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SPME-GC-HRTOF-MS dataset of fermented maize flour volatilome

[version 1; peer review: 1 approved]
PUBLISHED 20 Oct 2022
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Abstract

Background: The volatilome of fermented food products are essential metabolites that significantly contribute to such foods’ overall composition and sensorial quality. The dataset presented herein represents the volatilome of raw and fermented maize flour samples.
Methods: Maize grains were milled and naturally fermented at 35°C into sourdough at different periods (24, 48 and 72 h) and, at each point, the profile of the volatiles was investigated. Samples at the different fermentation periods were analyzed using solid phase microextraction coupled with a gas chromatography-high resolution time of flight-mass spectrometry (SPME-GC-HRTOF-MS).
Results: Data obtained were classified into different compound groups such as alcohols, aldehydes, aromatic compounds, esters, organic acids, terpenes, ketones, among others and their characteristics such as the retention time, observed mass, molecular formular, mean peak areas and mass spectra also presented.
Conclusion: These datasets of fermented maize volatilome can be used as biomarkers for maize fermentation.

Keywords

Volatiles, SPME-GC-HRTOF-MS, whole maize grain, Sourdough, Fermentation, gas chromatography

Introduction

Maize (Zea mays L.) is an edible staple grain and one of the most sought-after cereals for human consumption in sub-Saharan Africa (Erenstein et al., 2022). The recent production statistics suggested that maize is the most globally produced cereal, followed by rice (paddy) and wheat (http://www.fao.org/faostat/en/#data/QCL). South Africa is among the top ten largest producers of maize, with over 15 million tonnes in 2020. A whole maize grain comprises macro and micro phytochemicals of nutritional and health significance. Simple processing means for maize grain use include food fermentation, a biological process that produces sourdough and other intermediate fermented products. Such products represent a critical product developmental phase, are sensorially distinct and typically contain appreciable levels of bioactive components for improving human wellness (Achi & Asamudo, 2019; Pswarayi & Gänzle, 2022).

The volatilome of fermented food products are essential metabolites that significantly contribute to such foods’ acceptance in terms of aroma and taste (Annan et al., 2003; Saa et al., 2019; Adebo et al., 2021). Important dough fermentation conditions, including time-dependent changes, can significantly define the volatilome profile of the resulting fermented dough, with implications for its use in further product development (Lee et al., 2016; Huang et al., 2022). The previous study on aroma volatiles in fermented maize dough (72 hours) identified 64 volatile compounds using gas chromatography-mass spectrometry (GC-MS), and the injected extracts were prepared through the Likens-Nickerson simultaneous distillation and extraction method (Annan et al., 2003). In this present work, a solvent-free extraction procedure, solid-phase micro-extraction (SPME) and gas chromatography-high resolution time of flight-mass spectrometry (GC-HRTOF-MS) were employed to provide a robust dataset detailing volatilome changes in maize flour and resulting sourdough with varying fermentation time. Thus, the data in this study represents a profile of volatiles in fermented maize (sourdough) and unfermented maize, which could indicate the compounds that contribute to the aroma of these products.

Methods

Maize fermentation

Maize (Zea mays) grains were obtained from the Agricultural Research Council (ARC Grain Crops), Potchefstroom, South Africa (26°43′31.0″S 27°04′53.8″E). The grains were milled (Perten Laboratory Mill 3310, Perten Instruments AB, Helsinki, Finland) and the resulting maize flour was mixed with sterile distilled water (1:1, v/w) and spontaneously fermented at 35 oC (Incotherm, Labotec, Johannesburg, South Africa) for 24, 48 and 72 h. Each fermentation process was done in triplicate.

