Authenticity control

Oebelmann, J., Juchelka, D., Hilkert, A., Avak, H., Douthitt Ch. Authenticity control by multiple element isotope ratio determination. Unpublished Materials. Thermo Finnigan, 2001. 

Mosandl A, Enantioselective capillary gas chromatography and stable isotope ratio mass spectrometry in the authenticity control of flavors and essential oils, Food Rev Int. 537—SSA, 1995. 

Casabianca H, Graff JB, Faugier V, Fleig F, Grenier C, Enantiomeric distribution studies of linalool and linalyl acetate A powerful tool for authenticity control of essential oAs, J High Resol Chromatogr 21 107—112, 1998. 

Selective transfer of compounds of interest into a second column Enantioresolution of lactones for authenticity control of fruit products [20-24]... 

Enantioresolution of ter-penes for authenticity control in essential oils [24-26]... 

Kreis, P. and Mosandl, A. 1992. Chiral compounds of essential oils. Part XII. Authenticity control of rose oils, using enantioselective multidimensional gas chromatography. Flavour Fragrance J. 7 199-203. 

Much progress has also been made in the development of methods for authenticity control of flavor compounds, such as chiral separations or isotope ratio analysis. However, a comprehensive discussion of this subject would have gone beyond the limits of this chapter. The interested reader is, therefore, referred to some recent articles published in this field [109-111],... 

Frank, C., Dietrich, A., Kremer, U. and Mosandl, A. (1 995) GC-IRMS in the authenticity control of the essential oil of Coriandrum sativum L. Journal of Agricultural and Food Chemistry 43(6), 1634-1 637. 

Additionally, hydroxycinnamates are important constituents of acylated antho-cyanins. In red wine, the 6-6>-coumaroylglucosides and caffeoylglucosides are common constituents (Mazza and Miniati 1993). In the authenticity control of red wine the relation of acetylated and coumaroylated anthocyanins can be used for the assessment of the grape variety (Holbach et al. 2001 Otteneder et al. 2002). 

Summarising the advantages and problems of NMR as a tool for authenticity control in the flavouring and aroma field one can state ... 

R. Braunsdorf, U. Hener, S. Stein, A. Mosandl (1993) Comprehensive cGC-lRMS analysis in the authenticity control of flavours and essential oils. Part 1 Lemon oil. Z. Lebensm. Unters. Forsch. 197. 137-141... 

A. Mosandl, R. Braunsdorf, A. Dietrich, B. Faber, V. Karl, T. Kopke, D. Lehmann, B. Maas (1994) Recent development in the authenticity control of flavours and fragrances. In H. Maarse, D.G. van der Heij (eds.) Trends in Flavour Research. Elsevier Science B.V., Amsterdam, pp. 89-98... 

H.-L. Schmidt, D. Weber, A. Rossmann, R.A. Werner (1999) The potential of intermolecular and intramolecular isotopic correlations for authenticity control, in R. Teranishi, E.L.Wick, 1. Horn-stein (edts). Flavor Chemistry, Thirty Years of Progress, Kluver Academic/Plenum Press, New York 1999, pp. 55-61... 

The essential oils of the Mentha species are known to be valuable ingredients of pharmaceutical and cosmetic preparations. Menthone, isomenthone, menthol and menthyl acetate, the most important Mentha oil constituents, are defined by their amounts as substantial parameters of mentha oil quality. Even off-line HPTLC/enan-tio-GC coupling has proved to be a valuable method in authenticity control of mint and peppermint oils. After preseparating by HPTLC (silica gel dichloromethane) the menthyl acetate fraction is isolated and directly injected for stereodifferentiation with permethyl p-cyclodextrin. Racemic menthyl acetate was detected by Kreis et al. as a frequently used adulteration of Mentha oils [20]. 

Chirality evaluation of linalyl acetate and linalool have been introduced as new and substantial criteria in the authenticity control of lavender oils. In particular, linalyl acetate from genuine lavender oils has high enantiomeric purity favouring the R-configuration, irrespective of the Lavandula species, and storage or work-up conditions [32]. Using 2,3-di-0-acylated-6-0-silylated cyclodextrins as a new generation of chiral stationary phases in enantio-cGC, most of chiral compounds of Lavandula oil, are stereoanalyzed simultaneously (Fig. 6.37 Fig. 6.38). 

