【作者】 李舒；

【导师】 占金华； 陈静；

【作者基本信息】 山东大学 ， 分析化学， 2025， 博士

【摘要】 表面增强拉曼光谱(Surface-Enhanced Raman Spectroscopy,SERS)具有高灵敏度和分子指纹图谱等优点,已被广泛开发应用于环境监测、食品安全分析和生物医学诊断等领域。近年来,随着药品及个人护理品与微/纳塑料两类新兴污染物的生态风险凸显,SERS进一步发展应用于其定性定量分析。然而,SERS在实际环境基质中分析药品及个人护理品与微/纳塑料时仍面临复杂基质干扰强、多组分同步分析困难和微/纳塑料形态分析困难等挑战。本文通过结合分离技术、化学计量学与SERS分析技术,建立了多种针对新兴污染物(PPCPs、纳塑料)的高效分离萃取与多维度分析的SERS联用新方法,构建针对复杂基质中污染物的分离-富集-分析联用方法体系,成功实现了PPCPs和纳塑料的分离富集与高灵敏原位SERS分析,为复杂环境样品中痕量污染物的精准识别与定量分析提供方法学支撑。本文主要研究内容分为以下四个部分:(1)针对SERS分析复杂环境中PPCPs时基底亲和力有限导致的分析速度慢、灵敏度低等问题,构建了动态电场调控的固相微萃取-表面增强拉曼光谱(EE-SPME-SERS)联用新方法。以r-Ag/Au基底作为电场驱动、SPME吸附和SERS检测分析的平台,实现了 PPCPs萃取与分析一体化,大大缩短了方法分析时间,能够在1秒内完成联苯胺的SERS分析。EE-SPME-SERS实现了对多种类PPCPs(抗生素等)的分析检测。同时,EE-SPME-SERS通过动态调控电场方向,驱动联苯胺在SERS基底上快速吸附与脱附,实现了原位实时监测洗衣废水中联苯胺浓度变化(100-700 μg·L-1)过程,为连续动态监测环境水体中的PPCPs提供方法学支撑。(2)针对SERS分析复杂环境中PPCPs时的竞争性吸附和基质干扰问题,发展了一体化纸离心分离富集-SERS(PC-SERS)联用新方法。以P-AgNPs基底作为纸离心平台和SERS基底,通过离心力和分子-基底作用力的差异,有效抑制了抗生素分析中的竞争性吸附干扰,构建了一体化在线高灵敏度SERS分析平台。同时,PC-SERS方法还消除了样品转移步骤导致的样品损失,提升了分析效率,在20分钟内实现了 SERS分析信号14倍的增强。在强干扰物存在时,PC-SERS成功分离检出了痕量磺胺类抗生素分析物与干扰物,其中磺胺检测限达到1μg·L-1。成功在复杂环境基质(再生水、萝卜提取液)中实现了磺胺类抗生素的高灵敏度SERS分析,为原位快速分析环境水体中的PPCPs提供方法学支撑。(3)针对SERS对多组分复合污染物同步分析难,发展了离心-毛细驱动局域类咖啡环富集-SERS(CCR-SERS)联用新方法。构建基于SP-AgNPs基底的分离富集一体化平台,通过离心力与毛细作用的协同作用,同时实现痕量抗生素污染物的离心富集与纳塑料局域类咖啡环富集,并进行原位SERS检测,解决了多组分复合污染物同步分析难的问题。该方法对磺胺和PS NPs的方法检出限分别为5μg·L-1和10-5 g·L-1。CCR-SERS对快餐杯盖浸出液中小分子污染物和小分子-纳塑料复合污染物成功分离检测,实现了环境水样中游离态磺胺、纳塑料与磺胺-纳塑料复合污染物的分离富集与原位SERS检测。为PPCPs和纳塑料复合污染物体系有效分离与高灵敏度分析提供方法学支撑。(4)针对SERS对微/纳塑料形态分析难,利用正交偏最小二乘判别分析(OPLS-DA)辅助重构纳塑料及纳塑料复合污染物SERS成像,实现对其化学成分与空间分布的同步解析。经过初步分类、模型拟合与评估、异常点剔除后模型拟合,成功利用OPLS-DA将纳塑料、吸附污染物的纳塑料及背景干扰信号分类。其中OPLS-DA的正交得分与纳塑料特征峰显著相关,利用正交得分对SERS成像进行图像重构,实现了纳塑料复合污染体系空间分布和化学组成的精准分析。更多还原

