{"title":"层状多孔共价有机框架掺杂整体柱用于微升血液中非甾体抗炎药的在线芯片阵列微萃取","authors":"Qiulin Zhang, Beibei Chen, Man He, Bin Hu","doi":"10.1016/j.aca.2024.343332","DOIUrl":null,"url":null,"abstract":"<h3>Background</h3>Traditional blood drug analysis involves large blood consumption and complicated operations and a further reduction in blood consumption is urgently needed. Chip-based monolithic column microextraction is a good strategy for the pretreatment of small-volume samples, and new monolithic materials is the critical factor. Covalent organic frameworks (COFs) are good adsorbents due to large specific surface area and rich conjugated structure. However, the poor dispersion ability of COFs in prepolymer solution severely hinders the preparation of COFs doped monolithic columns. Herein, high internal phase emulsion with viscoelastic properties was adopted to fixed COF particles.<h3>Results</h3>The COFs doped monolith exhibited a hierarchical porous structure and improved extraction efficiency for interest nonsteroidal anti-inflammatory drugs (NSAIDs) (68.2-77.3 <em>vs</em> 28.4-57.7%). A chip-based monolithic column array was fabricated and coupled with high-performance liquid chromatography (HPLC)-ultraviolet detection for online determination of five NSAIDs in microlitre volume of blood. The throughput of the developed method was approximately 3 h<sup>-1</sup>, mainly determined by the separation time (22 min) of target NSAIDs in HPLC. Under the optimal conditions (200 μL sample solution, pH=3 at a sampling folw rate of 5 μL min<sup>-1</sup> and 20 μL of acetonitrile/10 mmol L<sup>-1</sup> NaOH (9/1, v/v) as desorbent), the detection limit of 4.39-15.5 μg L<sup>-1</sup> was obtained for target NSAIDs in blood with RSD of 7.8-15.3% and R<sup>2</sup> of 0.9943-0.9978. The method was applied to the analysis of human serum (20 μL) and dried blood spot, with recovery of 82.0-118% for target NSAIDs.<h3>Significance</h3>A method was proposed for the preparation of COF doped monolithic columns by emulsion polymerization, avoiding uneven distribution of COFs caused by their easy sedimentation in traditional free radical preparation of monolithic columns. Then a chip-based monolithic column array coupled with on-line HPLC-UV detection was established for the quantification of five NSAIDs in microlitre-blood samples. The developed method merits high automation and good anti-interference ability, with extremely low sample/reagents consumption.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":5.7000,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hierarchically porous covalent organic framework doped monolithic column for on-line chip-based array microextraction of nonsteroidal anti-inflammatory drugs in microlitre volume of blood\",\"authors\":\"Qiulin Zhang, Beibei Chen, Man He, Bin Hu\",\"doi\":\"10.1016/j.aca.2024.343332\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<h3>Background</h3>Traditional blood drug analysis involves large blood consumption and complicated operations and a further reduction in blood consumption is urgently needed. Chip-based monolithic column microextraction is a good strategy for the pretreatment of small-volume samples, and new monolithic materials is the critical factor. Covalent organic frameworks (COFs) are good adsorbents due to large specific surface area and rich conjugated structure. However, the poor dispersion ability of COFs in prepolymer solution severely hinders the preparation of COFs doped monolithic columns. Herein, high internal phase emulsion with viscoelastic properties was adopted to fixed COF particles.<h3>Results</h3>The COFs doped monolith exhibited a hierarchical porous structure and improved extraction efficiency for interest nonsteroidal anti-inflammatory drugs (NSAIDs) (68.2-77.3 <em>vs</em> 28.4-57.7%). A chip-based monolithic column array was fabricated and coupled with high-performance liquid chromatography (HPLC)-ultraviolet detection for online determination of five NSAIDs in microlitre volume of blood. The throughput of the developed method was approximately 3 h<sup>-1</sup>, mainly determined by the separation time (22 min) of target NSAIDs in HPLC. Under the optimal conditions (200 μL sample solution, pH=3 at a sampling folw rate of 5 μL min<sup>-1</sup> and 20 μL of acetonitrile/10 mmol L<sup>-1</sup> NaOH (9/1, v/v) as desorbent), the detection limit of 4.39-15.5 μg L<sup>-1</sup> was obtained for target NSAIDs in blood with RSD of 7.8-15.3% and R<sup>2</sup> of 0.9943-0.9978. The method was applied to the analysis of human serum (20 μL) and dried blood spot, with recovery of 82.0-118% for target NSAIDs.