchored carbon sphere-doped vanadium oxide nanocomposites were developed using co-precipitation method. The electrochemical measurements were conducted using square wave voltammetric (SWV) technique in optimal conditions. The designed modified electrode showed excellent voltammetric responses towards DCF and POS with 0.18 V difference in the oxidation peak potentials, making the developed modified nano-sensor suitable for simultaneous determination of the interested compounds. The physico-chemical properties of the fabricated nanocomposites were characterized by cyclic voltammetry, scanning electron microscope, powder X-ray diffraction, infrared spectroscopy, and electrochemical impedance spectroscopy. In terms of low limits of detection (LOD) 10.2 nM DCF and 3.81 nM POS, the established voltammetric sensor provided worthy analytical behavior for sensing DCF and POS. The applicability of the designed senor was effectively presented in the spiked human urine and plasma samples.
{"title":"Electrochemical sensor based on molybdenum-doped graphene oxide nanorods anchored carbon spheres/vanadium pentoxide nanocomposites for simultaneous determination of diclofenac sodium and posaconazole","authors":"Marwa R. El-Zahry","doi":"10.1016/j.microc.2024.111593","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111593","url":null,"abstract":"Herein, the current study describes a simple and low-cost electrochemical platform for simultaneous estimation of diclofenac sodium (DCF) and posaconazole (POS) that is proved to be effective treatment of fungal mycetoma. Molybdenum-doped graphene oxide nanorods anchored carbon sphere-doped vanadium oxide nanocomposites were developed using co-precipitation method. The electrochemical measurements were conducted using square wave voltammetric (SWV) technique in optimal conditions. The designed modified electrode showed excellent voltammetric responses towards DCF and POS with 0.18 V difference in the oxidation peak potentials, making the developed modified nano-sensor suitable for simultaneous determination of the interested compounds. The physico-chemical properties of the fabricated nanocomposites were characterized by cyclic voltammetry, scanning electron microscope, powder X-ray diffraction, infrared spectroscopy, and electrochemical impedance spectroscopy. In terms of low limits of detection (LOD) 10.2 nM DCF and 3.81 nM POS, the established voltammetric sensor provided worthy analytical behavior for sensing DCF and POS. The applicability of the designed senor was effectively presented in the spiked human urine and plasma samples.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212498","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 : 2024-09-06DOI: 10.1016/j.microc.2024.111571
Iare Soares Ribeiro, Tatianny de Araujo Andrade, Tiago Almeida Silva, Márcio José da Silva, Jemmyson Romário de Jesus
The neurotransmitter dopamine (DA) plays a crucial role as a messenger in the brain and various organs. Assessing DA levels in biological fluids is critical to identifying stress-related disorders, substance abuse, and neurochemical imbalances. Monitoring DA levels in urine and saliva samples is crucial for diagnosing neurological disorders. In this study, we successfully synthesized and confirmed a novel electrochemical sensor based on the coordination compound Cobalt-benzenedicarboxylate, [Co(BDC)], through extensive characterization via Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDS) and Thermogravimetric Analysis (TGA) analyses. Using this material, it was developed an electrochemical sensor ([Co(BDC)]/CPE) for DA detection from biological samples (urine and saliva). After optimizing the main parameters, DA was detected using an electrode modified with 25 % (m/m) [Co(BDC)] in pH 6 solution, with an applied potential increment of 5 mV, a frequency of 75 Hz and a amplitude of 100 mV. The sensor demonstrated satisfactory performance in urine samples with limit of detection (LOD) and limit of quantification (LOQ) of 1.7 μmol/L and 5.7 μmol/L, respectively. In saliva samples, the LOD and LOQ were 0.5 μmol/L and 1.7 μmol/L, respectively, with good linearity (R > 0.9922), indicating a strong linear relationship between analyte concentration and sensor response. Recovery rates between 84.9 % and 97.1 % indicate the reliable accuracy of the modified electrode in detecting DA, with relative standard deviation (RSD) < 8.0 % (n = 3) in complex samples. This method shows potential for practical applications in analyzing real samples contributing for diagnosing neurological diseases associated with this neurotransmitter.
