NMR and chemometric methods: a powerful combination for characterization of Balsamic and Traditional Balsamic Vinegar of Modena.

This work presents the capability of NMR spectroscopy combined with Chemometrics in predicting the ageing of Balsamic and Traditional Balsamic Vinegar of Modena. The need of an analytical method is an important requirement for both research oriented and commercial evaluation of these very valuable products. (1)H NMR spectroscopy, based on the advantage of rapid sample analysis without any manipulation or derivatization, is here proposed as a valid tool to describe Balsamic and Traditional Balsamic Vinegar of Modena. For this purpose, 72 reliable samples, were divided into three different groups according to their ageing process: young (<12 years), old (>12 and <25 years) and extra old (>25 years). Hierarchical Projection to Latent Structures Discriminant Analysis (PLS-DA) allowed us to characterize the ageing process. Variables showing the largest VIP (Variable Importance in the Projection) were extracted from PLS-DA model, thus shedding lights onto the role played by specific compounds in this complex ageing process. Two robust classification models, were built by PLS-DA and Naïve Bayes classifier and compared to prove the accuracy of the representation on both training and test sets. The predictions obtained for 41 "unknown" vinegar samples with these both methods gave more than 80% agreement among them.

[1]  J. Spangenberg,et al.  The application of NMR and MS methods for detection of adulteration of wine, fruit juices, and olive oil. A review , 2003, Analytical and bioanalytical chemistry.

[2]  M. Gullo,et al.  Characterization of acetic acid bacteria in "traditional balsamic vinegar". , 2006, International journal of food microbiology.

[3]  S Landi,et al.  Molecular assessment of indigenous yeast population from traditional balsamic vinegar , 2006, Journal of applied microbiology.

[4]  S. Wold,et al.  PLS-regression: a basic tool of chemometrics , 2001 .

[5]  M. Cocchi,et al.  Simultaneous determination of sugars and organic acids in aged vinegars and chemometric data analysis. , 2006, Talanta.

[6]  A. M. Gil,et al.  Composition of beer by 1H NMR spectroscopy: effects of brewing site and date of production. , 2006, Journal of agricultural and food chemistry.

[7]  C. Guillou,et al.  A coupled NMR and MS isotopic method for the authentication of natural vinegars , 1992 .

[8]  David E. Goldberg,et al.  Genetic algorithms and Machine Learning , 1988, Machine Learning.

[9]  Alessandro Ulrici,et al.  Determination of carboxylic acids in vinegars and in Aceto Balsamico Tradizionale di Modena by HPLC and GC methods. , 2002, Journal of agricultural and food chemistry.

[10]  A. Ulrici,et al.  A study of the relationships among acidity, sugar and furanic compound concentrations in set of casks for Aceto Balsamico Tradizionale of Reggio Emilia by multivariate techniques , 2005 .

[11]  Yizeng Liang,et al.  Uniform design and its applications in chemistry and chemical engineering , 2001 .

[12]  Andrea Antonelli,et al.  HPLC Determination of Organic Acids in Traditional Balsamic Vinegar of Reggio Emilia , 2003 .

[13]  R. Consonni,et al.  1H NMR studies on Italian balsamic and traditional balsamic vinegars. , 2004, Journal of agricultural and food chemistry.

[14]  M. Brenes,et al.  Comparison of analytical methodologies based on 1h and 31p NMR spectroscopy with conventional methods of analysis for the determination of some olive oil constituents. , 2007, Journal of agricultural and food chemistry.

[15]  A. Hermann.  Determination of D/H isotope ratio in acetic acid from vinegars and pickled products by 2H-NMR-spectroscopy , 2001 .

[16]  S. Fanali,et al.  Chiral MEKC‐LIF of amino acids in foods: Analysis of vinegars , 2006, Electrophoresis.

[17]  Ing-Marie Olsson,et al.  D-optimal onion designs in statistical molecular design , 2004 .

[18]  M. Sáiz-Abajo,et al.  Multi-objective optimisation strategy based on desirability functions used for chromatographic separation and quantification of L-proline and organic acids in vinegar , 2005 .

[19]  A. Caligiani,et al.  Identification and quantification of the main organic components of vinegars by high resolution 1H NMR spectroscopy. , 2007, Analytica chimica acta.

[20]  Roberto Todeschini,et al.  A new algorithm for optimal, distance based, experimental design , 1992 .

[21]  Svante Wold,et al.  Hierarchical multiblock PLS and PC models for easier model interpretation and as an alternative to variable selection , 1996 .

[22]  A. M. Gil,et al.  High-resolution nuclear magnetic resonance spectroscopy and multivariate analysis for the characterization of beer. , 2002, Journal of agricultural and food chemistry.

[23]  Davide Bertelli,et al.  Extraction and identification by GC-MS of phenolic acids in traditional balsamic vinegar from Modena , 2006 .

[24]  R. Consonni,et al.  NMR relaxation data for quality characterization of Balsamic vinegar of Modena. , 2007, Talanta.

[25]  Y. Vodovotz,et al.  Profiling of carotenoids in tomato juice by one- and two-dimensional NMR. , 2006, Journal of agricultural and food chemistry.

[26]  Jacob Cohen.  A Coefficient of Agreement for Nominal Scales , 1960 .

[27]  Thomas D. Nielsen,et al.  Classification using Hierarchical Naïve Bayes models , 2006, Machine Learning.

[28]  E. Anklam,et al.  Determination of 5-Hydroxymethylfurfural in Vinegar Samples by HPLC , 1998 .