<h3>Significance</h3>A method was proposed for the preparation of COF doped monolithic columns by emulsion polymerization, avoiding uneven distribution of COFs caused by their easy sedimentation in traditional free radical preparation of monolithic columns. Then a chip-based monolithic column array coupled with on-line HPLC-UV detection was established for the quantification of five NSAIDs in microlitre-blood samples. The developed method merits high automation and good anti-interference ability, with extremely low sample/reagents consumption.\",\"PeriodicalId\":240,\"journal\":{\"name\":\"Analytica Chimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.7000,\"publicationDate\":\"2024-10-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Analytica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1016/j.aca.2024.343332\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ANALYTICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Analytica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.aca.2024.343332","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
Hierarchically porous covalent organic framework doped monolithic column for on-line chip-based array microextraction of nonsteroidal anti-inflammatory drugs in microlitre volume of blood
Background
Traditional blood drug analysis involves large blood consumption and complicated operations and a further reduction in blood consumption is urgently needed. Chip-based monolithic column microextraction is a good strategy for the pretreatment of small-volume samples, and new monolithic materials is the critical factor. Covalent organic frameworks (COFs) are good adsorbents due to large specific surface area and rich conjugated structure. However, the poor dispersion ability of COFs in prepolymer solution severely hinders the preparation of COFs doped monolithic columns. Herein, high internal phase emulsion with viscoelastic properties was adopted to fixed COF particles.
Results
The COFs doped monolith exhibited a hierarchical porous structure and improved extraction efficiency for interest nonsteroidal anti-inflammatory drugs (NSAIDs) (68.2-77.3 vs 28.4-57.7%). A chip-based monolithic column array was fabricated and coupled with high-performance liquid chromatography (HPLC)-ultraviolet detection for online determination of five NSAIDs in microlitre volume of blood. The throughput of the developed method was approximately 3 h-1, mainly determined by the separation time (22 min) of target NSAIDs in HPLC. Under the optimal conditions (200 μL sample solution, pH=3 at a sampling folw rate of 5 μL min-1 and 20 μL of acetonitrile/10 mmol L-1 NaOH (9/1, v/v) as desorbent), the detection limit of 4.39-15.5 μg L-1 was obtained for target NSAIDs in blood with RSD of 7.8-15.3% and R2 of 0.9943-0.9978. The method was applied to the analysis of human serum (20 μL) and dried blood spot, with recovery of 82.0-118% for target NSAIDs.
Significance
A method was proposed for the preparation of COF doped monolithic columns by emulsion polymerization, avoiding uneven distribution of COFs caused by their easy sedimentation in traditional free radical preparation of monolithic columns. Then a chip-based monolithic column array coupled with on-line HPLC-UV detection was established for the quantification of five NSAIDs in microlitre-blood samples. The developed method merits high automation and good anti-interference ability, with extremely low sample/reagents consumption.
期刊介绍:
Analytica Chimica Acta has an open access mirror journal Analytica Chimica Acta: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review.
Analytica Chimica Acta provides a forum for the rapid publication of original research, and critical, comprehensive reviews dealing with all aspects of fundamental and applied modern analytical chemistry. The journal welcomes the submission of research papers which report studies concerning the development of new and significant analytical methodologies. In determining the suitability of submitted articles for publication, particular scrutiny will be placed on the degree of novelty and impact of the research and the extent to which it adds to the existing body of knowledge in analytical chemistry.