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  • Journal of Chromatography A, 1216 (2009) 71107129

    Contents lists available at ScienceDirect

    Journal of Chromatography A

    journa l homepage: www.e lsev ier .com/ locate /chroma

    Review

    Multidimensional chromatography in food analysis

    Miguel Herreroa,b, Elena Ibnezb, Alejandro Cifuentesb,, Jose Bernalb

    a Seccin Departamental Ciencias de la Alimentacin, Universidad Autnoma de Madrid, Campus de Cantoblanco, 28049 Madrid, Spainb Instituto de Fermentaciones Industriales (CSIC), Juan de la Cierva 3, 28006 Madrid, Spain

    a r t i c l e i n f o

    Article history:Available online 13 August 2009

    Keywords:LC LCGC GCLCGCBidimensional chromatographyTwo-dimensionalFoodsBeverages

    a b s t r a c t

    In this work, the main developments and applications of multidimensional chromatographic techniquesin food analysis are reviewed. Different aspects related to the existing couplings involving chromato-graphic techniques are examined. These couplings include multidimensional GC, multidimensional LC,multidimensional SFC as well as all their possible combinations. Main advantages and drawbacks of eachcoupling are critically discussed and their key applications in food analysis described.

    2009 Elsevier B.V. All rights reserved.

    Contents

    1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71102. Multidimensional gas chromatography (MDGC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7111

    2.1. Conventional and advanced heart cutting MDGC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71112.2. Comprehensive two-dimensional gas chromatography (GC GC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7114

    3. Multidimensional liquid chromatography (MDLC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71183.1. Off-line MDLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71183.2. On-line MDLC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71193.3. Comprehensive two-dimensional LC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7120

    4. Multidimensional LCGC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7124

    5. Other multidimensional chromatography couplings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71266. Conclusions and future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7127

    . . . .. . . . .

    1

    bi[pmOo

    0d

    Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    . Introduction

    Single column (one-dimensional) chromatography analysis haseen used for many years as a standard separation tool for analyz-

    ng compounds in a broad variety of fields including food analysis16]. At present, attention is being paid to avoid laborious sample

    re-treatments that can in fact be an important source of errorsainly for complex matrices as e.g., food or food-related matrices.ne-dimensional chromatography does not always provide the res-lution and separation power required to obtain the best results

    Corresponding author. Tel.: +34 915 622 900; fax: +34 915 644 853.E-mail address: acifuentes@ifi.csic.es (A. Cifuentes).

    021-9673/$ see front matter 2009 Elsevier B.V. All rights reserved.oi:10.1016/j.chroma.2009.08.014. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7127. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7127

    in terms of identification of analytes in food samples. This prob-lem frequently comes out even considering the large number ofdetectors developed in the past years, including MS detectors.

    Multidimensional chromatography has emerged as an inter-esting alternative to analyze complex samples in a situation inwhich technological improvements, such as new column technolo-gies, seem to be close to their maximum level. Thus, peak capacityenhancement achievable by multidimensional chromatography isby far higher than the obtained after improving by any meanone-dimensional separations. Multidimensional chromatographyallows combination of two or more independent or nearly indepen-

    dent separation steps, increasing significantly the separation powerof the corresponding one-dimensional techniques and, therefore,the physical separation of compounds in complex samples.

    http://www.sciencedirect.com/science/journal/00219673http://www.elsevier.com/locate/chromamailto:acifuentes@ifi.csic.esdx.doi.org/10.1016/j.chroma.2009.08.014

  • M. Herrero et al. / J. Chromatogr. A 1216 (2009) 71107129 7111

    Fig. 1. Evolution of the published works in the last decade in food analysis usingmultidimensional chromatography (data up to July 2009). The sources of informa-tion were the databases: Isi-Web of Knowledge, Scirus, Scopus and Science Direct.The search has been done using as keywords. [(Multidimensional Liquid Chromatog-raphy) or (Multidimensional Gas Chromatography) or (Two-dimensional LiquidCLFo

    tadaalgm

    st(d

    gdTaer

    2

    pu(cOaswalwdcustsstG

    Fig. 2. Designs of different multidimensional gas chromatography systems incor-porating (ad) heartcut valves, multiple detectors (D1, D2), multiple columns, dual

    switcher [2226]. By using a valve, control of pressure and flow ishromatography) or (Two-dimensional Gas Chromatography) or (Comprehensiveiquid Chromatography) or (Comprehensive Gas Chromatography) or (Supercriticalluid Chromatography) or (LC LC) or (GC GC) or (LCLC) or (GCGC) or (LCGC)r (MDGC) or (MDLC) or (SFC SFC) or (SFC LC)] and (Food or Beverages).]

    The main goal of this review is to describe the present state-of-he-art of multidimensional chromatography in the field of foodnalysis. For this purpose, the different existing couplings areescribed and their most important advantages and drawbacksre commented. Besides, the most remarkable applications in foodnalysis are critically discussed. Different couplings involving gas,iquid and supercritical fluid chromatography, for the analysis of areat variety of compounds in different food matrices (honey, wine,ilk, cheese, oils, etc.) are considered.To illustrate the increasing importance of the use of multidimen-

    ional chromatographic techniques in food analysis, Fig. 1 showshe evolution of the number of published papers on this topici.e., multidimensional chromatography in food analysis) in the lastecade.

    Several interesting works have already been published oneneral aspects (fundamentals, design and applications) of theifferent chromatographic multidimensional techniques [714].herefore, only a brief description of each multidimensionalpproach will be given in the following sections. Readers inter-sted on more specific instrumental or fundamental details can takeesort of the aforementioned review works.

    . Multidimensional gas chromatography (MDGC)

    Single-column gas chromatography actually offers quite higheak capacities along with a diverse number of available config-rations and detectors. However, when highly complex sampleslike food matrices) have to be studied, some peak overlappingan occur leading to ambiguous or problematic peak identification.ne option to improve the separation power is to couple, throughn interface, two or more independent columns giving rise to theo-called multidimensional gas chromatography (MDGC). MDGCas developed several decades ago [15] and it has been used to

    nalyze a large variety of samples [9]. Few years ago, Bertsch pub-ished two reviews dealing with the principles of MDGC [9,11]; it

    as stated that two-dimensional gas chromatography (and higherimensional systems) consists of an arrangement of two or moreolumns where distinctive segments of effluent from the first col-mn are fed into one or more columns. Different designs of MDGCyste