Determination of chemical hazards in foods using surface-enhanced Raman spectroscopy coupled with advanced separation techniques

BackgroundSurface-enhanced Raman spectroscopy (SERS) has been validated as a highly accurate and specific technique for the discrimination, identification, and potential quantification of different types of chemical compounds. However, its application for the detection of potential hazardous chemical targets in foods has not yet been well developed due to interferences from the complicated food matrices, which could lead to challenges in spectral deconvolution and interpretation. The accurate separation and enrichment of the analyte from food samples are major challenges for analytical chemists and food technologists.Scope and approachFour promising “capturing” techniques (molecularly imprinted polymers, aptamer, antibody, and microfluidics) coupled with SERS were introduced in this review paper for the reliable and ultrafast determination of chemical hazards in food systems. These developed “one-step” or “two-step” SERS methods can achieve accurate and sensitive detection of trace level chemical hazards in agricultural products including foods.Key findings and conclusionsTandem SERS methods can be applied for rapid and reliable detection of trace level of chemical hazards in foods.     

Recent advances in nanofabrication techniques for SERS substrates and their applications in food safety analysis

ABSTRACT

The ability to analyze food safety and quality in a quick, sensitive, and reliable manner is of high importance in food industry. Surface-enhanced Raman scattering (SERS), which is popular for its significant enhancement, excellent sensitivity, and the fingerprinting ability to identify special molecules, has shown vast potential for rapid detection of chemical constitutes, chemical contaminants, and pathogens in food sample. For SERS, the enhancement of Raman signals is related to not only the SERS-active substrates, but also the interactions between sample and substrates. In the current review, colloidal and solid surface-based substrates are briefly described, fabrication techniques for SERS substrates are presented, and applications of SERS for food matrixes, correlation between substrates and food samples are also introduced. Finally, some outlook on further developments is presented. The current review is therefore intended to provide a comprehensive overview on the nanofabrication of SERS substrates, and the potential of applying SERS as an important food analysis platform.     

Functionalization techniques for improving SERS substrates and their applications in food safety evaluation: A review of recent research trends

BackgroundFood 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 approachThe 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 findingsIt 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.     

新烟碱类农药的快速检测技术研究进展

农药是制约我国农产品安全的首要因素。新烟碱类农药是继有机磷、氨基甲酸酯和拟除虫菊酯类杀虫剂之后的一类新型农药，是目前世界上使用最广泛的杀虫剂。研究表明，新烟碱类农药可与乙酰胆碱受体相结合，阻断中枢神经正常传导，同时对淋巴细胞产生基因毒性和细胞毒性。长期滥用和违规使用，使得食品尤其是农产品中新烟碱类农药严重超标。2019年，我国农业部发布的GB 2763—2019《食品安全国家标准食品中农药最大残留限量》明确规定了新烟碱类农药在食品中的最大残留量。为此，新烟碱类农药检测技术的开发对实现新烟碱类农药残留高效监控，保障食品安全意义重大。现有新烟碱类农药检测技术以仪器确证类方法和快速检测方法为主，前者往往依赖于大型仪器如气相色谱仪、高效液相色谱仪、质谱仪等的使用，存在仪器昂贵、操作复杂、预处理繁琐等不足之处，难以满足当下对农药残留实时、快速监测的现实需求。近年来，以光学分析法、电化学分析法、免疫分析法等为主的快速检测技术应运而生，得到了迅猛发展，快速检测技术的应用和推广有望突破传统检测技术瓶颈，实现对新烟碱类农药的高效检测与有力控制。本文就近年来新烟碱类农药的快速检测技术的研究进展进行简要综述。     

表面增强拉曼光谱法在果蔬农药残留检测中的应用

农药的使用对果蔬产业的提升起到了重要作用,但不合理的施用必然会对环境及果蔬产品造成污染,因此必须加强检测和管控工作。相较于质谱法,表面增强拉曼光谱检测法可以通过将痕量的农残分子吸附于基底表面达到增强拉曼散射信号的效果,因其具有快速、无损、易操作等优点,被视为一款新型的农药残留快速检测技术。本文针对果蔬农残检测领域,综述了表面增强拉曼光谱在基底制备、样品前处理、农药残留定性判别和定量分析方面的国内外研究进展。总结了贵金属纳米材料的形状、尺寸、组成对拉曼信号稳定性和灵敏度的影响,重点介绍了柔性基底材料、光谱数据模型构建的最新研究进展,同时展望了表面增强拉曼光谱农残检测技术的发展方向和应用前景。     

