Xiao Xia Han

Detection of Pesticide Residues in Food Using Surface-Enhanced Raman Spectroscopy: A Review

Pesticides directly pollute the environment and contaminate foods ultimately being absorbed by the human body. Their residues contain highly toxic substances that have been found to cause serious problems to human health even at very low concentrations. The gold standard method, gas/liquid chromatography combined with mass spectroscopy, has been widely used for the detection of pesticide residues. However, these methods have some drawbacks such as complicated pretreatment and cleanup steps. Recent technological advancements of surface-enhanced Raman spectroscopy (SERS) have promoted the creation of alternative detection techniques. SERS is a useful detection tool with ultrasensitivity and simpler protocols. Present SERS-based pesticide residue detection often uses standard solutions of target analytes in conjunction with theoretical Raman spectra calculated by density functional theory (DFT) and actual Raman spectra detected by SERS. SERS is quite a promising technique for the direct detection of pesticides at trace levels in liquid samples or on the surface of solid samples following simple extraction to increase the concentration of analytes. In this review, we highlight recent studies on SERS-based pesticide detection, including SERS for pesticide standard solution detection and for pesticides in/on food samples. Moreover, in-depth analysis of pesticide chemical structures, structural alteration during food processing, interaction with SERS substrates, and selection of SERS-active substrates is involved.

Surface-Enhanced Raman Scattering (SERS) Active Gold Nanoparticles Decorated on a Porous Polymer Filter

In this work, we designed a process to assemble gold nanoparticles onto a three-dimensional (3D) polymer surface, which can then be monitored using surface-enhanced Raman scattering (SERS). This work is the first demonstration of the assembly of gold nanoparticles on a filter film and in situ measurement with Raman spectroscopy. Herein, a polyhexamethylene adipamide (Nylon66) film embedded in the organic filter film was used as a template to fabricate a tunable SERS-active substrate. A “hotspot”-rich gold-nanoparticle-decorated polymer substrate for SERS was prepared; this substrate exhibited high sensitivity in trace detection of targets. The study was conducted using 4-mercaptobenzoic acid as a probe molecule with the aim of comparing the scattering efficiency and the homogeneity of the Raman signal on selected substrates. In addition, we used the gold-decorated polymer film to detect a biotin-avidin complex. The most powerful advantage of the proposed microanalytical device is the in situ SERS application. The 3D nanoporous structures described in this work hold strong potential for use in various applications such as environmental monitoring and biomolecule detection.

Nickel electrodes as a cheap and versatile platform for studying structure and function of immobilized redox proteins.

Practical use of many bioelectronic and bioanalytical devices is limited by the need of expensive materials and time consuming fabrication. Here we demonstrate the use of nickel electrodes as a simple and cheap solid support material for bioelectronic applications. The naturally nanostructured electrodes showed a surprisingly high electromagnetic surface enhancement upon light illumination such that immobilization and electron transfer reactions of the model redox proteins cytochrome b5 (Cyt b5) and cytochrome c (Cyt c) could be followed via surface enhanced resonance Raman spectroscopy. It could be shown that the nickel surface, when used as received, promotes a very efficient binding of the proteins upon preservation of their native structure. The immobilized redox proteins could efficiently exchange electrons with the electrode and could even act as an electron relay between the electrode and solubilized myoglobin. Our results open up new possibility for nickel electrodes as an exceptional good support for bioelectronic devices and biosensors on the one hand and for surface enhanced spectroscopic investigations on the other hand.

