Applications of Raman Spectroscopy in Agricultural Products and Food Analysis: A Review

Abstract

Raman spectroscopy has been gaining popularity as an analytical tool due to advances in development of Raman spectrometry and the power of personal computers. Due to to its narrow and highly resolved bands, Raman spectroscopy allows for nondestructive extraction of chemical and physical information about samples and aids in rapid on-line analysis without any special sample preparation. In this review, Raman spectroscopic techniques such as dispersive Raman spectroscopy, Fourier transform Raman spectroscopy, surface-enhanced Raman spectroscopy, and spatially offset Raman spectroscopy are briefly introduced. In addition, applications of Raman spectroscopy are explored, within various fields of agricultural products and food, including fruits and vegetables, crops, meat and dairy products, oil, as well as beverages. In addition, some discussion on the importance of Raman spectroscopy as fundamental and applied research of agricultural products and food is provided.     

薄层色谱与表面增强拉曼散射光谱联用技术的研究进展

表面增强拉曼光谱（SERS）作为一种快速、灵敏的分析技术,被广泛应用于分析化学、环境检测及食品安全等领域。在实际生活中的样品大多为混合物,直接使用SERS技术无法对复杂样品中的分析物进行准确测定。薄层色谱（TLC）分离技术具有操作简便,成本低廉及分离速度快等特点,TLC作为一种高通量的分离技术在合成化学、分析化学、药物化学及食品科学等研究领域得到了广泛的应用。TLC对待测物体系进行分离后,通过碘显色或荧光对分离的斑点进行可视化处理,再结合质谱,红外光谱、荧光光谱及SERS光谱等分析技术可以对分离物质进行定性及定量分析。TLC与SERS联用技术的出现,使得SERS光谱可以应用于混合物中分析物的有效测定。TLC-SERS技术同时具备良好的分离作用和灵敏的光谱检测性能,适用于对复杂样品进行分离检测。在TLC-SERS检测过程中,样品用量少且无需使用复杂的实验设备即可实现对混合物现场快速检测。介绍了SERS的增强机理以及活性基底的制备,对TLC-SERS技术在环境污染物检测、食品安全、中草药鉴定及生物医学等方面的应用做了概括性综述。给出了TLC-SERS技术在有害物快检领域的应用实例,为TLC-SERS技术未来用于食品安全、法医鉴定及环境治理中快速检测方法建立及仪器设备研发提供参考。     

Applications of Raman spectroscopy in detection of water quality

Water pollution is hazardous to the health of humans and other organisms, and detection of pollutants in aquatic environments is of primary importance for water quality monitoring. Raman spectroscopy offers an effective tool for qualitative analysis and quantitative detection of contaminants in a water environment. This article focuses on applications of Raman spectroscopy for detection of water quality. In this article, various Raman spectroscopy techniques employed for water quality detection are presented based on the types of pollutants: organics, inorganics, and biological contaminants. Additionally, the relevant detection parameters are reviewed, such as detection materials, limit of detection, detection range, peak positions, and selectivity. Furthermore, the advantages and limitations of various Raman spectroscopy techniques are summarized. Finally, the future development of Raman spectroscopy for detection of water quality is discussed.     

拉曼光谱技术的应用及研究进展

本文简述了拉曼光谱产生的机理以及与红外光谱的区别,讨论了拉曼光谱在聚合物、生物分子、蛋白质和无机物等方面研究及应用,介绍了傅立叶变换拉曼、共焦显微拉曼、表面增强激光拉曼、固体光声拉曼光谱的原理及其应用以及拉曼光谱和其他检测手段的联用技术。     

3D-assembled Ag nanowires for use in plasmon-enhanced spectroscopic sensors

Surface plasmon-enhanced spectroscopic sensors for fluorescence and Raman spectroscopy use high-density metallic nanostructures to strongly enhance the light–matter interaction. In this contribution, we will review the processes by which three-dimensional (3D) multilayered Ag nanowires assemble from one-dimensional Ag nanowires and their plasmon-enhanced sensing applications, giving emphasis to the physical mechanism underlying the plasmon-enhanced spectroscopy. In particular, we discuss the practical aspects of 3D porous and flexible plasmonic platforms used for spectroscopic sensing applications. Combining a portable spectrometer with a low-cost but highly sensitive and flexible plasmonic substrate is potentially useful for on-site chemical analysis in the contexts of environmental monitoring, food safety, forensic science, and point-of-care healthcare medical diagnostics.     

