Key Laboratory of Analytical Chemistry for Biology and Medicine, Department of Chemistry, Wuhan University , Wuhan 430072, P. R. China.
FI-TRACE group, Department of Chemistry, University of the Balearic Islands , Carretera de Valldemossa, km. 7.5, E-07122 Palma de Mallorca, Spain.
Anal Chem. 2017 Nov 21;89(22):12541-12549. doi: 10.1021/acs.analchem.7b03767. Epub 2017 Oct 31.
In this work, the concept of 3D-printed microflow injection (3D-μFI) embodying a dedicated multifunctional 3D-printed stator onto a rotary microvalve along with a mesofluidic sample preparation platform is proposed for the first time. A transparent 3D-printed stereolithographic mesofluidic chip device accommodating polyaniline (PANI) decorated magnetic nanoparticles (32.5 ± 3.8 mg) is harnessed to in-line sorptive microextraction as a front end to liquid chromatography with peak focusing. As a proof-of-concept application, the 3D-μFI assembly was resorted to matrix cleanup and automatic programmable-flow determination of organic emerging contaminants (4-hydroxybenzoate analogues and triclosan as antimicrobial model analytes) in human saliva and urine samples. By using a sample volume of 1.0 mL with a loading flow rate of 200 μL min, an eluent volume of 120 μL at 80 μL min, and online HPLC injection of 300 μL of the mixture of eluate and Milli-Q water (in a 1:2 ratio) to prevent band broadening effects of the most polar analytes, the limits of detection (3σ criterion) ranged from 1.1 to 4.5 ng mL for methylparaben (MP), ethylparaben (EP), propylparaben (PrP), phenylparaben (PhP), butylparaben (BP), and triclosan (TCS). Enhancement factors of 16-25 were obtained for the target analytes. Spike recoveries ranged from 84 to 117% for both saliva and urine samples. The online 3D-μFI hyphenated method is synchronized with the chromatographic separation and features a chip lifetime of more than 20 injections with minimal losses of moderately nonpolar compounds on the walls of the mesofluidic device.
在这项工作中，首次提出了一种将专用多功能 3D 打印定子嵌入旋转微阀并结合中流体制样平台的 3D 打印微流动注射（3D-μFI）的概念。利用一个透明的 3D 打印立体光刻中流道芯片装置，容纳聚邻苯二胺（PANI）修饰的磁性纳米粒子（32.5 ± 3.8 mg），作为在线吸附微萃取的前端，与高效液相色谱联用，实现峰聚焦。作为概念验证应用，3D-μFI 组件被用于基质净化和自动可编程流动测定人唾液和尿液样品中的有机新兴污染物（4-羟基苯甲酸酯类似物和三氯生作为抗菌模型分析物）。通过使用 1.0 mL 样品体积、200 μL min 的加载流速、120 μL 的洗脱体积和 80 μL min 的流速、以及在线 HPLC 进样 300 μL 洗脱液和 Milli-Q 水（1:2 比例）的混合物，以防止最极性分析物的带宽展宽效应，甲基对羟基苯甲酸酯（MP）、乙基对羟基苯甲酸酯（EP）、丙基对羟基苯甲酸酯（PrP）、对羟基苯甲酸苯酯（PhP）、丁基对羟基苯甲酸酯（BP）和三氯生（TCS）的检出限（3σ 标准）范围为 1.1-4.5ng mL。目标分析物的增强因子为 16-25。唾液和尿液样品的加标回收率范围为 84-117%。在线 3D-μFI 联用方法与色谱分离同步进行，具有超过 20 次注射的芯片寿命，并且在中流道装置的壁上对中等非极性化合物的损失最小。
