1 3 DOI 10.1007/s10337-016-3159-0 Chromatographia (2016) 79:1553–1559 ORIGINAL Binary Simple Sugar Profiling in Corn and Small Grain Flour Authentication Using GC/EI-qMS Approach Kristian Pastor 1 · Marijana Ac ˇanski 1 · Ðura Vujic ´ 2 · Ankica Kondic ´-Špika 3 Received: 28 April 2016 / Revised: 11 July 2016 / Accepted: 12 August 2016 / Published online: 24 August 2016 © Springer-Verlag Berlin Heidelberg 2016 Introduction Food choices and eating behavior are increasingly dis- cussed from health-related viewpoints [1, 2]. Currently, there is also a general trend in food science toward the con- nection between food and health. Thus, food is considered today not only as a source of energy, but also as an afford- able way to prevent future diseases [3]. Cereal grains are an important energy source throughout the world. Grain-based foods provide the majority of the carbohydrate and dietary fiber intakes in many countries [4, 5]. Cereal grains and products have also gained popularity in contributing to healthy eating behavior because of their antioxidant properties associated with protection against chronic diseases [6]. Furthermore, whole grains consump- tion is protective against stroke and metabolic syndrome. They contain antioxidants, dietary fiber (inulin, beta-glu- can, resistant starch), phenolics, phytate, phyto-estrogens, phytostanols, phytosterols, vitamins (carotenoids, tocot- rienols, tocopherols) and minerals. Fiber-rich cereals con- sumption helps reduce cholesterol, hypertension, constipa- tion and obesity [5, 7]. With a view to producing quality products, verifying compliance with food standards and labeling legislation, and to detect food fraud, European standards include regu- lar laboratory control of raw materials, semi-finished and finished products [8, 9]. There are several destructive and non-destructive tech- niques for food authentication that have been the most suc- cessful, including: DNA-based speciation techniques, trace elements and stable isotope ratios analysis, 1 H, 2 H, 13 C nuclear magnetic resonance, etc. [9, 10]. Fingerprinting includes a variety of analytical tech- niques or methods that provide analytical signals, such as spectra or chromatograms, related to the composition Abstract There is an increasing demand for mixed flour bakery products in the world market, considering the health benefits of various cereal grains. The aim of this work was to develop a rapid approach for corn and small grain flour authentication. Simple sugars present in flour samples were extracted with 96 % ethanol solution, derivatized into cor- responding trimethylsilyl oximes (TMSO), and analyzed on a GC/EI-qMS device. The presence of a specific simple sugar at a specific retention time was confirmed using mass spectrometer, thus providing a semi-qualitative approach. Binary matrices were developed based on the presence/ absence of detected simple sugar compounds in the investi- gated cereal species, to minimize the influence of variabil- ity between investigated cultivars of the same species. By performing exploratory data analysis: hierarchical cluster analysis (HCA), principal coordinate analysis (PCO), and principal component analysis (PCA), flour samples of corn species were strongly separated from every investigated species of small grains, using all three multivariate tools, thus enabling its authentication in a small grain/corn flour mixture. Keywords GC/EI-qMS · Exploratory data analysis · Corn flour · Small grain flour · TMSO * Kristian Pastor pastor@tf.uns.ac.rs 1 Department of Applied and Engineering Chemistry, Faculty of Technology, University of Novi Sad, Bul. Cara Lazara 1, 21000 Novi Sad, Serbia 2 University of Novi Sad, Dr Zorana Ðinđića 1, 21000 Novi Sad, Serbia 3 Institute of Field and Vegetable Crops, Maksima Gorkog 30, 21000 Novi Sad, Serbia