{"title":"Electrochemical sensor based on coordination compound [Co(BDC)]n allows detection of catecholamine neurotransmitter associated with neurological disorder from biological samples","authors":"Iare Soares Ribeiro, Tatianny de Araujo Andrade, Tiago Almeida Silva, Márcio José da Silva, Jemmyson Romário de Jesus","doi":"10.1016/j.microc.2024.111571","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111571","url":null,"abstract":"The neurotransmitter dopamine (DA) plays a crucial role as a messenger in the brain and various organs. Assessing DA levels in biological fluids is critical to identifying stress-related disorders, substance abuse, and neurochemical imbalances. Monitoring DA levels in urine and saliva samples is crucial for diagnosing neurological disorders. In this study, we successfully synthesized and confirmed a novel electrochemical sensor based on the coordination compound Cobalt-benzenedicarboxylate, [Co(BDC)], through extensive characterization via Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDS) and Thermogravimetric Analysis (TGA) analyses. Using this material, it was developed an electrochemical sensor ([Co(BDC)]/CPE) for DA detection from biological samples (urine and saliva). After optimizing the main parameters, DA was detected using an electrode modified with 25 % (m/m) [Co(BDC)] in pH 6 solution, with an applied potential increment of 5 mV, a frequency of 75 Hz and a amplitude of 100 mV. The sensor demonstrated satisfactory performance in urine samples with limit of detection (LOD) and limit of quantification (LOQ) of 1.7 μmol/L and 5.7 μmol/L, respectively. In saliva samples, the LOD and LOQ were 0.5 μmol/L and 1.7 μmol/L, respectively, with good linearity (R > 0.9922), indicating a strong linear relationship between analyte concentration and sensor response. Recovery rates between 84.9 % and 97.1 % indicate the reliable accuracy of the modified electrode in detecting DA, with relative standard deviation (RSD) < 8.0 % (n = 3) in complex samples. This method shows potential for practical applications in analyzing real samples contributing for diagnosing neurological diseases associated with this neurotransmitter.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212501","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 : 2024-09-06DOI: 10.1016/j.microc.2024.111586
Ahmed Emad F. Abbas, Mohammed Gamal, Ibrahim A. Naguib, Michael K. Halim, Basmat Amal M. Said, Mohammed M. Ghoneim, Mohmeed M.A. Mansour, Yomna A. Salem
This study presents an innovative, sustainable approach for the simultaneous quantification of glycopyrronium (2–14 μg/mL), indacaterol (6–18 μg/mL), and mometasone (4–20 μg/mL) in a recently approved fixed-dose breezhaler formulations and biological fluids, along with two genotoxic impurities: methyl -toluene sulfonate (2–10 μg/mL) and 4-dimethylamino pyridine (2–10 μg/mL). We developed robust UV spectrophotometric machine-learning chemometric models to address the limitations of existing chromatographic methods. The calibration set was carefully selected at five concentration levels using the multilevel-multifactor experimental design, resulting in 25 calibration mixtures. The Kennard-Stone Clustering Algorithm was employed to construct a representative 13-mixture validation set, overcoming biases associated with random data splitting. Five chemometric models (CLS, PCR, PLS, GA-PLS, and MCR-ALS) were rigorously evaluated, with MCR-ALS demonstrating superior performance. This model achieved 98–102 % recovery percentages for all analytes, with low root mean square error of calibration and prediction of (RMSEC: 0.0225 to 0.5246) and (RMSEP: 0.0039 to 0.4226). The method exhibited excellent relative root mean square error of prediction (RRMSEP: 0.1306 to 0.8517 %), a negligible bias-corrected mean square error of prediction (BCMSEP: −0.0073 to 0.0025), and good sensitivity (LOD: 0.022 to 0.893 μg/mL) across all analytes. Green solvents were selected using the Green Solvents Selection Tool and Greenness Index Spider Charts. The method’s sustainability was comprehensively evaluated using seven state-of-the-art assessment tools. This approach not only offers a green alternative to traditional chromatographic methods but also ensures high accuracy in quantifying both active ingredients and genotoxic impurities, thereby enhancing pharmaceutical quality control and patient safety.
{"title":"Sustainable quantification of glycopyrronium, indacaterol, and mometasone along with two genotoxic impurities in a recently approved fixed-dose breezhaler formulations and biological fluids: A machine learning-augmented UV-spectroscopic approach","authors":"Ahmed Emad F. Abbas, Mohammed Gamal, Ibrahim A. Naguib, Michael K. Halim, Basmat Amal M. Said, Mohammed M. Ghoneim, Mohmeed M.A. Mansour, Yomna A. Salem","doi":"10.1016/j.microc.2024.111586","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111586","url":null,"abstract":"This study presents an innovative, sustainable approach for the simultaneous quantification of glycopyrronium (2–14 μg/mL), indacaterol (6–18 μg/mL), and mometasone (4–20 μg/mL) in a recently approved fixed-dose breezhaler formulations and biological fluids, along with two genotoxic impurities: methyl -toluene sulfonate (2–10 μg/mL) and 4-dimethylamino pyridine (2–10 μg/mL). We developed robust UV spectrophotometric machine-learning chemometric models to address the limitations of existing chromatographic methods. The calibration set was carefully selected at five concentration levels using the multilevel-multifactor experimental design, resulting in 25 calibration mixtures. The Kennard-Stone Clustering Algorithm was employed to construct a representative 13-mixture validation set, overcoming biases associated with random data splitting. Five chemometric models (CLS, PCR, PLS, GA-PLS, and MCR-ALS) were rigorously evaluated, with MCR-ALS demonstrating