Fast Screening of Cocaine in Beverages Using Nano Extractive Electrospray Ionization Tandem

Fast quantitative detection of cocaine in beverages using nano extractive electrospray ionization tandem mass spectrometry

Bin Hu a, Xuejiao Penga, Shuiping Yanga, Haiwei Gua, Huanwen Chen*a, Yanfu Huanb,Tingting Zhangc, Xiaolin Qiao*c

a College of Chemistry, Biology and Material Science, East China Institute of Technology, Fuzhou 34400 P. R. China; b College of Chemistry, Jilin University, Changchun, 130023 P. R. China; c College of Information Science and Engineering, Harbin Institute of Technology at Weihai, Weihai 264000 P. R. China

Supporting Information

Tandem mass spectral data

Red Bull® energy drink

The functional ingredients in Red bull® are: water, sucrose, glucose, sodium citrates, carbon dioxide, taurine, glucuronolactone, caffeine, inositol, niacin, pantothenic acid, vitamin B6, vitamin B12, caramel and riboflavin.

Figure S1 Mass spectra collected from Red Bull® energy drink using nanoEESI mass spectrometry.

(a)NanoEESI mass spectrum of Red Bull® sample spiked with cocaine (1 ppt), the inset shows the zoomed view of the signal of VB12, showing sodiated VB12 at m/z 1378.

(b) MS/MS spectrum of protonated lysine. Thefragment ions at m/z129, 130, 119, and 84 could arise from the loss ofH2O, NH3, CO, [NH3, HCOOH]from the precursor ions.

(c) MS/MS spectrum of protonated caffeine, the major fragment ions at m/z 138, 110 were generated by the loss of CH3N=C=O, [CH3N=C=O, CO], respectively.

(d) Protonated vitamin B6 molecules (m/z 170) generated product ions of m/z 152 and m/z 134 by the loss of H2O, successively. In the MS3 spectrum of m/z 152 (inset of Figure S1 d), the precursor ions (m/z 170) yielded the major fragments of m/z 124, 134 by the loss of H2O, CO, respectively.

(e) MS/MS spectrum of protonated taurine. The major fragment ions at m/z 108, 109 were created by the loss of H2O, NH3, respectively.

(f) MS/MS spectrum of protonated inositol. The major fragment ions atm/z163, 180, 181 were produced by the loss of [H2O, NH3],H2O, NH3. respectively.

(g) MS/MS spectrum of the protonated nicotinamide. The major fragment ion atm/z106, 95, 81, 80, 67 were derived from the precursor ions by the loss of NH3, CO,[CO, •HCH•], O=C=NH, [CO, 2•HCH•]. respectively.

(h) MS/MS of the sodiated vitamin B12 [M+Na]+. The major fragments at m/z 1016 represents to [M+ H-basesugar-PO3]+, the ions of m/z 931 corresponds to [M+ H-base-sugar-PO3-CN-Co]+, which is in agreement with the previous results[1].

Figure S2 Mass spectra collected from Coca-Cola® and Pepsi® drink samples using nanoEESI mass spectrometry.

(a) NanoEESI mass spectrum of Coca-Cola® sample spiked with cocaine (1 ppt).

(b) Mass spectrum of Pepsi® sample spiked with cocaine (1 ppt). Note that these spectra(Figure S2 a, b) are similarly with the same major compounds such as sodiated H3PO4 [H3PO4+Na]+ at m/z 121, [H3PO4+H2O+Na]+ at m/z 139, sodiated Fructose [Fru-H2O+Na]+ at m/z185, [Fru+Na]+ at m/z203 [2Fru-H2O+Na]+ at m/z 365, [2Fru-2H2O+Na]+ at m/z 347, and [2Fru-3H2O+Na]+ at m/z 329, respectively. The ammonium adducts was clearly obseved at m/z 198, 180, 162, 144 for [Fru+NH4]+, [Fru+NH4 –H2O]+, [Fru+NH4–2H2O]+, and [Fru+NH4–3H2O]+, respectively. These observations are in good agreement with the previous results [2, 3]. However, many small peaks detected in these two spectra were not identified, probably due to other ingredients in the samples.

(c) MS/MS spectrum of the sodiated Fructose[2Fru-H2O+Na]+ (m/z 365). The major fragments of m/z 185, 203 correspondto[Fru-H2O+Na]+, [Fru+Na]+; the other fragment ions atm/z305，329，347 were generated by the loss of [CH2CO+H2O],H2O, 2H2O, respectively.

(d) MS/MS spectrum of the sodiated Fructose[Fru-H2O+Na]+ (m/z 185). The fragment ions atm/z 167, 125 were bereaved by the loss of H2O, [CH2CO+H2O], respectively.The ions atm/z 145 maybe correspondto[Fru-2H2O+H]+.

(e) MS/MS spectrum of the sodiated Glu[Fru+Na]+. The fragment ions atm/z 185, 143, 113 were produced by the loss of H2O, [CH2CO+H2O], [CH2CO+H2O+CH2O], respectively.

(f) MS/MS spectrum of the ammonium adducts [Glu+NH4–2H2O]+. The fragment ions atm/z 163, 145, 127, 85 were detected due to the loss of NH3, [NH3+H2O], [NH3+2H2O+CH2CO], respectively.

(g)MS/MS spectrum of the sodiated phosphoric acid. The fragment ions atm/z 121 were created by the loss of H2O. In the MS3 spectrum (inset of Figure S 2g), the precursor ions yielded the major fragments of m/z 105, 93 probably by the loss of •O, and H2O, respectively.

References

1.Luo, X.; Chen, B.; Ding, L.; Tang, F.; Yao, S., HPLC-ESI-MS analysis of Vitamin B12 in food products and in multivitamins-multimineral tablets. Analytica Chimica Acta 2006, (562), 185–189.

2.Engelhardt, A. K. U. H., Thermospray-LC-MS analysis of various groups of polyphenols in tea I. Catechins, flavonol O-glycosides and flavone C-glycosides. Z Lebensm Unters Forsch 1996, 202, 48-54.

3.Taylora, V. F.; March, R. E.; Longerich, H. P.; Stadey, C. J., A mass spectrometric study of glucose, sucrose, and fructose using an inductively coupled plasma and electrospray ionization. International Journal of Mass Spectrometry 2005, 243, 71－84.

1