拉曼光谱技术在农产品药物残留检测中的应用

近年来,农产品药物残留超标引发了一系列食品安全问题,为了保障国家食品安全、保护消费者健康,需要对农产品中的药物残留进行定性定量检测。表面增强拉曼散射技术 (Surface-enhanced Raman scattering , SERS) 是一种极具吸引力的工具,可用于高效检测农药残留。本文介绍了表面增强拉曼光谱检测技术的概况,简介了拉曼增强基底,分析了表面增强拉曼光谱技术在药物标准溶液、农产品(肉类、水产品、果蔬和其他部分农产品等)药物残留检测领域中的研究现状,并针对当前农产品药物残留检测的发展趋势进行前景展望。     

表面增强拉曼技术在农药残留检测中的应用研究进展

食品的农药残留问题是威胁人类健康的全球性问题,表面增强拉曼光谱技术(surface-enhanced Raman spectroscopy, SERS)作为一种操作简便、快速灵敏的指纹光谱技术,在农药残留检测方面已展现出较大潜力。本文首先描述了SERS增强原理,然后简单概括了SERS基底制备的方法,以基底功能性出发,介绍了食品中农残检测中常见的两种类型的SERS基底：通用型基底、特异性基底,通过综述近年来在食品农残检测中的应用,总结了二者在检测食品中农残的特点和常用的制备工艺,旨在为更多农残检测需求提供关于SERS技术方面的启发。最后展望了SERS技术在农残检测的挑战并提出可行的建议。     

表面增强拉曼光谱在乳和乳品有害物质检测中的研究进展

乳和乳制品作为人类必不可少的食品之一,其中的有害物质,如农兽药残留、真菌毒素、非法添加物质以及其他污染物对消费者的健康安全构成了严重威胁,同时也阻碍了乳制品行业的发展。表面增强拉曼光谱法（Surface Enhanced Raman Spectroscopy,SERS）作为一种新兴的检测方法,有望能够满足目前乳和乳制品高通量,高灵敏度的检测需求。本文总结了SERS方法在牛奶检测中的研究进展,包括金属纳米检测探针和SERS固相平台的制备、抗体和适配体等分子识别技术的应用、核酸扩增技术以及微流控技术等与SERS的结合。最后,对SERS在乳制品的研究发展方向和应用前景做了总结和展望。     

Determination of Tricyclazole Content in Paddy Rice by Surface Enhanced Raman Spectroscopy

Abstract: An ultrasensitive method based on Surface enhanced Raman scattering (SERS) has been developed to determine content of a pesticide which is tricyclazole in paddy rice using sliver colloid as a substrate and pyridine as an internal standard. The peaks at 424 and 1035 cm^?1 in a SERS spectrum were selected as analytic and internal peaks, respectively, and their intensity ratio I_t/I_p was used to calculate the regression concentration of tricyclazole. The correlation between I_t/I_p and concentration showed significant linear relationship with a correlation coefficient of R²= 0.995 in a concentration range of 0.05 to 0.70 mg/L and the tricyclazole solution can be detected to be low as 0.002 mg/L by SERS. The method was applied to determine tricyclazole contents of 3 real rice samples with a standard addition method in order to eliminate interference of matrix. The errors of SERS measurements for the 3 samples were 0.0008 to 0.0246, 0.0013 to 0.0028, and 0.0129 to 0.0304 mg/kg, respectively, compared with the results obtained by high performance liquid chromatography method. This also showed a good reproducibility with low values of relative standard deviation (n= 3) for the 3 samples ranged from 3.63% to 4.64%. Practical Application: SERS is a simple, rapid, and sensitive method to detect pesticides residue in agricultural food. Our results demonstrate that coupled with silver colloid, SERS is able to rapidly determine tricyclazole residue in paddy rice, indicating that SERS can provide rapid, accurate, and reproducible results for tricyclazole determination at trace level in paddy rice.     

有机磷农药快速检测方法的研究进展

目前有机磷农药在农业生产中应用广泛,但是其在食品、水及环境中的残留对人体产生较严重的健康威胁。传统的检测方法比较耗时,且需要大型仪器设备,不适合现场测定,因此有机磷农药的快速检测方法的开发十分重要。本文综述了免疫分析法、酶抑制法及生物传感器法在有机磷农药检测中的应用,以期为相关检测人员的工作和对有机磷农药残留的快速检测方法的继续研究提供参考。     

