Determination of non-steroidal anti-inflammatory drugs in the environmental water samples by a polyvinylimide-modified magnetic nanoparticles-based solid phase extraction coupled with high-performance liquid chromatography
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摘要:
环境水样中非甾体抗炎药（NSAIDs）的长期存在不仅会影响水生生物的生命安全，扰乱生态系统环境，而且会对人类健康构成严重威胁。采用溶剂热法首先制备了氨基功能化Fe3O4纳米粒子（Fe3O4-NH2）。随后，通过室温下水溶液中的席夫碱反应，以戊二醛为交联剂，将具有支链结构的聚乙烯亚胺（PEI）成功地接枝到Fe3O4纳米粒子上，合成了一种可回收的PEI接枝磁性纳米吸附剂（Fe3O4@PEI）并将其应用于环境水中NSAIDs的检测。通过各种表征手段研究了Fe3O4@PEI的组成特性，并对影响NSAIDs萃取效果的参数进行了优化。Fe3O4@PEI对4种NSAIDs具有高吸附性，与高效液相色谱联用可对环境水样中的酮洛芬、萘普生、双氯芬酸和托芬那酸4种NSAIDs进行定量分析，在1～500 µg/mL范围内，色谱峰面积与质量浓度呈良好的线性关系，样品在3种不同添加水平下的加标回收率在85.6%～107.8%，日内精密度均小于7.8%（n=6），日间精密度均小于9.5%（n=3）。该方法操作简单、准确高效，可用于环境水样中非甾体抗炎药的测定。
Abstract:The long-term presence of non-steroidal anti-inflammatory drugs (NSAIDs) in the environmental water samples not only affects the life safety of aquatic organisms and disturbs the ecoenvironment, but also poses a serious threat to human health. In this study, amino-functionalized Fe3O4 nanoparticles (Fe3O4-NH2) were firstly prepared by solvothermal method. Subsequently, polyethyleneimine (PEI) with a branched chain structure was successfully grafted onto Fe3O4 nanoparticles by Schiff base reaction in aqueous solution at room temperature using glutaraldehyde as a cross-linking agent, and a recyclable PEI-grafted magnetic nano-sorbent (Fe3O4@PEI) was synthesized and applied for the detection of NSAIDs in the environmental water samples. The compositional properties of Fe3O4@PEI were investigated by different characterization methods and the parameters affecting the extraction of NSAIDs were optimized. Due to high adsorption of Fe3O4@PEI for NSAIDs, the quantitative analysis of four NSAIDs in the environmental water samples, ketoprofen, naproxen, diclofenac and tolfenamic acid, was performed in combination with high-performance liquid chromatography. A good linear relationship between the chromatographic peak area and concentration was observed in the range of 1−500 µg/mL. The recoveries of the samples at three different spiked levels ranged from 85.6% to 107.8%; the intra-day precision was less than 7.8% (n=6); and the inter-day precision was less than 9.5% (n=3). The method is simple, rapid, accurate and reliable, and can be used for the analysis of NSAIDs in the environmental water samples．
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Figure 1. Results of characterization of relevant materialsResults of characterization of relevant materials A:Ninhydrin colorimetry(a. Fe3O4; b. Fe3O4-NH2; c. Fe3O4-CHO; d. Fe3O4@PEI); B:SEM diagram of Fe3O4@PEI, inset is particle size distribution of Fe3O4@PEI; C: VSM diagram for Fe3O4-NH2 and Fe3O4@PEI; D:XRD pattern of Fe3O4@PEI, inset is its physical image
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Figure 2. Selection of adsorbent and optimization of preparation conditions($\bar{x} \pm s,\;n=3 $) A:Selection of adsorbent; B:Effect of concentration of PEI on extraction efficiencies of NSAIDs KPF: Ketoprofen; NPX: Naproxen; DCF: Dclofenac; TOL: Tolfenamic acid
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Figure 3. Optimization of sample pretreatment conditions($\bar{x} \pm s,\;n=3 $) A:Effect of adsorption time on extraction efficiencies of NSAIDs; B:Effect of pH on extraction efficiencies of NSAIDs; C:Effect of amount of adsorbent on extraction efficiencies of NSAIDs; D:Effect of various elute agents on extraction efficiencies of NSAIDs; E:Effect of desorption time on extraction efficiencies of NSAIDs
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Figure 4. Specificity of Fe3O4@PEI to NSAIDs in water sample (a) injection after MSPE treatment (blank water sample), Inset: magnified chromatogram of (a); (b) injection after MSPE treatment (50 mL of water sample with 10 µg/L standard solution)1: KPF, 2: NPX, 3: DCF, 4: TOL
Table 1 Linear ranges, linear equations, correlation coefficients (r2) and limits of quantitation(LOQ) for 4 analytes
Analyte Linear range/ (μg/L) Regression equation r2 LOQ/(μg/L) KPF 1−500 y = 49.26x+30.06 0.9997 0.69 NPX 1−500 y = 48.33x+47.74 0.9989 0.56 DCF 1−500 y = 108.22x+81.74 0.9996 0.29 TOL 1−500 y = 19.31x+117.16 0.9988 0.75 
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