Raman spectroscopy of carbon nanotubes

The use of Raman spectroscopy to reveal the remarkable structure and the unusual electronic and phonon properties of single wall carbon nanotubes (SWNTs) is reviewed comprehensively. The various types of Raman scattering processes relevant to carbon nanotubes are reviewed, and the theoretical foundations for these topics are presented. The most common experimental techniques used to probe carbon nanotubes are summarized, followed by a review of the novel experimental findings for each of the features in the first order and second order Raman spectra for single wall carbon nanotubes. These results are presented and discussed in connection with theoretical considerations. Raman spectra for bundles of SWNTs, for SWNTs surrounded by various common wrapping agents, and for isolated SWNTs at the single nanotube level are reviewed. Some of the current research challenges facing the field are briefly summarized.     

拉曼光谱在安检领域中的应用

拉曼光谱技术在很多领域都有广泛的应用。本文将拉曼光谱技术应用到公共安全检查领域, 利用自行研发的拉曼安检仪(型号: RT1003, 同方威视技术股份有限公司), 检测了常见易燃易爆危险液体、有毒化学试剂及强氧化强腐蚀液体共400余种, 如汽油、煤油、柴油、苯、甲苯、乙醚、四氯化碳、双氧水、浓硫酸、浓硝酸等, 建立了常见危险液体的拉曼谱图库, 并用于北京南站的安全检查, 取得了良好效果。     

Automated detection and characterization of graphene and few‐layer graphite via Raman spectroscopy

Several processes have to be automated in order to use graphene in future industrial applications. One of these is the detection and characterization of graphene and few‐layer graphite (FLG) flakes on a substrate. Raman spectroscopy is an ideal tool for this purpose, as it allows not only the identification of these graphitic materials on arbitrary substrates but also monitoring the quality of flakes within the sample. In this paper, we report how graphene and FLG crystallites can be automatically detected and characterized by monitoring the evolution of Raman bands. We present an algorithm that achieves this purpose and thus has special potential in industrial applications of graphene. Copyright © 2010 John Wiley & Sons, Ltd.     

Insight into thermally induced solid‐state polymorphic transformation of sulfathiazole using simultaneous in situ Raman spectroscopy and differential scanning calorimetry

Pharmaceutical solids exposed to thermal stress during manufacturing processes undergo various phase transformations in bulk drug substances or excipients, resulting in altered dosage form performance. Due to its relatively rapid spectral acquisition rate, as well as the possibility of incorporation into in‐line monitoring, Raman spectroscopy is ideally suited to monitoring the transformation between different solid‐state forms. In this study, we demonstrate that the transition temperature for polymorphs can be estimated from the transformation profiles obtained from real‐time, in situ, simultaneous Raman spectroscopic, and differential scanning calorimetric data. Using this method, we have estimated the transition temperature of the solid‐state transformation of the enantiotropically related sulfathiazole polymorphs III and I. These results suggest that this method is a useful approach to determine transition temperatures in systems that are not amenable to accessing other methods. Copyright © 2009 John Wiley & Sons, Ltd.     

INFRARED AND RAMAN SPECTROSCOPY IN PAPER AND PULP ANALYSIS

Infrared and Raman spectroscopy are essential analytical tools for the structural analysis of paper and pulp chemistry. The studies of cellulose, hemicellulose, lignin, thermal- and photo-induced oxidation; cross-linking; and various chemical treatments of pulp and paper products are all made possible using these forms of molecular spectroscopy. In this review, containing 70 references, a broad range of applications into pulp and paper materials, components, and processes is described from recent and classic research over predominantly the past 20 years.     