农林副产品基纳米纤维素在食品工业中的应用

纤维素是自然界中含量丰富的天然聚合物之一,具有可再生、环境友好和生物相容性等特性。纳米纤维素是以纤维素为原料通过物理或化学方式制备而来。不同的制备方式对纳米纤维素的形态特征、物理化学性质产生显著的影响,使其呈现出不同的特性。纳米纤维素因具有较高的表面积和模量、两亲性、生物相容性和安全性等优异特性,在食品工业中备受关注。本文重点对近年来国内外关于农林副产品制备的纳米纤维素在食品包装、乳化稳定剂、酶固定化和基于表面增强拉曼光谱(SERS)的食品污染物的无损快速检测方面的应用进行了总结,分析了其在食品工业应用中的挑战,对今后研究进行了展望。     

Quantitative Detection of Isofenphos-Methyl in Corns Using Surface-Enhanced Raman Spectroscopy (SERS) with Chemometric Methods

Residual pesticides in agricultural production are one of the major food safety concerns around the world. In this study, we investigated the amount of isofenphos-methyl in corns by using surface-enhanced Raman spectroscopy (SERS) coupled with chemometric methods. The highest isofenphos-methyl peak at 1043 cm^?1 was used to detect and quantify the amount of isofenphos-methyl spiked in methanol-water (1:1) solvent and corns. The limits of detection (LODs) of isofenphos-methyl in methanol-water solvent and corns were 0.01 μg/mL and 0.01 μg/g, respectively. Quantitative detection of isofenphos-methyl residues (0–5 μg/mL) was conducted using partial least squares (PLS) model. Based upon the results of leave-one-out cross-validation, isofenphos-methyl could be predicted by PLS (the correlation coefficient was 0.9964) with a low root mean square error of calibration (RMSEC=0.146). The developed SERS method provides a much simpler and more sensitive way to monitor isofenphos-methyl for safe production of corns, which can be extended to the other agricultural products.     

动物源性食品安全检测技术研究进展

随着人民生活水平的提高和健康意识的增强,动物源性食品的质量安全问题受到广泛关注。化学污染（三聚氰胺添加、兽药残留、食品添加剂残留等）及致病微生物是导致动物源性食品安全问题的主要原因,不仅威胁人类健康,而且影响社会经济及产业发展。因此,建立动物源性食品安全的快速检测方法非常必要。表面增强拉曼光谱法（surface-enhanced Raman spectroscopy,SERS）具有检测速度快、选择性好、灵敏度高等优点,在食品安全检测领域展现出巨大的应用潜力而成为研究热点之一。本文综述了表面增强拉曼光谱技术在动物源性食品安全检测中的应用,详细介绍了SERS对三聚氰胺、食源性致病菌、农兽药残留和食品添加剂的检测应用及发展现状,并对SERS技术在食品中快速残留检测方面的应用进行了总结和展望,旨在为SERS技术在食品安全检测领域的进一步发展提供参考。     

表面增强拉曼光谱在食品污染物快速检测中的应用

随着科技的发展,食品的种类越来越丰富,随之而来的问题是食品中引入的污染物也越来越复杂,这使得食品安全成为当今全球关注的一个重要话题,快速有效地检测食品中污染物已然成为食品检测的热点。表面增强拉曼光谱(surface-enhanced Raman spectroscopy, SERS)由于其极高的灵敏度、快速检测、指纹图谱解释能力,以及高达单分子级别的检测水平,逐渐成为检测食品中污染物的常用方法。本文针对SERS基底的发展现状,如特殊形态金属纳米颗粒和固相SERS平台,以及SERS在农兽药,掺假,天然毒素以及食源性病原体等污染物中的检测方法进行了论述,以期为表面增强拉曼光谱未来在食品污染物快速检测中的应用提供参考。     

Potential of SERS for rapid detection of melamine and cyanuric acid extracted from milk

Melamine, a nitrogen-rich chemical, was implicated in the pet and human food recalls in 2007 and in the global food safety scares in 2008 involving milk and other milk-derived products. In this study, we investigated the feasibility of using surface-enhanced Raman spectroscopy (SERS) coupled with SERS-active gold substrates for rapid detection of trace amounts of melamine and its analogue (that is, cyanuric acid) in liquid milk. Raman signals of tested samples were significantly enhanced by SERS. The identification limit for SERS using gold substrate can reach 2 ppm of melamine in liquid milk. Partial least squares (PLS) models were established for the quantification of melamine in liquid milk by SERS: R = 0.90, RMSEP = 1.48 × 10⁻⁵. Our results demonstrate that rapid detection of melamine in milk can be achieved by SERS; while detection of cyanuric acid in milk remains a challenging task due to rapid enol-keto tautomerism of cyanuric acid. The SERS method is faster and simpler than other traditional methods, and requires minimum sample preparation. These results demonstrate that SERS could be used to detect food contaminants such as melamine in foods and food ingredients quickly and accurately.     

