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Journal ArticleDOI: 10.1021/ACS.ANALCHEM.1C00234

Simultaneous In Situ Extraction and Self-Assembly of Plasmonic Colloidal Gold Superparticles for SERS Detection of Organochlorine Pesticides in Water

02 Mar 2021-Analytical Chemistry (American Chemical Society)-Vol. 93, Iss: 10, pp 4657-4665
Abstract: Rapid component separation and reliable surface-enhanced Raman scattering (SERS) detection of organochlorine pesticide (OCP) residues in real water samples remain major challenges because of sample complexity, trace content, and low molecular affinity for a metal surface. Here, we report a novel strategy of simultaneous in situ extraction and fabrication of plasmonic colloidal gold superparticles (AuSPs) to perform rapid SERS detection of OCPs in environmental water. In this protocol, multiple components of OCPs in complex water were facilely diffused into dichloromethane (DCM) microdroplets and specifically bound to octadecylamine-modified gold nanoparticles (Au-ODAs), affording the SERS substrate through self-assembly of the OCP-trapped Au-ODA into AuSPs with the evaporation of DCM. SERS signals of the specifically prepared Au-ODA could be used as an internal standard to calibrate the absolute signal of OCPs, and multiplex detection could be achieved depending on their molecularly narrow Raman peaks. As for simultaneously sensing four kinds of OCPs (4,4'-DDT, α-endosulfan, tetradifon, and chlordane) in water, the established method showed strong anti-interference ability and comparable quantification ranges with a low limit of detection (LOD). The recoveries ranged from 90.20 to 109.4% for OCPs in farmland, river, and fishpond water, indicating that the established AuSP-based platform is reliable and applicable to the detection of OCPs in real water samples.

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Journal ArticleDOI: 10.1016/J.MOLLIQ.2021.116608
Abstract: Surface-Enhanced Raman Scattering (SERS) using colloidal metal (Ag, Au) nanoparticles has been regarded as a powerful method for detecting organic pollutants at vestigial levels. Although less investigated, the controlled synthesis of binary nanostructures comprising two metals provides an alternative route to SERS platforms with tuned surface plasmon resonances. Here, we demonstrate that the use of dendrimers allows the formation of distinct combinations of Ag:Au nanostructures that are composed of smaller metal nanocrystals. Our research highlights the role of the dendrimer macromolecules as a multipurpose ligand in the generation of such hybrid nanostructure, including as a reducing agent, an effective long-term colloidal stabilizer and as a molecular glue for interconnecting the primary metal nanocrystals. Noteworthy, the dendrimer-based Ag:Au hybrid nanostructures are more SERS sensitive as compared to the corresponding colloidal blends or to the single-phase metals, as revealed by using molecular pesticides as analytes in spiked water samples. We suggest that the high SERS sensitivity of the hybrid nanostructures is due to interparticle plasmonic coupling occurring between the primary metal nanoparticle aggregates, whose arrangement is templated by the presence of the dendrimer macromolecules.

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Topics: Dendrimer (53%), Nanoparticle (52%)

2 Citations


Journal ArticleDOI: 10.1021/ACS.ANALCHEM.1C03019
Zhongning Yu1, Lu Huang1, Zhuomin Zhang1, Gongke Li1Institutions (1)
Abstract: Rapid and accurate analysis of multiple targets in complex samples is still a big challenge in the fast detection field. Herein, we developed a rapid and accurate strategy for simultaneous quantification of trace multiple antibiotic residues in complex aquatic samples by surface-enhanced Raman scattering (SERS) using a Ti3C2Tx/DNA/Ag membrane substrate. This membrane substrate was proven to have good uniformity, reproducibility, stability, and SERS activity by a series of characterizations. Also, this substrate combined excellent electromagnetic enhancement and chemical enhancement effects, which endowed it with good sensitivity and selectivity during SERS analysis. It achieved the integration of multitarget separation, enrichment, and in situ detection, which significantly improved the selectivity, sensitivity, accuracy, and detection throughput by membrane substrate coupling with SERS for real-sample analysis. Finally, this rapid SERS analysis strategy was successfully applied to the simultaneous quantification of trace nitrofurantoin (NFT) and ofloxacin (OFX) in aquatic samples. It was observed that trace NFT and OFX were actually detected and simultaneously quantified to be 8.0-13.7 and 42.6-49.1 μg/kg in aquatic samples, respectively, with good recoveries of 88.0-107% and relative standard deviations of 0.3-5.5%. The results were verified by a traditional high-performance liquid chromatography method with relative errors of -9.8 to 5.3%. This strategy provided a methodological reference for accurate SERS quantification of multiple targets in complex samples.

