Rapid analysis of trace volatile formaldehyde in aquatic products by derivatization reaction-based surface enhanced Raman spectroscopy

Abstract

Toxic formaldehyde is sometimes used illegally as a food preservative, however, on-site rapid analysis of trace formaldehyde in aquatic products remains a challenge. In this work, a simple on-site rapid quantification method for trace volatile formaldehyde in aquatic products was developed by a derivative reaction-based surface enhanced Raman spectroscopy (SERS) technique coupled with a homemade portable purge-sampling device. Trace formaldehyde separated from complicated aquatic matrices via a purge-sampling procedure was reacted with a derivative reagent to produce a Raman-active analyte for consequent SERS analysis. Au/SiO2 nanoparticles (NPs) were employed as the enhancement substrate to achieve significant enhancement of Raman signal intensity. Conditions of derivative reaction and SERS detection were optimized in detail, and the selectivity of this analytical method was also evaluated based on related analogs. Under optimal conditions, an extremely low detection limit of 0.17 μg L(-1) was achieved. Trace volatile formaldehyde can be found in fresh squid and shrimp samples without obvious matrix interference, and this was quantified to be 0.13-0.21 mg kg(-1) using the described method. The recoveries of spiked aquatic product samples were found to be 70.0-89.1% with RSDs of 2.3-7.2% (n = 3). The results suggest that the proposed method is reliable and suitable for on-site rapid analysis of trace formaldehyde in aquatic products.

SERS detection of food contaminants by means of portable Raman instruments

“…in order to increase the affinity of the analyte towards the substrate surface. In addition, it also possible to transform the analytes of interest by chemical reaction into new species with improved cross section and/or affinity to the metallic substrate: This method was used, for example, to detect nitrites and formaldehyde . A further development of these methodologies and their integration with plasmonic substrates is crucial for a widespread use of SERS.…”

“…Sulfite i-Raman (B&W Tek) Au NPs on ZnO (μPAD) (b) 2 μg/ml Chen et al [147] Nitrite (Little Swan) Ag NPs (a) 0.01 mg/L Ma et al [148] Nitrite is chemically transformed in another species with higher SERS activity Formaldehyde (DeltaNu) Au@SiO 2 NPs (a) 0.17 μg/L (fish) Zhang et al [149] Formaldehyde is chemically transformed in another (Continues) such as gastroenteritis and urinary tract infections: For example, the verocytotoxin-producing E. coli caused an outbreak in 2011 in France and Germany and was found in raw milk, cheese, and undercooked beef. [152] Madyar et al [70] proposed a detection procedure on the basis of the use of multishell SERS tags.…”

Trace analysis of organic compounds in foods with surface‐enhanced Raman spectroscopy: Methodology, progress, and challenges

“…SERS has been applied to analyze trace chemicals in various foods, mainly hazardous compounds that may pose health risks. These typically include residual pesticides, herbicides, or insecticides in plant source foods (Fan et al., , ; Kang, Wu, Chen, Li, & Du, ; Liou, Nayigiziki, Kong, Mustapha, & Lin, ; Sun, Yu, & Lin, ; Zhao, Huang, Fan, & Lai, ), banned and restricted drugs (such as growth hormones and antibiotics) in muscle foods such as fish and chicken (Li et al., ; Xu et al., ), naturally occurred toxicants such as aflatoxins in grains (Lee, Herrman, Bisrat, & Murray, ) and histamine in fish (Janči et al., ), as well as prohibited or restricted additives such as melamine in processed foods (Lin et al., ; Zhao et al., ), formaldehyde in shrimp and squid (Zhang, Zhao, Ma, & Li, ), Sudan dyes in chili flakes (Ou et al., ), Sunset Yellow and Allura Red in beverages (Ou et al., ), and tert‐butylhydroquinone (TBHQ) in vegetable oils (Pan et al., ).…”

HCHO-reactive molecule with dual-emission-enhancement property for quantitatively detecting HCHO in near 100% water solution

“…Although there are many types of formaldehyde detection methods, including piezoelectric sensors [9], electrochemical biosensors [10], quartz crystal microbalance [11,12], Raman spectroscopy [13], gas chromatography [14,15], liquid chromatography [16,17], X-ray diffraction (XRD), transmission electron microscopy (TEM) [18] and biosensor methods [19][20][21]. Novel sensor technologies are needed to enable real time, in situ detection of formaldehyde in a compact and reusable manner [22,23].…”