Non-targeted screening of pesticides for food analysis using liquid chromatography high-resolution mass spectrometry-a review

ABSTRACT

Targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a robust and reliable tool in quantitative analysis of pesticide residues in food samples. However, these methods have been only targeted to a predefined set of pesticides. Many other unexpected pesticides and/or their (bio)transformation products present in food matrices that may be harmful to consumers need to be discovered for food safety monitoring purpose. Therefore, non-targeted screening approaches using liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) have gained much attention in food monitoring recently. However, the development and implementation of non-targeted screening of potential pesticides and their (bio)transformation products in food samples are particularly challenging due to the inherent sample complexity and large quantity of MS data. To provide guidance on how to use non-targeted screening approaches for pesticide screening, three different aspects, namely, sample preparation, data acquisition and data processing, encompassed in the workflow of non-targeted screening approaches have been discussed, and current strategies, advances and challenges regarding these three aspects are reviewed. In addition, the recent application of non-targeted screening analysis of pesticide residues and their (bio)transformation products in food samples has been overviewed in this paper.     

表面增强拉曼光谱技术在快速检测保健食品中非法添加药物中的应用

表面增强拉曼光谱(surface-enhanced Raman spectroscopy,SERS)技术作为一种新型的快速检测技术正在被广泛应用于保健食品非法添加化学药物的检测中。通过设计不同的SERS基底,可以搭建出集样品前处理、上机分析、匹配定性的一体化拉曼光谱检测系统。与传统的检测方式相比,SERS技术具有无损、快速、图谱指纹特性强等优点,在保健食品非法添加化学药物的快速检测中具有巨大潜力。本文主要综述了SERS的技术原理、SERS基底分类以及SERS技术在保健食品中非法添加化学药物检测中的应用,并对SERS技术在保健食品中非法添加化学药物检测方面的应用前景进行了展望,以期为保健食品中未知违禁物的识别提供理论支撑。     

Advanced synchrotron-based and globar-sourced molecular (micro) spectroscopy contributions to advances in food and feed research on molecular structure,mycotoxin determination,and molecular nutrition

ABSTRACT

Mycotoxin contamination has been a worldwide problem for food and feeds production for a long time. There is an obviously increased focus of the food and feed industry toward the reduction of mycotoxin concentration in both the raw materials and finished products. Therefore, both effective qualitative and quantitative techniques for the determination of mycotoxins are required to minimize their harmful effects. Conventional wet chemical methods usually are time-consuming, expensive, and rely on complex extraction and cleanup pretreatments. Synchrotron-based and globar-based molecular spectroscopy have shown great potential to be developed as rapid and nondestructive tools for the determination of molecular structure, molecular nutrition and mycotoxins in feed and food. This article reviews the common types of mycotoxins in feed and food, their toxicity, as well as the conventional detection methods. The principle of advanced molecular spectroscopy techniques and their application prospects for mycotoxin detection are discussed. Recent progress in food and feed research with molecular spectroscopy techniques is highlighted. This review provides a potential and insight into how to determine the structure and mycotoxins of feed and food on a molecular basis with advanced Synchrotron-based and globar-based molecular (micro) spectroscopy.     

2012~2018年曲靖市蔬菜中农药残留监测结果分析

目的 了解2012~2018年曲靖市市售蔬菜中农药残留状况。方法 2012~2018年随机采集市售蔬菜232份, 按照《国家食品中化学污染物及有害因素监测工作手册》检测农药含量, 依据GB 2763-2016《食品中农药最大残留限量》进行判断评价。结果 232件蔬菜中检出农药残留102件, 检出率43.97%, 超标13件, 超标率5.60%。机磷类农药、拟除虫菊酯类农药、氨基甲酸酯类农药检出率分别为25.86%、40.09%、21.71%。检出率最高的是拟除虫菊酯类农药; 检出超标最多的是有机磷类农药; 检出率和超标率最高的均为叶菜类蔬菜。结论 曲靖市售蔬菜存在不同程度的农药污染, 建议相关部门加大监测和监管力度。     

表面增强拉曼光谱在食品添加剂和违法添加物检测中的应用

表面增强拉曼光谱技术作为一种新兴的分析检测技术,在食品快速检测行业具有广阔的应用前景。文章简述了表面增强拉曼光谱技术在食品添加剂及违法添加物快速检测中的最新研究状况,并展开讨论,以期为表面增强拉曼光谱技术在食品检测领域提供参考。