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Journal ArticleDOI: 10.1021/ACS.ANALCHEM.1C02139
Danyang Liu1, Chuanyu Liu1, Yuan Yuan1, Yuan Yuan2  +3 moreInstitutions (2)
Abstract: For its ultrahigh sensitivity, the microfluidic system combined with surface-enhanced Raman spectroscopy (SERS) becomes one of the most interesting topics in integrated online monitoring related fields. In previous reports, the commonest surface plasmon-enhanced substrates in microfluidics consist of immobilized metal nanostructures on the channel surface to overcome the disturbance of Brownian motion. In this work, a hybrid optoplasmonic microfluidic conveyer is developed, in which the movable, highly ordered optoplasmonic particles are delivered to the detection spot for SERS detection. Here, the optoplasmonic particle is the SiO2 microsphere with in situ photochemical reduced Ag nanoparticles on the surface. Because of the converged light at the SiO2 microsphere surface, the SERS spectra collected at this optoplasmonic particle in the channel exhibit excellent performance, which is confirmed by the simulated electric field distribution. In addition, the experimental data also demonstrate that the quantitative analysis is achieved at 1 nM in this optoplasmonic microfluidic conveyer. Furthermore, the used optoplasmonic particle can be ejected from the microfluidic channel by modulating the velocity of injected fluid such that the new optoplasmonic particle will be delivered to the detection spot for repeatable SERS detection in the same channel. The dynamic process of optoplasmonic particle transport is investigated in this microconveyer, and the built theoretical model to predict the particle release is highly identical with the experimental data. These data point out that our hybrid optoplasmonic microfluidic conveyer has repeatable enhanced substrates with the high SERS sensitivity to overcome the cross-contamination of different target molecules in repeatable detection.

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Journal ArticleDOI: 10.1007/S00604-021-05025-3
De Zhang1, De Zhang2, Pei Liang1, Chen Wenwen2  +6 moreInstitutions (2)
07 Oct 2021-Mikrochimica Acta
Abstract: Surface-enhanced Raman spectroscopy is an alternative detection tool for monitoring food security. However, there is still a lack of a conclusion of SERS detection with respect to pesticides and real sample analysis, and the summary of intelligent algorithms in SERS is also a blank. In this review, a comprehensive report of pesticides detection using SERS technology is given. The SERS detection characteristics of different types of pesticides and the influence of substrate on inspection are discussed and compared by the typical ways of classification. The key points, including the progress in real sample analysis and Raman data processing methods with intelligent algorithm, are highlighted. Lastly, major challenges and future research trends of SERS analysis of pesticide residue are also addressed. SERS has been proven to be a powerful technique for rapid test of residue pesticides in complex food matrices, but there still is a tremendous development space for future research.

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34 results found


Journal ArticleDOI: 10.1021/ACS.CHEMREV.7B00027
Zhuyuan Wang1, Shenfei Zong1, Lei Wu1, Dan Zhu1  +1 moreInstitutions (1)
23 May 2017-Chemical Reviews
Abstract: Owing to their excellent multiplexing ability, high sensitivity, and large dynamic range, immunoassays using surface-enhanced Raman scattering (SERS) as the readout signal have found prosperous applications in fields such as disease diagnosis, environmental surveillance, and food safety supervision. Various ever-increasing demands have promoted SERS-based immunoassays from the classical sandwich-type ones to those integrated with fascinating automatic platforms (e.g., test strips and microfluidic chips). As recent years have witnessed impressive progress in SERS immunoassays, we try to comprehensively cover SERS-based immunoassays from their basic working principles to specific applications. Focusing on several basic elements in SERS immunoassays, typical structures of SERS nanoprobes, productive optical spectral encoding strategies, and popular immunoassay platforms are highlighted, followed by their representative biological applications in the last 5 years. Moreover, despite the vast advances achieved ...