superior performance. This model achieved 98–102 % recovery percentages for all analytes, with low root mean square error of calibration and prediction of (RMSEC: 0.0225 to 0.5246) and (RMSEP: 0.0039 to 0.4226). The method exhibited excellent relative root mean square error of prediction (RRMSEP: 0.1306 to 0.8517 %), a negligible bias-corrected mean square error of prediction (BCMSEP: −0.0073 to 0.0025), and good sensitivity (LOD: 0.022 to 0.893 μg/mL) across all analytes. Green solvents were selected using the Green Solvents Selection Tool and Greenness Index Spider Charts. The method’s sustainability was comprehensively evaluated using seven state-of-the-art assessment tools. This approach not only offers a green alternative to traditional chromatographic methods but also ensures high accuracy in quantifying both active ingredients and genotoxic impurities, thereby enhancing pharmaceutical quality control and patient safety.","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212499","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 : 2024-09-06DOI: 10.1016/j.microc.2024.111595
Dan Zhao, Jianqin Gan, Wei Xiong, Miaoxiu Ge, Hang Su, Xiangyu Wang, Xiangyu Kong, Hongping Zeng, Xiaoming Du, Luhong Wen
Acute pesticide poisoning can cause several symptoms that threaten life safety, and the development of a rapid detection method is conducive to identifying toxicants early. In this work, we proposed a facile post-modification method to fabricate functional metal-organic frameworks (UIO-66-Py) with high specific surface area, stability and target recognition sites. UIO-66-Py-coated extraction bar could be fabricated by using PDMS as a “solid glue” to immobilize UIO-66-Py, where UIO-66-Py interpenetrated into PDMS uniformly to form functional film. The UIO-66-Py-coated extraction bar could work as an efficient solid-phase microextraction device for extraction of toxicants (pesticides) in the fetal bovine serum, which ascribed to great binding energy between UIO-66-Py and pesticides. Moreover, the immobilized membrane fabricated by PDMS would increase penetration of pesticides and diffusion path, thus promoting the retention of pesticides to afford more affinity sites for capturing pesticides. In addition, rotation speed, extraction time, elution solvent, and desorption time were investigated to achieve excellent recovery, and the corresponding optimal conditions were 200 rpm, 10 min, methanol, and 3 min, respectively. Through the established quantitative method, low limit of detections (LODs) of 0.15 − 0.37 ng/mL with relative standard deviations (RSDs) of less than 4.5 %, and linear correlation coefficients (R ) of 0.99 for these pesticides were achieved. The proposed on-site detection method exhibited an excellent performance with great sensitivity, anti-interference, and reusability, which demonstrated that synergistic effect from UIO-66-Py and PDMS facilitated highly sensitive detection and selective extraction. The findings in this work develop efficient detection methods for toxicants in biological sample and provide deep insights to further improve treatment efficiency of pesticide poisoning and afford a great potential in clinical point-of-care testing (POCT).
{"title":"Preparation and characterization of functional metal–organic frameworks-coated extraction bars and their application in the simultaneous determination of pesticides in fetal bovine serum","authors":"Dan Zhao, Jianqin Gan, Wei Xiong, Miaoxiu Ge, Hang Su, Xiangyu Wang, Xiangyu Kong, Hongping Zeng, Xiaoming Du, Luhong Wen","doi":"10.1016/j.microc.2024.111595","DOIUrl":"https://doi.org/10.1016/j.microc.2024.111595","url":null,"abstract":"Acute pesticide poisoning can cause several symptoms that threaten life safety, and the development of a rapid detection method is conducive to identifying toxicants early. In this work, we proposed a facile post-modification method to fabricate functional metal-organic frameworks (UIO-66-Py) with high specific surface area, stability and target recognition sites. UIO-66-Py-coated extraction bar could be fabricated by using PDMS as a “solid glue” to immobilize UIO-66-Py, where UIO-66-Py interpenetrated into PDMS uniformly to form functional film. The UIO-66-Py-coated extraction bar could work as an efficient solid-phase microextraction device for extraction of toxicants (pesticides) in the fetal bovine serum, which ascribed to great binding energy between UIO-66-Py and pesticides. Moreover, the immobilized membrane fabricated by PDMS would increase penetration of pesticides and diffusion path, thus promoting the retention of pesticides to afford more affinity sites for capturing pesticides. In addition, rotation speed, extraction time, elution solvent, and desorption time were investigated to achieve excellent recovery, and the corresponding optimal conditions were 200 rpm, 10 min, methanol, and 3 min, respectively. Through the established quantitative method, low limit of detections (LODs) of 0.15 − 0.37 ng/mL with relative standard deviations (RSDs) of less than 4.5 %, and linear correlation coefficients (R ) of 0.99 for these pesticides were achieved. The proposed on-site detection method exhibited an excellent performance with great sensitivity, anti-interference, and reusability, which demonstrated that synergistic effect from UIO-66-Py and PDMS facilitated highly sensitive detection and selective extraction. The findings in this work develop efficient detection methods for toxicants in biological sample and provide deep insights to further improve treatment efficiency of pesticide poisoning and afford a great potential in clinical point-of-care testing (POCT).","PeriodicalId":391,"journal":{"name":"Microchemical Journal","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142212497","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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