SPME sampling and GC-HRTOF-MS analysis

The volatilome analysis was carried out at the University of Johannesburg (Doornfontein Campus), Johannesburg, South Africa (26o11′32.6″S 28o03′28.9″E). Five grams (5 g) of the respective sample was loaded into amber headspace vials (Restek, Bellefonte, USA). The vial was heated and incubated at 40 oC for 20 min with intermittent agitation on and off for 10 and 1 seconds (s), respectively, at 250 rpm. Subsequently, sampling was done by exposing the 50/30 μm SPME fiber coated with divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) (Supelco, Inc., Bellefonte, USA) at 54 mm injection penetration vial depth for 20 min. The extracted volatiles were analyzed on a GC-HRTOF-MS system (Agilent 7890A gas chromatograph, Agilent Technologies, Inc., Wilmington, DE, USA and LECO Corporation, St. Josheph, MI, USA), equipped with a Gerstel MPS multipurpose sampler (Gerstel Inc. Mülheim an der Ruhr, Germany) and Rxi®-5 ms column (30 m × 0.25 mm ID × 0.25 μm) (Restek, Bellefonte, USA). The extracts were injected in a spitless mode and desorped for 60 s, with helium as the carrier gas. Inlet and transfer line temperatures were set at 250 and 225 oC, respectively, and the ion source temperature was 250 oC. The oven temperature cycle used was: initial temperature of 30 oC for 0.5 min; then an increase of 10 oC/min to 220 oC held for 0.5 min; then ramped to 270 oC for the fiber at 43 mm penetration to ‘bake-out’ for 5 min pre-and post-bake out times. Experiments for blanks were also conducted to observe possible impurities and contamination. To identify the metabolites, spectra were matched with the National Institute of Standards and Technology (NIST), Mainlib and Feihn reference library databases, and their identities were determined. To process raw data, parameters such as signal-to-noise ratio of 100, similarity match above 70% and the occurrence of metabolites at least two times out of the triplicate data were strictly adopted (Achi & Asamudo, 2019). The raw and processed data (Adebo et al., 2022a, 2022b) provides information on the volatilome of maize and derived fermented products at different fermentation periods (24, 48 and 72 h). The retention time, observed mass, average peak area and volatilome class of each compound are presented in Table 1. The compounds were also classified and the percentage distribution is shown in Figure 1.

Table 1. Compounds in the volatilome of maize and fermented maize sourdoughs.

