Article pubs.acs.org/JAFC

Rapid Screening of Multiclass Syrup Adulterants in Honey by Ultrahigh-Performance Liquid Chromatography/Quadrupole Time of Flight Mass Spectrometry Bing Du,†,‡ Liming Wu,§ Xiaofeng Xue,*,‡,§ Lanzhen Chen,‡,§ Yi Li,§ Jing Zhao,⊗ and Wei Cao*,† †

Department of Food Science and Engineering, School of Chemical Engineering, Northwest University, 229 North TaiBai Road, Xi’an 710069, China ‡ Institute of Apiculture Research, Chinese Academy of Agricultural Sciences, Beijing 100093, China § Risk Assessment Laboratory for Bee Products Quality and Safety, Ministry of Agriculture, Beijing 100093, China ⊗ Bee Product Quality Supervisionand Testing Center, Ministry of Agriculture, Beijing 102202, China ABSTRACT: Honey adulteration with sugar syrups is a widespread problem. Several types of syrups have been used in honey adulteration, and there is no available method that can simultaneously detect all of these adulterants. In this study, we generated a small-scale database containing the specific chromatographic and mass spectrometry information on sugar syrup markers and developed a simple, rapid, and effective ultrahigh-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UHPLC/Q-TOF-MS) method for the detection of adulterated honey. Corn syrup, high-fructose corn syrup, inverted syrup, and rice syrup were used as honey adulterants; polysaccharides, difructose anhydrides, and 2-acetylfuran-3glucopyranoside were used as detection markers. The presence of 10% sugar syrup in honey could be easily detected in 11) as markers of honey adulteration. The chromatographic profile of polysaccharides (DP 12−19) is shown in Figure 3a. Polysaccharides exist in the form of multicharged ions. In our experiments, polysaccharides E

DOI: 10.1021/acs.jafc.5b01410 J. Agric. Food Chem. XXXX, XXX, XXX−XXX

Article

Journal of Agricultural and Food Chemistry Table 1. Characteristics of Sugar Syrup Markers target compound 2-acetylfuran-3-glucopyranoside (AFGP) difructose anhydride III (DFA III)a maltododecaose (DP 12) maltotridecaose (DP 13) maltotetradecaose (DP 14) maltopentadecaose (DP 15) maltohexadecaose (DP 16) maltoheptadecaose (DP 17) maltooctadecaose (DP 18) maltononadecaose (DP 19) a

molecular formula

retention time (min)

mass

C12H16O8

1.188

288.0845

C12H20O10

1.522

324.1056

10.523 10.596 10.664 10.738 10.802 10.875 10.946 11.012

1962.6444 2124.6973 2286.7501 2448.8029 2610.8557 2772.9086 2934.9614 3097.0142

C72H122O61 C78H132O66 C84H142O71 C90H152O76 C96H162O81 C102H172O86 C108H182O91 C114H192O96

m/z values of characteristic ions 287.0772 [M − H]−, 575.1618 [2M − H]−, 333.0822 [M + HCOO]− 323.0984 [M − H]−, 647.204 [2M − H]−, 369.1033 [M + HCOO]− 1961.6372 [M − H]−, 980.3149 [M − 2H]2− 2123.69 [M − H]−, 1061.3414 [M − 2H]2− 2285.7428 [M − H]−, 1142.3678 [M − 2H]2− 2447.7956 [M − H]−, 1223.3942 [M − 2H]2− 2609.8485 [M − H]−, 1304.4206 [M − 2H]2− 2771.9013 [M − H]−, 1385.447 [M − 2H]2− 1466.4734 [M − 2H]2− 1547.4998 [M − 2H]2−

allowance error (ppm)