Ministry of Education Key Laboratory of Analytical Science for Food Safety and Biology, Fujian Provincial Key Laboratory of Analysis and Detection Technology for Food Safety, College of Chemistry, Fuzhou University, Fuzhou, 350116, Fujian, China.
State Key Laboratory of Environmental and Biological Analysis, Department of Chemistry, Hong Kong Baptist University, 224 Waterloo Road, Kowloon Tong, 999077, Hong Kong SAR, China.
Mikrochim Acta. 2020 Jun 5;187(7):370. doi: 10.1007/s00604-020-04340-5.
Core-shell structured magnetic covalent organic framework (FeO@COF) nanospheres were rapidly synthesized at room temperature using the monodisperse FeO nanoparticles (NPs) as magnetic core and benzene-1,3,5-tricarbaldehyde (BTA) and 3,3'-dihydroxybenzidine (DHBD) as two building blocks (denoted as FeO@BTA-DHBD), respectively. They can serve as a mass spectrometry probe for rapid and high-throughput screening of bisphenols (BPs) from pharmaceuticals and personal care products (PPCPs) by surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF-MS). The FeO@BTA-DHBD nanospheres showed some superior features involving average pore size distribution (2.82 nm), high magnetization values (42.5 emu g), high specific surface area (82.96 m g), and good chemical/thermal stability. It was used as both ideal adsorbent for enrichment of BPs and new substrate to assist ionization in SELDI-TOF-MS. The method exhibited good linearity in the range 0.05-4000 ng mL with correlation coefficients (r) higher than 0.9920. Low limits of detection (LODs) (500 pg mL for bisphenol A (BPA), 2 pg mL for bisphenol B (BPB), 28 pg mL for bisphenol C (BPC), 60 pg mL for bisphenol F (BPF), 33 pg mL for bisphenol AF (BPAF), 200 pg mL for bisphenol BP (BPBP), 10 pg mL for bisphenol S (BPS), 90 pg mL for tetrabromobisphenol A (BPA(Br)), and 380 pg mL for tetrabromobisphenol S (BPS(Br))) and good recoveries (80.6-115%) of BPs in PPCPs were achieved. The relative standard deviations (RSDs) of spot-to-spot (n = 10) and sample-to-sample (n = 5) were in the ranges 5-11% and 5-12%, respectively. The dual-function platform was successfully applied to the quantitative determination of BPs in PPCPs. It not only expanded the scope of the application of COFs but also provided an alternative strategy for the determination of hazardous compounds in PPCPs. Graphical abstract Schematic representation of the synthesis of core-shell structured magnetic covalent organic framework nanospheres (FeO@COFs) and its application in the analysis of bisphenols by using FeO@BTA-DHBD nanospheres as a MS probe based on surface-enhanced laser desorption/ionization time-of-flight mass spectrometry.
核壳结构磁性共价有机框架（FeO@COF）纳米球在室温下快速合成，所用的磁性核为单分散的 FeO 纳米颗粒（NPs），而苯-1,3,5-三甲酰基（BTA）和 3,3'-二羟基联苯胺（DHBD）分别作为两个构建块（分别表示为 FeO@BTA-DHBD）。它们可以作为一种质谱探针，通过表面增强激光解吸/电离飞行时间质谱（SELDI-TOF-MS），从药品和个人护理产品（PPCPs）中快速、高通量筛选双酚（BPs）。FeO@BTA-DHBD 纳米球具有一些优异的特性，包括平均孔径分布（2.82nm）、高磁化值（42.5emu/g）、高比表面积（82.96m²/g）和良好的化学/热稳定性。它既可用作 BPs 的理想富集吸附剂，也可用作 SELDI-TOF-MS 中辅助离子化的新型基质。该方法在 0.05-4000ng/mL 范围内表现出良好的线性，相关系数（r）高于 0.992。低检测限（LOD）（500pg/mL 对双酚 A（BPA）、2pg/mL 对双酚 B（BPB）、28pg/mL 对双酚 C（BPC）、60pg/mL 对双酚 F（BPF）、33pg/mL 对双酚 AF（BPAF）、200pg/mL 对双酚 BP（BPBP）、10pg/mL 对双酚 S（BPS）、90pg/mL 对四溴双酚 A（BPA(Br)）和 380pg/mL 对四溴双酚 S（BPS(Br)）），以及 PPCPs 中 BPs 的良好回收率（80.6-115%）。BPs 在 PPCPs 中的 Spot-to-Spot（n=10）和 Sample-to-Sample（n=5）的相对标准偏差（RSD）分别在 5-11%和 5-12%的范围内。双功能平台成功应用于 PPCPs 中 BPs 的定量测定。它不仅扩展了 COFs 的应用范围，还为 PPCPs 中有害化合物的测定提供了一种替代策略。
