Multivariate spectroscopy for targeting phenolic choreography in wine with A-TEEM^TM and NMR crosscheck non-targeted metabolomics

Abstract

Present work comprises the use of different multivariate spectroscopic methods for tracking novel metabolomics signatures related to red wine chemistry. It is presented for the first time the proton nuclear magnetic resonance metabolomics fingerprint of a monovarietal Mexican Merlot, obtained with acquisition improvements recently proposed to the OIV Methods of Analysis sub-commission. Effective multi-presaturation solvent schemes have revealed a rich (poly)-phenolics aromatic region, so far not exploited for wine-fingerprinting or – targeted profiling routines. It is presented as well for the first time the use of simultaneous absorbance-transmission and fluorescence excitation-emission matrix “push-one-bottom” method (A-TEEMTM) at specific chemical conditions for a rapid, effective and high-sensitivity characterization of phenolic choreography in wines, as novel observables to quantify oenological practices and aging.

Comparative NMR Metabolomics Profiling between Mexican Ancestral & Artisanal Mezcals and Industrialized Wines to Discriminate Geographical Origins, Agave Species or Grape Varieties and Manufacturing Processes as a Function of Their Quality Attributes

“…Counties per region are labelled as follows: (i) VG: Valle de Guadalupe, (ii) P: Parras and (iii) EM: Ezequiel Montes. Different ageing strategies were used for Merlot and Cabernet Sauvignon samples and coded as [ 37 ]: (i) Merlot 2017 aged within a 2017- Tonnellerie d’Aquitaine French barrel, (ii): Merlot 2017 Gran Reserva taken from a 24-months bottled aging, (iii): Merlot 2018 aged within a 2018-Tonnellerie d’Aquitaine French barrel, (iv): Merlot 2018 aged within a 2016-Tonnellerie d’Aquitaine French barrel, (v): Merlot 2018 directly taken from the fermentation tank, (vi): Merlot 2018 aged within a 2016-Boutes French barrel, and (vii): Merlot 2018 aged within a 2018-Demptos American barrel. Full data set comprising type of ageing, regions, counties, and varieties are resumed in Table 2 .…”

“…7778-70-0) buffer were prepared and pH adjusted to a value of 3.1 [ 1 , 37 ]. The following NMR schemes were acquired for the full set of wine and mezcal samplings, which, respectively, comprise 31 and 60 samples: Standard direct-excitation one-dimensional proton nuclear magnetic resonance spectra needed to prepare water-to-ethanol off-resonance multipresaturations [ 37 , 38 , 39 ] were carried out by recording a total of 64 transients, which were collected in 28,844 complex data, with a spectral width of 20 ppm (12,019 Hz), an optimized recovery delay of 6 s and acquisition times of 1.2 s, produced experimental times of 6 min per spectrum. No apodization function was applied during the Fourier Transform.…”

“…7789-20-0) and 0.1% of phosphonate KH 2 PO 4 (CAS No. 7778-70-0) buffer were prepared and pH adjusted to a value of 3.1 [1,37]. The following NMR schemes were acquired for the full set of wine and mezcal samplings, which, respectively, comprise 31 and 60 samples:…”

Polyphenol-based nuclear magnetic resonance non-targeted metabolomics of temperature- and time-controlled blue and red maize sprouting

“…1, signal to noise ratio of metabolites' proton resonances in standard 1D-1 H-NMR are severely penalized due to the presence of intense water and methanol signals. For that, a solvent multi-suppression scheme is needed for obtaining a 16-fold signal-tonoise ratio gain of maize sprouts' extracts [18][19][20], needed to prepare the output data matrix for multivariate statistical analysis. Figure 2 resumes the workflow to prepare the NMR output data matrix needed to PCA and OPLS-DA analysis: i) spectra processing (ppm calibrations, base-line corrections and frequency alignments) and ii) reduction of data dimensionality by frequency binning.…”

Impact of Hanseniaspora Vineae in Alcoholic Fermentation and Ageing on Lees of High-Quality White Wine

“…(a) Standard 1H-one-dimensional NMR experiment was carried out as step for calibration of the water-to-ethanol multi-presaturation module: with 4 transients of 32,768 complex points, having recycling delays of 5 s and with acquisition times of 1700 milliseconds, produced an experimental time of 26 s. No apodization function was applied during Fourier Transform. (b) {1Hwater_presat NMR}: 1D single pulse NOESY experiment with a homemade shaped-pulse water-to-ethanol presaturation during both the relaxation delay (5 s) and mixing times (100 milliseconds), with a 8.18 × 10 −4 W power irradiation level for the solvent signals' elimination, centering the transmitter frequency at 4.7 ppm and shifting the decoupler frequency between 3.55 ppm (CH2-ethanol) and 1.08 ppm (CH3-ethanol) for accurate multi-presaturation of all signals [16,17] were acquired for each sample as follows: a total of 128 transients were collected into 32,768 complex data points, with a spectral width of 9615.4 Hz and acquisition times of 1700 ms, produce experimental times of 10 58 '. (c) NMR post-processing was carried out as follows: ppm calibration and manual phase corrections were conducted with the use of Bruker TopSpin 4.0.8 software.…”