Direct Detection of Toxic Contaminants in Minimally Processed Food Products Using Dendritic Surface-Enhanced Raman Scattering Substrates

We present a method for the surface-enhanced Raman scattering (SERS)-based detection of toxic contaminants in minimally processed liquid food products, through the use of a dendritic silver nanostructure, produced through electrokinetic assembly of nanoparticles from solution. The dendritic nanostructure is produced on the surface of a microelectrode chip, connected to an AC field with an imposed DC bias. We apply this chip for the detection of thiram, a toxic fruit pesticide, in apple juice, to a limit of detection of 115 ppb, with no sample preprocessing. We also apply the chip for the detection of melamine, a toxic contaminant/food additive, to a limit of detection of 1.5 ppm in milk and 105 ppb in infant formula. All the reported limits of detection are below the recommended safe limits in food products, rendering this technique useful as a screening method to identify liquid food with hazardous amounts of toxic contaminants.

[1]  Jinkai Zheng,et al.  Surface-Enhanced Raman Spectroscopy for the Chemical Analysis of Food. , 2014, Comprehensive reviews in food science and food safety.

[2]  P Hajdú,et al.  [Analytical methods I]. , 1975, Arzneimittel-Forschung.

[3]  Steven D. Christesen,et al.  Role of the Micro- and Nanostructure in the Performance of Surface-Enhanced Raman Scattering Substrates Assembled from Gold Nanoparticles , 2005, Applied spectroscopy.

[4]  George C Schatz,et al.  Resonance Raman scattering of rhodamine 6G as calculated using time-dependent density functional theory. , 2006, The journal of physical chemistry. A.

[5]  Qiang Wang,et al.  Ag dendritic nanostructures for rapid detection of thiram based on surface-enhanced Raman scattering , 2015 .

[6]  Quansheng Chen,et al.  Highly sensitive and label-free determination of thiram residue using surface-enhanced Raman spectroscopy (SERS) coupled with paper-based microfluidics , 2017 .

[7]  C. Escobedo,et al.  In situ assembly of active surface-enhanced Raman scattering substrates via electric field-guided growth of dendritic nanoparticle structures. , 2017, Nanoscale.

[8]  Carlos Escobedo,et al.  Rapid identification and quantification of illicit drugs on nanodendritic surface-enhanced Raman scattering substrates , 2018 .

[9]  A. Tritscher,et al.  The Melamine Incident: Implications for International Food and Feed Safety , 2009, Environmental health perspectives.

[10]  Sergey Arzhantsev,et al.  Selective melamine detection in multiple sample matrices with a portable Raman instrument using surface enhanced Raman spectroscopy-active gold nanoparticles. , 2012, Analytica chimica acta.

[11]  R. Narayanan,et al.  Solution-based direct readout surface enhanced Raman spectroscopic (SERS) detection of ultra-low levels of thiram with dogbone shaped gold nanoparticles. , 2011, The Analyst.

[12]  Jing Li,et al.  Efficient sample clean-up and online preconcentration for sensitive determination of melamine in milk samples by capillary electrophoresis with contactless conductivity detection. , 2014, Journal of separation science.

[13]  R. Dasari,et al.  Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS) , 1997 .

[14]  A. Malik,et al.  Thiram: degradation, applications and analytical methods. , 2003, Journal of environmental monitoring : JEM.

[15]  Hu Yongjun,et al.  Development of aptamer-modified SERS nanosensor and oligonucleotide chip to quantitatively detect melamine in milk with high sensitivity , 2016 .

[16]  H. Morgan,et al.  Ac electrokinetics: a review of forces in microelectrode structures , 1998 .

[17]  L. Dick,et al.  Metal film over nanosphere (MFON) electrodes for surface-enhanced Raman spectroscopy (SERS): Improvements in surface nanostructure stability and suppression of irreversible loss , 2002 .

[18]  G. Dent,et al.  Modern Raman Spectroscopy: A Practical Approach , 2005 .

[19]  Yaxi Hu,et al.  Rapid Detection of Melamine in Milk Using Immunological Separation and Surface Enhanced Raman Spectroscopy. , 2015, Journal of food science.

