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固定化钛(IV)共价有机聚合物的制备及其在弱酸性pH条件下同时富集核苷酸和儿茶酚胺的应用。

Preparation of titanium (IV)-immobilized covalent organic polymer and use for simultaneous enrichment of nucleotides and catecholamines at weakly acidic pH.

作者信息

Wang Yuelin, Zhang Yangyue, Cheng Yan, Shen Jiwei, Wei Yinmao, Wang Chaozhan

机构信息

Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, Shaanxi, China.

Department of Infectious Diseases, Tangdu Hospital, Fourth Military Medical University, Xi'an 710038, Shaanxi, China.

出版信息

J Chromatogr A. 2025 Aug 30;1757:466128. doi: 10.1016/j.chroma.2025.466128. Epub 2025 Jun 5.

DOI:10.1016/j.chroma.2025.466128
PMID:40505360
Abstract

Simultaneous analysis of catecholamines (CAs) and nucleotides (NTs) is very important for early diagnosis of diseases and physiological function monitoring. In this study, a titanium (IV)-immobilized affinity adsorbent, TpBD-(COOH)@AS@Ti, was prepared by functionalizing hydroxyl bearing covalent organic polymer (COP) with alendronate, and the adsorbent was used for simultaneous enrichment of CAs and NTs under weakly acidic conditions (pH 6.0), which can prevent the oxidation of CAs and improve the accuracy of their analysis. Selective adsorption is primarily driven by Ti⁴⁺-mediated coordination. Extraction parameters were systematically optimized, and analytical methods for determination of CAs and NTs in human urine have been established by coupling the TpBD-(COOH)@AS@Ti based dispersive solid phase extraction (dSPE) with HPLC equipped with two tandem detectors of ultraviolet (UV) and fluorescence (FL). With the UV detector, the limits of detections (LODs) of CAs and NTs were 0.17-3.97 ng/mL and 0.32-1.46 ng/mL, respectively. The recoveries in spiked urine were 73.8 %-116.1 % with relative standard deviations (RSDs) below 15 %. Meanwhile, CAs achieved higher sensitivity with LODs of 0.24-0.79 ng/mL when using the FL detector. Therefore, this study has important application potential for providing more comprehensive clinical diagnostic information and early diagnosis of diseases.

摘要

同时分析儿茶酚胺(CAs)和核苷酸(NTs)对于疾病的早期诊断和生理功能监测非常重要。在本研究中,通过用阿仑膦酸盐对含羟基的共价有机聚合物(COP)进行功能化制备了一种固定化钛(IV)亲和吸附剂TpBD-(COOH)@AS@Ti,并将该吸附剂用于在弱酸性条件(pH 6.0)下同时富集CAs和NTs,这可以防止CAs氧化并提高其分析准确性。选择性吸附主要由Ti⁴⁺介导的配位作用驱动。系统优化了萃取参数,并通过将基于TpBD-(COOH)@AS@Ti的分散固相萃取(dSPE)与配备紫外(UV)和荧光(FL)双串联检测器的HPLC联用,建立了测定人尿中CAs和NTs的分析方法。使用UV检测器时,CAs和NTs的检测限(LODs)分别为0.17 - 3.97 ng/mL和0.32 - 1.46 ng/mL。加标尿液中的回收率为73.8% - 116.1%,相对标准偏差(RSDs)低于15%。同时,使用FL检测器时,CAs的检测限为0.24 - 0.79 ng/mL,具有更高的灵敏度。因此,本研究对于提供更全面的临床诊断信息和疾病早期诊断具有重要的应用潜力。

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