In summary, scope and limitations of linalool s enantiomeric ratio in the authenticity control of flavourings and fragrances are obvious ... 

Nevertheless, under the conditions of good manufacturing practice (GMP) the chirality evaluation of linalool has proved to be a reliable indicator in the authenticity control of lavender, bergamot, and orange oils. This fact will be of considerable importance in the quality assurance for the flavour and fragrance industry. 

Comparative investigations on the enantiomeric purity of linalool and linalyl acetate in the essential oils of Lavandula angustrfolia MILLER leads to quick and simple techniques of gas chromatographic chirality evaluation of lavender oil compounds. Their usefulness in the authenticity control of lavender oil compounds is demonstrated in Lig. 6.39 [95]. 

Direct-infusion MS is a very interesting approach, especially when sample characteristics allow MS analysis with minimum sample treatment. Thus, ESI can be used to directly ionize analytes in liquid samples in a high electric field. A small flow of the liquid sample is conducted through a capillary to the high electric field for ESI. Usually, sample solutions must be carefully cleaned and filtered to avoid potential capillary blocking. Following this idea, direct-infusion ESI-FTICR (Fourier transform ion cyclotron resonance) MS of a coffee drink combined with partial least-squares multivariate statistical analysis was successfully employed to predict the blend composition of commercial coffee varieties (28). In a different work, minimal sample manipulation was carried out to obtain detailed molecular composition of edible oils and fats analyzed by flow-injection ESI-Orbitrap MS for quality assessment and authenticity control purposes (29). Commonly, when using direct infusion approaches, sample needs to be treated to dissolve the compounds of interest in the appropriate solvent. 

The increasing need for analytical methods to establish food authenticity has led to the development of a number of approaches, many of which involve the use of NMR spectroscopy. Some texts have reviewed the generally accepted methods for quality and authenticity control.15-167-172... 

The data collected so far (23-28) has shown that the norisoprenoids 8-11 are present in natural substrates in well-defined mixtures, thus enabling inter alia authenticity control of natural flavoring material. (Note The only exception are raspberries, which showed considerable variations in their composition of isomeric theaspiranes depending on their origin). The data also shows that obviously different enzymes are operative in plants, catalyzing the formation of different optical antipodes of Ci3-volatiles. TWs is evident from the fact that, e.g., vanilla beans were found to contain optically pure (2S)-isomers of vitispiranes lOb/d, whereas white-beam (Sorbus aria) leaves contain mainly the (2/f)-configured isomers lOa/c (25). 

Faulharber et al (5,6) and other researchers (7-9) have described how the determination of the isotope values of constituents is of increasing importance, especially in view of the demand for authenticity control and origin determination of essential oils and foods. To determine isotope values, g chromatography-isotope ratio mass spectrometry (GC-IRMS) has been used, although not widely. The present authors (70) have studied the possibility of a more convenient and common means of analysis of isotope values, based on the isotope peak in the mass spectrum of a compound. The present study focuses on the development of a new analytical method for the differentiation of quality in commercial citrus oils of various origins. 

Chiral GC is successfiilly used for the precise determination of the enantiomeric composition of volatile natural compounds, authenticity control of essential oils, flavors, fragrances, some chiral research tiiemicals, auxiliaries, a few volatile drugs, drug metabolites, pesticides, fungicides, herbicides, pheromones, etc. [13]. 

Fliigel, R., Carle, R., Schieber, A. Quality and authenticity control of fruit purees, fruit preparations and jams - a review. Trends Food Sci. Technol. 16, 433 (2005)... 

In the field of essential oils, separation of individual enantiomers and determination of enantiomer excess play an important role in the characterization of plant material, in the investigation of the origin of the essential oil, and in the search of possible adulterations. Reliable assessment of the genuineness of essential oils is a difficult task, since synthetic analogs of essential oil components are commercially available. Therefore, suitable specific methods in the authenticity control of essential oils are of fundamental interest. Two-dimensional GC is a useful technique for both analytical and preparative purposes. After a separation of aroma components on a first column, they are on-line transferred to a second... 

Enantioselective GC-IRMS and two-dimensional GC-IRMS represent other powerful techniques in the authenticity control of natural flavors and fragrances using IRMS, identical 5 C ratios are expected for enantiomers from genuine substances. Interesting investigations have been recently accomplished by using GC-IRMS in the authenticity control of essential oils [29-31]. 

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