Ret time (min)Compound nameObserved ion m/zm/z fragmentsMolecular formulaRaw24 h48 h72 h
Alcohols
4.9502,3-Butanediol90.067545.0336, 57.0336C4H10O2NDND1089124612989970
5.951Isohexanol102.046743.0544, 56.0622C6H14OND50819174748546ND
5.953Hexanol103.054343.0544, 56.0622C6H14O3102173NDNDND
7.5951-Heptanol119.085156.0623, 70.0778C7H16O288274397331437168392731
7.747Morillol131.034857.0337, 72.0571C8H16O313018551685629962555170
8.550Ethylhexanol131.081643.0545, 57.0701C8H18ONDND121812154517
9.174trans-1-Oct-2-enol131.062741.0388, 57.0337C8H16OND310064NDND
9.2095-Octen-2-yn-4-ol124.088355.0544, 95.0857C8H12ONDND173840166460
9.340(5-Ethylcyclopent-1-enyl)methanol126.104067.0544, 79.0544C8H14OND167894196441191298
9.563Mequinol124.0519109.0285, 124.0519C7H8O2ND445479ND572875
9.962Phenethyl alcohol122.072765.0387, 91.0544C8H10OND273393319248250145
12.380p-Ethylguaiacol152.0833137.0597, 152.0833C9H12O2ND115820141880133976
12.872para-Vinylguaiacol150.0675135.0441, 150.0675C9H10O2780664ND12406031012466
Aldehydes
6.453Heptanal115.075341.0388, 55.0545C7H14OND288482708098742617
4.828Hexanal100.089244.0258, 56.0622C6H12ONDND3052268ND
9.012trans-Oct-2-enal125.096393.0700, 97.0649C8H14OND169368460139511967
9.734Nonanal134.013243.0545, 56.0623C9H18ONDND63266ND
10.585trans-Non-2-enal136.393655.0545, 70.0414C9H16ONDND7755795451
12.752trans-2, trans-4-Decadienal152.119867.0543, 81.0336C10H16ONDND169895105602
Aromatic compounds
6.354m-Xylene106.077891.0544, 106.0779C8H10NDND416594ND
7.479Benzaldehyde106.041377.0386, 105.0336C7H6ONDNDND3433552
7.786Cumene120.093577.0387, 105.0700C9H12128132NDNDND
8.142Toluene120.0935105.0700, 120.0935C9H12NDND61876ND
8.329m-Dichlorobenzol145.9685110.9997, 145.9685C6H4Cl2ND833257766866ND
8.335Chloroben145.9685110.9997, 145.9685C6H4Cl21124234NDND120098
8.497Hemellitol120.0934105.0700, 120.0934C9H12227139NDND183818
8.826Benzeneacetaldehyde120.057065.0387, 91.0544C8H8ONDND151385187273
8.936Cumene aldehyde134.1091105.0700, 134.1091C9H10O122609NDNDND
9.306m-Cymene134.109191.0544, 119.0856C10H14152892NDNDND
9.881Isodurene134.1091119.0856, 134.1091C10H14NDND10232099071
10.012Prehnitol134.1091119.0856, 134.1091C10H14148142NDNDND
10.0141,3-Dimethyl-5-ethyl benzene134.1091119.0856, 134.1091C10H14NDNDND84952
Esters
6.157Acetic acid, pentyl ester131.233743.0180, 70.0778C7H14O2ND7745281203944ND
6.658Acetic acid, propyl ester103.038615.0538, 42.0670C5H10O2NDND369294ND
8.266Acetic acid, hexyl ester147.047397.0650, 101.0598C8H16O2ND396717605660651234
10.7522-Propenoic acid, octyl ester219.030941.0388, 55.0545C11H20O2ND115002ND109256
10.799p-Benzoquinone dioxime dibenzoate270.2896105.0336, 122.0364C20H14N2O4NDNDND62287
11.373Oxalic acid, isohexyl neopentyl ester224.894543.0545, 71.0856C13H24O4ND44628NDND
13.421Butyric acid, 4-pentadecyl ester324.987043.0545, 71.0493C19H38O2NDND81914ND
13.422Pentanoic acid, 2,2,4-trimethyl-3-hydroxy-, isobutyl ester219.090043.0545, 71.0493C12H24O311017588224NDND
13.423Butyric acid, 3-tridecyl ester268.874243.0545, 71.0493C17H34O2NDNDND55393
13.518Tetrahydropyran Z-10-dodecenoate268.980385.0285, 119.1458C17H30O3NDNDND102232
13.681Propanoic acid, 2-methyl-, 2-ethyl-3-hydroxyhexyl ester219.022043.0545, 71.0492C12H24O3NDND10381783351