拉曼光谱技术在食品质量安全检测中的应用

拉曼光谱技术具有样品无需前处理、操作简便、时间短、灵敏度高等优点,可获得样品的物理化学及深层结构信息,已广泛应用于石油化工、生物医学、地质考古、刑事司法、宝石鉴定等领域。拉曼光谱对水等极性物质极其不敏感,在食品质量安全检测方面具有良好的应用前景。论文简述了拉曼光谱技术的检测原理、分类以及系统的组成,综述了拉曼光谱技术在食品成分分析和农药残留检测中的最新研究进展,指出了该技术在食品质量安全检测中的关键技术并对今后的研究进行了展望。     

Applications of Infrared Spectroscopy to Biochemical,Food, and Agricultural Processes

Abstract

Integrated investigations on infrared spectroscopic characteristics of metabolites and on applications of infrared spectroscopy to foodstuff production, food processing, and tasting are described. As the important metabolites, saccharides, which play very important roles in various functions, located in the central position of the metabolic pathways, were selected, and the spectral features of the saccharides and related materials are discussed. Additionally, the applications of spectral analysis to the monitoring of the enzyme reaction and the sugar metabolic processes, which are the main materials in food processing, are described. Furthermore, the studies on the spectroscopic measurements during the cultivation of agricultural products as foodstuffs and in the tasting as the final quality evaluation of foods are represented. These results suggest that infrared spectroscopy could be very effective for evaluating foodstuff production and the tasting of the processed foods and that the applied topics should provide fundamental information about the spectral behavior of the metabolites and bioproducts.     

采用显微拉曼光谱技术检测激光微加工质量

本文简要介绍了准分子激光微加工的原理;分析比较了几种微检测技术的特点和用途;提出了采用显微拉曼光谱检测准分子激光微加工质量的新技术,并在有机玻璃和光刻胶制成的齿轮上分别进行了探索。研究结果表明:显微拉曼散射技术确实可以成为一种新的检测微加工质量的有效手段。     

Applications of Raman spectroscopy in dentistry part II: Soft tissue analysis

Raman spectroscopy is rapidly moving from an experimental technique for the analysis of biological molecules to a tool for the real-time clinical diagnosis and in situ evaluation of the oral tissue in medical and dental research. The purpose of this study is to identify various applications of Raman spectroscopy, to evaluate the contemporary status, and to explore future directions in the field of dentistry. Several in-depth applications are presented to illustrate Raman spectroscopy in early diagnosis of soft tissue abnormalities. Raman spectroscopy allows researchers to analyze histological and biochemical composition of biological tissues. The technique not only demonstrates its role in the disclosure of dysplasia and malignancy, but also in performing guided biopsies, diagnosing sialoliths, and assessment of surgical margins. Raman spectroscopy is used to identify the molecular structures and their components to give substantial information about the chemical structure properties of these molecules. In this article, we acquaint the utilization of Raman spectroscopy in analyzing the soft tissues in relation to dentistry.     

两种常用合成抗氧化剂的拉曼光谱研究

随着社会的不断进步,食品工业得到快速发展,随之食品安全问题也层出不穷。由于合成抗氧化剂价格较低且对食品有较好的防腐保鲜作用,常被一些食品生产商过量添加在食品中,严重危及人们身心健康。因而,对于食品中合成抗氧化剂的检测研究是十分必要的。丁基羟基茴香醚(BHA)和叔丁基对苯二酚(TBHQ)是两种常见的合成抗氧化剂。实验上, 利用共聚焦显微拉曼光谱仪分别对BHA和TBHQ进行拉曼光谱检测,获得样品的拉曼散射谱。理论上,应用密度泛函理论DFT(B3LYP)的三参数混合方法及6-31G(d, p)基组对其进行空间结构优化并计算其拉曼光谱,给出了光谱强度图。将理论结果与实验结果进行对比发现,在50～4 000 cm-1范围内BHA及TBHQ分子拉曼特征明显且拉曼活性较强,其振动频率在实验上和理论上显示出较好的一致性。另外,给出了BHA和TBHQ分子的红外活性、拉曼活性以及各频率谱线对应的振动模式归属。结果表明,BHA和TBHQ分子的拉曼频移表征物质的特征结构,可以作为鉴定和识别的检测依据。该研究报道了抗氧化剂BHA和TBHQ的拉曼光谱,并对其理论机制进行分析,为拉曼光谱技术应用于食品添加剂研究领域提供了理论和实验依据。     

近场拉曼光谱在纳米结构表征中的应用

近场拉曼光谱是近场光学领域中的新型技术,因其可对纳米结构进行光谱表征而备受科学研究者的关注。 文章从光学的角度简述了将近场光学与拉曼光谱相结合成为近场拉曼光谱的原理,介绍了近场拉曼光谱技术的优势,详细阐述了近场拉曼光谱在单壁碳纳米管、生物样品、热电晶体、染料分子等纳米结构表征中的应用,展现了近场拉曼光谱技术广阔的应用前景。     