【Abstract】 Surface-Enhanced Raman Spectroscopy(SERS)has been extensively developed for environmental monitoring,food safety analysis,and biomedical diagnostics owing to its ultrahigh sensitivity and molecular fingerprinting capabilities.In recent years,the ecological risks posed by emerging contaminants—specifically pharmaceuticals and personal care products(PPCPs)and micro/nanoplastics(MNPs)—have driven the application of SERS toward their qualitative and quantitative analysis.Nevertheless,SERS analysis of PPCPs and MNPs in authentic environmental matrices remains challenged by strong matrix interference,limitations in multi-component co-detection,and difficulties in morphological characterization of MNPs.This study establishes novel SERS-coupled methodologies integrating extraction techniques and chemometrics to achieve efficient extraction,preconcentration,and multidimensional profiling of emerging contaminants(PPCPs and nanoplastics).A methodological framework for integrated separation-enrichment-analysis has been developed,successfully enabling the isolation,preconcentration,and ultrasensitive in situ SERS detection of PPCPs and nanoplastics in complex environmental samples.This work provides critical methodological support for precise identification and quantification of trace pollutants.The study comprises four interconnected components:(1)To address the slow analysis speed and low sensitivity in SERS detection of PPCPs in complex environments caused by limited substrate affinity,a novel electrically enhanced solid-phase microextraction-SERS(EE-SPME-SERS)method was developed.The r-Ag/Au substrate served as an integrated platform for electric field-driven transport,SPME adsorption,and SERS detection,achieving unified extraction and analysis of PPCPs.This integration significantly reduced analytical time,enabling SERS detection of benzidine within 1 second.The EE-SPME-SERS method facilitated analysis of diverse PPCPs(antibiotics).By dynamically modulating the electric field direction,rapid adsorption-desorption of benzidine on the SERS substrate was achieved,allowing in situ real-time monitoring of benzidine concentration fluctuations(100-700 μg·L-1)in laundry wastewater,thereby providing methodological support for continuous dynamic surveillance of PPCPs in environmental water bodies.(2)To resolve competitive adsorption and matrix interference in SERS analysis of PPCPs in complex environments,an integrated paper centrifuge-SERS(PC-SERS)method was developed.Using the P-AgNPs substrate as both a paper centrifuge platform and SERS-active surface,competitive adsorption interference in antibiotic analysis was effectively suppressed by leveraging differences between centrifugal forces and molecule-substrate interactions.This integration established an online highsensitivity SERS analytical platform.The PC-SERS method eliminated sample loss from transfer steps,enhanced analytical efficiency,and achieved 14-fold SERS signal amplification within 20 minutes.In the presence of strong interferents,PC-SERS successfully separated and detected trace sulfonamide antibiotics with a detection limit of 1 μg·L-1.Highly sensitive SERS analysis of sulfonamide antibiotics was accomplished in complex environmental matrices(reclaimed water,radish extract),providing methodological support for in situ rapid analysis of PPCPs in environmental waters.(3)To address the difficulty in simultaneous SERS analysis of multi-component composite pollutants,a centrifugal-capillary-driven localized coffee-ring enrichmentSERS(CCR-SERS)method was developed.An integrated separation-enrichment platform based on the SP-AgNPs substrate was constructed.Through the synergistic effect of centrifugal force and capillary action,simultaneous centrifugal enrichment of trace antibiotic pollutants and localized coffee-ring-like enrichment of nanoplastics were achieved,followed by in situ SERS detection,resolving the challenge of synchronous analysis of multi-component composite pollutants.The method detection limits(MDLs)for sulfonamides and PS nanoplastics were 5 μg·L-1 and 10-5 g·L-1,respectively.CCR-SERS successfully separated and detected small-molecule contaminants and small-molecule-nanoplastic composite contaminants in fast-food cup lid leachates,achieving separation,enrichment,and in situ SERS detection of free sulfamethoxazole,nanoplastics,and sulfamethoxazole-nanoplastic composite contaminants in environmental water samples.This provides methodological support for the effective separation and highly sensitive analysis of PPCPs and nanoplastic composite pollutant systems.(4)To resolve the difficulty in SERS-based morphological analysis of micro/nanoplastics,a novel method for orthogonal partial least squares-discriminant analysis(OPLS-DA)-assisted reconstruction of SERS mapping for nanoplastics and nanoplastic composite pollutants was developed.After preliminary classification,model fitting,evaluation,and outlier elimination,OPLS-DA successfully classified nanoplastics,contaminant-adsorbed nanoplastics,and background interference signals.The orthogonal scores of OPLS-DA significantly correlated with characteristic peaks of nanoplastics,and these scores were utilized for SERS mapping reconstruction,enabling precise analysis of the spatial distribution and chemical composition of nanoplastic composite contaminant systems.更多还原