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299 Citations


Journal ArticleDOI: 10.1002/ADMA.201702275
Xuezhi Qiao1, Bensheng Su2, Cong Liu1, Qian Song1  +3 moreInstitutions (2)
01 Feb 2018-Advanced Materials
Abstract: Surface enhanced Raman scattering (SERS) is a trace detection technique that extends even to single molecule detection. Its potential application to the noninvasive recognition of lung malignancies by detecting volatile organic compounds (VOCs) that serve as biomarkers would be a breakthrough in early cancer diagnostics. This application, however, is currently limited by two main factors: (1) most VOC biomarkers exhibit only weak Raman scattering; and (2) the high mobility of gaseous molecules results in a low adsorptivity on solid substrates. To enhance the adsorption of gaseous molecules, a ZIF-8 layer is coated onto a self-assembly of gold superparticles (GSPs) in order to slow the flow rate of gaseous biomarkers and depress the exponential decay of the electromagnetic field around the GSP surfaces. Gaseous aldehydes that are released as a result of tumor-specific tissue composition and metabolism, thereby acting as indicators of lung cancer, are guided onto SERS-active GSPs substrates through a ZIF-8 channel. Through a Schiff base reaction with 4-aminothiophenol pregrafted onto gold GSPs, gaseous aldehydes are captured with a 10 ppb limit of detection, demonstrating tremendous prospects for in vitro diagnoses of early stage lung cancer.

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152 Citations


Journal ArticleDOI: 10.1016/J.TIFS.2017.12.012
Tehseen Yaseen1, Tehseen Yaseen2, Hongbin Pu1, Hongbin Pu2  +1 moreInstitutions (2)
Abstract: Background Food safety and quality have gained much attention in recent years and the capability to evaluate food quality and safety in a sensitive, rapid, and reliable manner is of great importance in the food industry. Therefore, surface-enhanced Raman scattering (SERS) with the advantages of excellent sensitivity, high selectivity, non-destructive nature and significant enhancement to identify the target has demonstrated a great potential for quick detection of chemical contaminants, chemical constitutes, and pathogens in food samples. Scope and approach The enhancement of Raman signals for SERS is not only related to the interactions between substrates and samples but also the functionalization of substrates to gain SERS active substrates. In the present review, different types of substrates are briefly discussed, functionalization techniques for SERS active substrates are discussed, and applications of functionalized SERS substrate in food samples are presented. Conclusions and key findings It is evident that functionalization techniques for improving SERS substrates have given encouraging outcomes, which provides possibility for identifying multiple target analytes within a complex matrix, and thus could be used as a powerful analytical tool in real-world applications in food safety analysis as well as for enhancing food quality surveillance.

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113 Citations


Journal ArticleDOI: 10.1021/AC503672F
Abstract: In this work, we report the detection of the organochlorine pesticides aldrin, dieldrin, lindane, and α-endosulfan by using surface-enhanced Raman spectroscopy (SERS) and optimization of the SERS-sensing substrate. In order to overcome the inherent problem of the low affinity of the above pesticides, we have developed a strategy consisting of functionalization of the metal surface with alkyl dithiols in order to achieve two different goals: (i) to induce the nanoparticle linkage and create interparticle junctions where sensitive hot spots needed for SERS enhancement are present, and (ii) to create a specific environment in the nanogaps between silver and gold nanoparticles, making them suitable for the assembly and SERS detection of the analyzed pesticides. Afterward, an optimization of the sensing substrate was performed by varying the experimental conditions: type of metal nanoparticles, molecular linker (aromatic versus aliphatic dithiols and the length of the intermediate chain), surface coverage, las...

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109 Citations


Open accessJournal ArticleDOI: 10.1016/J.JHAZMAT.2014.08.006
Abstract: Environmental analytical chemists face the challenge of investigating thousands of potential organic pollutants that may be present in the aquatic environment. High resolution mass spectrometry (HRMS) hyphenated to chromatography offers the possibility of detecting a large number of contaminants without pre-selection of analytes due to its accurate-mass full-spectrum acquisition at good sensitivity. Interestingly, large screening can be made even without reference standards, as the valuable information provided by HRMS allows the tentative identification of the compound detected. In this work, hybrid quadrupole time-of-flight (QTOF) MS was combined with both liquid and gas chromatography (using a single instrument) for screening of around 2000 compounds in waters. This was feasible thanks to the use of atmospheric pressure chemical ionization source in GC. The screening was qualitatively validated for around 300 compounds at three levels (0.02, 0.1, 0.5μg/L), and screening detection limits were established. Surface, ground water and effluent wastewater samples were analyzed, detecting and identifying a notable number of pesticides and transformation products, pharmaceuticals, personal care products, and illicit drugs, among others. This is one of the most universal approaches in terms of comprehensive measurement for broad screening of organic contaminants within a large range of polarity and volatility in waters.

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104 Citations