16.432Pentanoic acid, 2,2,4-trimethyl-3-carboxyisopropyl, isobutyl ester268.985943.0545, 71.0493C16H30O4ND158208NDND
Fatty acid ethyl ester
8.042Caproic acid ethyl ester145.122388.0520, 99.0806C8H16O2ND529880676557810363
9.608Heptanoic acid, ethyl ester134.109388.0520, 113.0962C9H18O2NDND7266486073
11.101Caprylic acid ethyl ester145.122588.0520, 101.0599C10H20O2ND195931289681302413
12.513Nonanoic acid, ethyl ester192.982957.0701, 88.0520C11H22O2ND407006325276308
Furan
7.9402-Pentylfuran138.103981.0335, 138.1040C9H14O234186212171932283533234278
Hydrocarbons
8.6291,3-Heptadiene, 5,5-dimethyl-124.119067.0543, 95.0857C9H16ND481768053599914586356
9.3363,3-Dimethylhexane113.132343.0545, 57.0701C8H18NDND128637ND
11.146Tridecane219.016043.0544, 57.0700C13H28101933151281164790119412
11.608Undecane136.125243.0545, 57.0701C11H2479200NDNDND
12.070Tetradecane219.131157.0701, 71.0856C14H30NDND7829776397
12.841Pentadecane219.085657.0701, 71.0856C15H32ND118475145996130364
12.987Hexadecane224.362043.0545, 57.0701C16H3468209120322NDND
13.2361-Iodo-2-methylundecane225.260043.0545, 57.0701C12H25I74788NDNDND
7.4872,2-dichloro-2-fluoro-1-phenylethanone219.082777.0387, 105.0336C8H5Cl2FOND388884NDND
Ketones
10.083Isophorone138.103854.0466, 82.0414C9H14ONDNDND80280
3.841Dihydroxydimethylsilane92.028844.9792, 77.0053C2H8O2Si3611272488013934433914702062
Miscellaneous compounds
3.8722-Propynenitrile, 3-fluoro-69.081819.4978, 69.1220C3FN26716NDNDND
4.994Tris (trifluoromethyl) bromomethane219.170469.0643, 131.1442C4BrF9NDND6500ND
6.620Oxime-, methoxy-phenyl-151.0241133.0135, 151.0241C8H9NO2NDNDND224332
7.3424-Trimethylsilyloxybenzoic anhydride219.5140192.9804, 209.0115C20H26O5Si2NDNDND173123
7.972Cyclotetrasiloxane, octamethyl-294.0630265.0201, 281.0514C8H24O4Si4ND269792930596461389306
7.973trisiloxane, 1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]-294.2585265.0200, 281.0512C9H28O3Si41924722NDND1196850
8.988Undecane, 4,7-dimethyl-219.070743.0545, 57.0701C13H2886318NDNDND
9.1622,4-Dimethyldecane145.999257.0701, 71.0856C12H26ND152181ND137124
10.416Cyclopentasiloxane, decamethyl-370.198973.0466, 266.9993C10H30O5Si55805665636326553275264987637
10.750Phosphine, tris (trifluoromethyl)-223.859018.0554, 69.0576C3F9P95007007103727944
11.717Trisiloxane, 1,1,1,5,5,5-hexamethyl-3,3-bis[(trimethylsilyl)oxy]-283.048473.0469, 147.0658C12H36O4Si521781NDNDND
12.889Cyclohexasiloxane, dodecamethyl-442.056173.0466, 341.0184C12H36O6Si64344585475011242054494093843
15.1243-Isopropoxy-1,1,1,7,7,7-hexamethyl-3,5,5-tris (trimethylsiloxy)tetrasiloxane507.103473.0468, 281.0513C18H52O7Si710717051001799776064793908
17.124Cyclooctasiloxane, hexadecamethyl-415.036173.0469, 355.0697C16H48O8Si89190410509881697ND
Organic acids
3.513Acetic acid60.020544.9972, 60.0207C2H4O2NDNDND36878336
7.8614-Hydroxybenzenephosphonic acid134.424866.0465, 94.0414C6H7O4PNDND730481ND
7.857Caproic acid101.060260.0208, 73.0285C6H12O2394450107802814975201115792
Phenol
10.734Paraethylphenol122.0727107.0492, 122.0727C8H10ONDNDND374015
Terpenes
6.351o-Xylene106.077891.0544, 106.0778C8H10405154NDND1461074
9.475p-Cymene134.109191.0543, 119.0856C10H14ND447326501478983
8.174Mesitylene120.0934105.0699, 120.0935C9H12601952ND73884625021
11.075Naphthalene128.062151.0232, 128.0621C10H875370610247060765505
bf2e8000-01bd-4658-bb24-004ab89ee4aa_figure1.gif