Direct detection of fluoride ions in aquatic samples by surface-enhanced Raman scattering

Given the strong hydration propensity of fluoride ions, it is difficult to detect fluoride, especially inorganic fluoride, in aqueous samples. Resolving the issue of fluoride detection in aqueous samples is a scientific undertaking of great practical significance. Herein, we propose a new method for the sensitive and selective detection of fluoride in aqueous samples without the addition of organic solvents. The method involves surface-enhanced Raman spectroscopy using 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) compounds and Ag nanoparticles. The method is based on a diketopyrrolopyrrole compound linked to 1-butyl iodide (DPP1), which can sense fluoride sensitively and selectively. When DPP1 was combined with Ag NPs and reacted with tetrabutylammonium fluoride or inorganic fluoride in aqueous samples, an obvious Raman enhancement was obtained at the excitation wavelength of 633nm. This response arises because the introduction of fluoride anions into the system changes the molecular orientation of DPP1 on the Ag NP substrate from horizontal to vertical, inducing a signal enhancement in the Raman spectrum. This system can detect inorganic fluoride at concentrations as low as 1.0μmolL-1 (0.018ppm), which is far below the public health service recommended levels for drinking water (0.7-1.2ppm). Furthermore, using the proposed method, a linear response for fluoride in the concentration range of 1.0 × 10-3-1.0 × 10-6molL-1 was obtained, which makes fluoride detection possible in practical samples, such as fluoride-containing toothpaste.

Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43×10-8mol·L-1 with a relatively wider linear concentration range (1.0×10-7-1.0×10-4mol·L-1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

Antibody-Free Discrimination of Protein Biomarkers in Human Serum Based on Surface-Enhanced Raman Spectroscopy

Protein biomarkers are very important indicators of diseases and have great potential in cancer early diagnosis. The majority of detection methods for protein biomarkers currently rely on specific capture antibodies or aptamers with chemiluminescent and fluorescent labels. Here, an antibody-free strategy for discrimination of versatile proteins is proposed based on surface-enhanced Raman spectroscopy. The SERS spectral variation of a linker molecule, perylenetetra carboxylic acid (PTCA), is found to directly correlate with the protein types, according to which protein biomarkers even homologous proteins with very similar molecular structures can be discriminated with the aid of hierarchical cluster analysis. Furthermore, the feasibility of the proposed approach has been proved in early liver cancer diagnosis with clinical samples. All the results indicate that PTCA as a universal SERS probe has great potential in rapid, accurate, and direct protein biomarker discrimination in cancer diagnosis.

Electron Transfer of Cytochrome c on Surface-Enhanced Raman Scattering-Active Substrates: Material Dependence and Biocompatibility

Surface-enhanced Raman spectroscopy (SERS) represents a powerful approach for studying the structure and reaction of proteins in fundamental and applied sciences. The surface properties of SERS-active materials determine important parameters such as Raman enhancement ability, biocompatibility, and electronic communication between supports and proteins. Here, electron transfer (ET) of Cyt c on noble metals and transition metals is investigated by SERS spectroscopy. The results here indicate that the ET occurs from the reduced state of Cyt c to silver substrate, depending on the laser wavelengths. Nickel and cobalt can directly transfer electrons to the oxidized state of Cyt c, which enables a reductive activity of these transition metal nanoparticles (NPs). This study demonstrates the role of transition metals as electron donors for Cyt c and has proved that the charge transfer theory for SERS is applicable for explanation of the ET between Cyt c and Ag NPs.

Quantitative Determination of Total Amino Acids Based on Surface-Enhanced Raman Scattering and Ninhydrin Derivatization

In the present study, we propose a simple and sensitive method for the determination of total amino acids without any separation steps. The procedure described here is based on the ninhydrin derivatization reaction with amino acids, followed by surface-enhanced Raman scattering (SERS) measurements of the producing mixtures. A good linear correlation of excess ninhydrin SERS signals and the log values of the total amino acids concentrations is obtained; the detection limit of the method is 4.3 × 10-9 mol L-1. The derivatization reaction is reliable and the whole experimental procedure is very simple. The sensitivity of the proposed protocol allows quantitative analysis of total amino acids at picomole levels without any separation procedures. On the basis of the conventional ninhydrin reaction, we put forward a simple SERS method for determining the total amino acids concentrations with high sensitivity, which is a promising way for routine detection.