Analysis of Anthocyanins in Red Wine and Fruit Juice Using MALDI-MS

Abstract

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a powerful new technique that will have a great impact on food analysis. This study is the first to demonstrate the applicability of MALDI-MS to perform both qualitative and quantitative analyses of anthocyanins in food. 2,4, 6-Trihydroxyacetophenone (THAP) was found to be a good matrix for analysis of anthocyanins, with the best spot-to-spot repeatability. After a simple sample preparation, the presence of anthocyanins as cations with molecular masses was found in ratios expected from their fruit sources. Quantification of anthocyanins should be possible by choosing appropriate internal standards. MALDI-MS responses were linear, groups of chemically similar anthocyanins had similar responses, and addition of an internal standard had no effect on relative responses of the other anthocyanins.

Extraction, separation, and detection methods for phenolic acids and flavonoids

“…Identification of phenolics separated after HPLC was also carried out using fast atom bombardment mass spectrometry [154,155] and electron impact mass spectrometry [154]. On the other hand, matrix-assisted laser desorption/ionisation mass spectrometry has been employed for qualitative and quantitative analysis of anthocyanins in foods [156].…”

Rapid MALDI-TOF-MS Detection of Anthocyanins in Wine and Grape Using Different Matrices

“…Application of modern mass spectrometry techniques, such as liquid chromatography mass spectrometry (LC-MS) and matrixassisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), became the most sophisticated techniques for anthocyanin analyses in grape and wine. Mass spectrometry technique is applicable and effective for studies of glycoside compounds, allowing characterization of the aglycone and sugar moiety (Pérez-Magariño et al 1999, de Villers et al 2004, Monagas et al 2005Baldi et al 1995, Cameira-dos-Santos et al 1996, Wang and Sporns 1999, Revilla and González-San José 2001, Núñez et al 2004). …”

High Pressure Processing Technology on Bioactives in Fruits and Cereals

“…Especially, this technique is very effective for studies of glycoside compounds, allowing characterization of the aglycone and sugar moiety de Villiers et al 2004;Monagas et al 2005). Coupling HPLC to mass spectrometry allows characterization and structure elucidation of the anthocyanin pigments present in trace amounts in grapes and wine (Baldi et al 1995;Cameira-dos-Santos et al 1996;Wang and Sporns 1999;Revilla and González-San José 2001;Núñez et al 2004;La Torre et al 2006). This especially counts for the ion trap mass spectrometers, which enable several subsequent fragmentation steps thus allowing identi cation of complex molecules in a step-by-step removal of the various groups.…”

“…The determination of molecular masses of polyphenols by mass spectrometry could be performed using the electrospray ionization (ESI; Cheynier et al 1997;Hayasaka and Asenstorfer 2002), the atmospheric pressure chemical ionization (APCI) or the matrix-assisted laser desorption/ionization (MALDI; Sugui et al 1998Sugui et al , 1999Wang and Sporns 1999;Robards 2003;Reed et al 2005;Es-Sa et al 2006;Tholey and Heinzle 2006;Carpentieri et al 2007). MALDI was rst demonstrated by Karas et al (1987) and originally developed for large biomolecules analyses.…”

“…The TOF gives access to a theoretically unlimited mass range and also Dp-3-glc 525 465 303 *, **, ***, **** Cy-3-glc 516 449 287 *, **, ***, **** Pt-3-glc 525 479 317 *, **, ***, **** Pn-3-glc 516 463 301 *, **, ***, **** Mv-3-glc 528 493 331 *, **, ***, **** Dp-3-acetylglc 527 507 303 *, **, ***, **** Cy-3-acetylglc 523 491 287 *, **, ***, **** Pt-3-acetylglc 529 521 317 *, **, ***, **** Pn-3-acetylglc 522 505 301 *, **, ***, **** Mv-3-acetylglc 530 535 331 *, **, ***, **** Dp-3-p-coumglc 530 611 303 *, **, ***, **** Cy-3-p-coumglc 520 595 287 *, **, ***, **** Pt-3-p-coumglc 532 625 317 *, **, ***, **** Pn-3-p-coumglc 526 609 301 *, **, ***, **** Mv-3-p-coumglc 532 639 331 *, **, ***, **** Dp-3-caffeoylglc 532 627 303 ** Pt-3-caffeoylglc 531 641 317 ** Pn-3-caffeoylglc 525 625 301 ** Mv-3-caffeoylglc 534 655 331 ** Dp-3,7-diglc 523 627 303 ** Pt-3,7-diglc 522 641 317 ** Pn-3,7-diglc 625 301 ** Mv-3,7-diglc 526 655 331 ** Dp-3-glc + L(+)lactic acid 537 ** Pt-3-glc + D(-)lactic acid 551 ** Pt-3-glc + L(+)lactic acid 551 317 ** Pn-3-glc + D(-)lactic acid 535 ** Pn-3-glc + L(+)lactic acid 535 301 ** Mv-3-glc + D(-)lactic acid 565 331 ** Mv-3-glc + L(+)lactic acid 565 331 ** Carboxy-pyrano-Dp-3-glc 507 533 371 ** Carboxy-pyrano-Pt-3-glc 508 547 385 *, ** Carboxy-pyrano-Pn-3-glc 503 531 369 *, ** Carboxy-pyrano-Mv-3-glc (Vitisin A) 510 561 399 *, ** Carboxy-pyrano-Dp-3-acetylglc 575 371 **** Carboxy-pyrano-Pt-3-acetylglc 589 385 **** Carboxy-pyrano-Pn-3-acetylglc 573 **** Carboxy-pyrano-Mv-3-acetylglc (acetylVitisin A) 603 399 *, **** Carboxy-pyrano-Dp-3-p-coumglc 679 371 **** Carboxy-pyrano-Pt-3-p-coumglc 693 **, **** Carboxy-pyrano-Pn-3-p-coumglc 508 677 369 **, **** Carboxy-pyrano-Mv-3-p-coumglc (Fulcrand et al 1998). Recent investigations demonstrated that MALDI as a sensitive and ef cient technique could be used for characterization of different molecules in food science: anthocyanins in red wine and fruit juice (Wang and Sporns 1999), carotenoids in crop plants (Fraser et al 2007), . ** Adapted from Alcalde-Eon, C., Escribano-Bailón, M. T., Santos-Buelga, C., and Rivas-Gonzalo, J. C., Changes in the detailed pigment composition of red wine during maturity and ageing.…”