Figure 1. Pie chart showing the percentage distribution of compounds in the volatilome of maize and fermented maize sourdoughs.

Data availability

Underlying data

Mendeley Data: Raw SPME-GC-HRTOF-MS data and spectra of maize and sourdough volatilome. https://data.mendeley.com/datasets/kytshjccrc/2 (Adebo et al., 2022a).

This project contains the following underlying data:

  • - Maize and Fermented Maize Volatilome SPME-GC-HRTOF-MS Spectra Data.pdf (Mass spectra of compounds from maize and fermented maize volatilome, obtained using solid phase microextraction coupled with a gas chromatography-high resolution time of flight-mass spectrometry (SPME-GC-HRTOF-MS))

  • - Processed Maize and Fermented Maize Volatilome SPME-GC-HRTOF-MS data.xlsx (The processed dataset of compounds from maize and fermented maize volatilome, obtained using SPME-GC-HRTOF-MS). Raw (unfermented maize); 24 h – sourdough fermented for 24 h; 48 h – sourdough fermented for 48 h and 72 h – sourdough fermented for 72 h

  • - Raw SPME-GC-HRTOF-MS data set.zip (The raw dataset (.csv) of compounds from maize and fermented maize volatilome, obtained using SPME-GC-HRTOF-MS). WM0H (unfermented maize); WM24H – sourdough fermented for 24 h; WM48H – sourdough fermented for 48 h and WM72H – sourdough fermented for 72 h

  • - Table 1 - Compounds in the volatilome of maize and fermented maize sourdoughs.xlsx (The processed and tabulated compounds from maize and fermented maize volatilome, obtained using SPME-GC-HRTOF-MS). Raw (unfermented maize); 24 h – sourdough fermented for 24 h; 48 h – sourdough fermented for 48 h and 72 h – sourdough fermented for 72 h

University of Johannesburg’s Open Access Data Repository: UJ Research Data. https://doi.org/10.25415/ujhb.20223447.v1 (Adebo et al., 2022b).

This project contains the following underlying data:

  • - (SPME-GC-HRTOF-MS dataset of fermented maize flour volatilome) (The raw dataset (.MZML) of compounds from maize and fermented maize volatilome, obtained using SPME-GC-HRTOF-MS). WM0H (unfermented maize); WM24H – sourdough fermented for 24 h; WM48H – sourdough fermented for 48 h and WM72H – sourdough fermented for 72 h

Data are available under the terms of the Creative Commons Attribution 4.0 International license (CC-BY 4.0).

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Adebo OA, Gbashi S, Kewuyemi YO et al. SPME-GC-HRTOF-MS dataset of fermented maize flour volatilome [version 1; peer review: 1 approved]. F1000Research 2022, 11:1198 (https://doi.org/10.12688/f1000research.126604.1)
NOTE: If applicable, it is important to ensure the information in square brackets after the title is included in all citations of this article.
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ApprovedThe paper is scientifically sound in its current form and only minor, if any, improvements are suggested
Approved with reservations A number of small changes, sometimes more significant revisions are required to address specific details and improve the papers academic merit.
Not approvedFundamental flaws in the paper seriously undermine the findings and conclusions
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Reviewer Report 07 Aug 2023
Dody Dwi Handoko, Indonesian Center for Rice Research, Indonesian Agency for Agricultural Research and Development, Subang, Indonesia 
Approved
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This article presented data on the effect of the natural fermentation of maize flour on volatile compounds.
 
The authors used tentative identification, using only the library database to identify the volatile compounds of the maize and fermented ... Continue reading
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Handoko DD. Reviewer Report For: SPME-GC-HRTOF-MS dataset of fermented maize flour volatilome [version 1; peer review: 1 approved]. F1000Research 2022, 11:1198 (https://doi.org/10.5256/f1000research.139033.r188199)
NOTE: it is important to ensure the information in square brackets after the title is included in all citations of this article.

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VERSION 1 PUBLISHED 20 Oct 2022
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Alongside their report, reviewers assign a status to the article:
Approved - the paper is scientifically sound in its current form and only minor, if any, improvements are suggested
Approved with reservations - A number of small changes, sometimes more significant revisions are required to address specific details and improve the papers academic merit.
Not approved - fundamental flaws in the paper seriously undermine the findings and conclusions
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