[20]  J. Jönsson,et al.  Determination of Melamine in Fresh Milk with Hollow Fiber Liquid Phase Microextraction Based on Ion-Pair Mechanism Combined with High Performance Liquid Chromatography , 2012 .

[21]  Hao Li,et al.  Use of a fractal-like gold nanostructure in surface-enhanced raman spectroscopy for detection of selected food contaminants. , 2008, Journal of agricultural and food chemistry.

[22]  T. Delatour,et al.  Screening and confirmatory methods for the determination of melamine in cow's milk and milk-based powdered infant formula: Validation and proficiency-tests of ELISA, HPLC-UV, GC-MS and LC-MS/MS , 2011 .

[23]  Eric C Le Ru,et al.  Single-molecule surface-enhanced Raman spectroscopy. , 2012, Annual review of physical chemistry.

[24]  Akhtar Hayat,et al.  Portable Nanoparticle-Based Sensors for Food Safety Assessment , 2015, Sensors.

[25]  Chul-Jae Lee,et al.  SERS of dithiocarbamate pesticides adsorbed on silver surface; Thiram , 2002 .

[26]  J. Ingelfinger.  Melamine and the global implications of food contamination. , 2008, The New England journal of medicine.

[27]  Jung-Rok Lee,et al.  Small Molecule Detection in Saliva Facilitates Portable Tests of Marijuana Abuse. , 2016, Analytical chemistry.

[28]  N. Pieczonka,et al.  Inherent complexities of trace detection by surface-enhanced Raman scattering. , 2005, Chemphyschem : a European journal of chemical physics and physical chemistry.

[29]  Gopalakrishnan Venkatasami,et al.  A rapid, acetonitrile-free, HPLC method for determination of melamine in infant formula. , 2010, Analytica chimica acta.

[30]  V. Chiș,et al.  FTIR, FT-Raman, SERS and DFT study on melamine , 2012 .

[31]  F. Fang,et al.  High performance surface-enhanced Raman scattering substrates of Si-based Au film developed by focused ion beam nanofabrication , 2012, Nanoscale Research Letters.

[32]  Amanda Deering,et al.  Melamine detection in infant formula powder using near- and mid-infrared spectroscopy. , 2009, Journal of agricultural and food chemistry.

[33]  Meikun Fan,et al.  A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry. , 2011, Analytica chimica acta.

[34]  B. Incledon,et al.  Optimization of protein precipitation based upon effectiveness of protein removal and ionization effect in liquid chromatography-tandem mass spectrometry. , 2003, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[35]  J. Irudayaraj,et al.  Surface-enhanced Raman spectroscopy applied to food safety. , 2013, Annual review of food science and technology.

[36]  P. Manzi,et al.  Melamine Detection in Milk and Dairy Products: Traditional Analytical Methods and Recent Developments , 2017, Food Analytical Methods.

[37]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[38]  Yongning Wu,et al.  A survey on occurrence of melamine and its analogues in tainted infant formula in China. , 2009, Biomedical and environmental sciences : BES.

[39]  U. Şireli,et al.  Determination of melamine in milk and dairy products by high performance liquid chromatography. , 2012, Journal of dairy science.

[40]  S. Yao,et al.  Simultaneous determination of melamine and related compounds by capillary zone electrophoresis , 2010 .

[41]  Rebecca L. M. Gieseking,et al.  Nanostructured organic semiconductor films for molecular detection with surface-enhanced Raman spectroscopy. , 2017, Nature materials.

[42]  Li Zhang,et al.  Synthesis of silver nanowires as a SERS substrate for the detection of pesticide thiram. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[43]  Hanqi Zhang,et al.  Rapid determination of melamine in milk and milk powder by surface-enhanced Raman spectroscopy and using cyclodextrin-decorated silver nanoparticles , 2013, Microchimica Acta.

[44]  Liguang Xu,et al.  Analytical methods and recent developments in the detection of melamine , 2010 .

[45]  S. Turnipseed,et al.  Determination of Melamine and Cyanuric Acid Residues in Infant Formula using LC-MS/MS , 2008 .