Raman spectroscopy can discriminate distinct glioma subtypes as defined by RNA expression profiling

Raman spectroscopy is a molecular spectroscopic technique that can measure the molecular composition of tissue samples within seconds without any extraction processes or dyes. In microbiology, Raman spectroscopy is used to identify bacteriae. In glioblastoma tissue, it was reported that necrosis, normal brain and tumor can be discriminated using Raman spectroscopy. Therefore, we hypothesized that Raman spectroscopy could discriminate glioblastoma tissue from different glioma subtypes defined by RNA expression profiling. We analyzed 20 glioma samples from two distinct molecular subtypes. Both subtypes consisted of glioblastoma samples showing a variety in glioma grading and typing. The Raman spectroscopic results could be grouped in two distinct clusters in an unsupervised cluster analysis. Further analysis of these clusters showed that they were fully congruent with the two clusters as defined by RNA expression profiling. Conclusion: our results demonstrate that Raman spectroscopy can discriminate between different molecular subtypes of glioma and, therefore, may prove to be a valuable tool in in vitro cancer research. Copyright © 2013 John Wiley & Sons, Ltd.     

分子振动光谱法与中药研究的最新进展

本文叙述了分子振动光谱法（傅半叶变换拉曼光谱技术和傅立叶变换红外光谱技术）的量新发展与中药的无损定性鉴别、定量分析、热稳定性监控及中药优化的最新应用。报道了利用傅立叶变换拉曼光谱技术（ＦＴ－Ｒａｍａｎ）和漫反射傅立叶变换２红外光谱技术（ＤＲ－ＦＴＩＲ）可以直接快速地鉴别生药材;利用漫反射傅立叶变换近红外光谱技术（ＤＲ－ＮＩＲ）可以无损定量分析中药材、中成药和方剂的组分含量利用ＦＴ－Ｒａｍａｎ和ＨＡ     

TLC原位拉曼光谱法快速检测减肥类保健食品中非法添加的四种成分

建立薄层色谱(TLC)与拉曼光谱联用方法,并对减肥类保健食品中非法添加的四种化学成分(茶碱、咖啡因、苯丙酸诺龙、螺内酯)进行检测。采用TLC法将掺杂成分与保健食品基质进行初步分离,在紫外灯(254 nm)下检视定位,以780 nm激光为光源,对TLC上微量掺杂成分的斑点原位,直接检测浓集点的拉曼光谱。考察不同配方保健食品基质对掺杂成分拉曼光谱的影响,并对检测限进行验证,初步建立了减肥类保健食品中四种掺杂成分的TLC原位拉曼光谱检测方法。常用保健食品基质对掺杂成分检测结果无干扰,检测限为2~4 μg,在九种减肥类保健食品中检测出两种含有咖啡因。该研究建立了TLC与拉曼光谱联用技术并采用此方法快速鉴别了减肥保健食品中茶碱等四种非法添加化学成分,本法专属、灵敏、快速、简便,可为保健食品中非法添加化学成分的快速检测技术研究提供新的参考依据。     

Raman spectroscopic analysis of cataract lens: A compendious review

Age-related cataracts is a pressing health issue with the increase in elderly populations. This creates an imminent demand for the development of an early, noninvasive method of cataracts diagnosis. Early detection of cataracts will improve quality of life and may prevent morbidity associated with advanced cataracts and surgery. Raman spectrum of proteins provides characteristic information regarding molecular interactions of peptide residues. Hence Raman spectroscopy is a promising tool for the study of protein-related diseases, such as cataracts. We surveyed the literature to assess the use of Raman technology in the studies of human lens and animal models. These studies included analysis of amino acids (i.e., cysteine, tryptophan, and tyrosine, etc.) and secondary protein structures (i.e., α-helix and β-sheet) in various Raman profiles. Other studies used Raman spectroscopy to analyze and monitor the development of cataracts in lens. Technological advances in the instrumentation of laser Raman spectroscopy, including Fourier transform Raman spectroscopy, Raman microspectroscopy, and confocal Raman microspectroscopy have improved the performance of Raman spectroscopic analysis. How to take advantage of these developments and make it closer to reality using Raman spectroscopic methods to diagnose cataracts in a timely manner is a key challenge for the scientific community of Raman spectroscopy.