Ethanol

Isolation of fungi from plants was conducted according to Taufiq et al. 2018 and Tong et al. 2011 [22 (link),23 ]. Tissue samples were washed under running tap water to remove surface soil, dust, and other contaminants. Samples with overgrown saprobes were swabbed with 70% ethanol (Scharlau, S.L; Sentmenat, Spain; Table S9). The diseased tissue pieces were cut from the leading edge of lesions using sterilized scalpels. The material was placed in 1% sodium hypochlorite for one minute. The tissue pieces were transferred from the sterilizing solution and washed by moving these briefly to sterile distilled water in three washes. The plant materials were dried on sterile filter paper, under filtered air in a laminar flow hood, and cut out into small tissue pieces (approx. 2 × 2 mm) and plated onto potato dextrose agar (PDA, Hi-media) (Table S8). Isolation plates were incubated at 25 °C, and examined daily. Data were collected from the third day to the seventh day of culture, observing, and recording the fungal growth morphology and sporulation in terms of colors, shape, texture, and sclerotia. Pure cultures were obtained from the primary isolation plates by plating on freshly prepared PDA and incubating at 27 °C for five to seven days.

Nonanal, trans-2-octenal (analytical standards), and dichloromethane were supplied by Merck KGaA (Darmstadt, Germany). Ethanol and acetone (GC grade) were purchased from Scharlab S.L. (Sentmenat, Spain). dichloromethane, methyl isobutyl ketone (MIBK), o-xylene, and toluene were purchased from Panreac S.A. (Barcelona, Spain), and propan-2-ol solvent (GC grade) was purchased from Labkem (Barcelona Spain). Decane, doDecane, and tetraDecane (analytical standards) were supplied by Aldrich (Steinheim, Germany). A real bioEthanol sample obtained from a winemaking residue was analyzed to validate the developed GFAD.

For 60 target polyphenols, their CAS numbers, molecular mass, retention time and MS/MS transitions are shown in Table S1. Water and methanol (MS grade), and ethanol were supplied by Scharlab (Barcelona, Spain). The Folin-Ciocalteu’s phenol reagent (2M), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox^®), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), formic acid, sodium carbonate and sand (200–300 µm mesh) were supplied by Sigma-Aldrich (Darmstadt, Germany).

The essential oils (EOs) evaluated in this work, (i) lavandin Grosso and lavandin Abrial extracted from two hybrids of Lavandula angustifolia × Lavandula latifolia, (ii) Origanum virens, and (iii) Rosmarinus officinalis, were obtained from plants collected from experimental fields of the Agri-Food Research and Technology Center of Aragon (CITA, Zaragoza, Spain). The plants were mechanically harvested at full flowering and then air-dried. The following air-dried plant material was used: flowers in spikes from lavandins, leaves and flowers from O. virens, and terminal shoots and leaves from R. officinalis. The EOs were obtained by hydrodistillation in a Clevenger-type apparatus for 2 h. At the end of the distillation period, the oils were decanted into sterilized brown glass vials and stored at 4 °C in the dark when not in use. The composition of the EOs was determined by a gas chromatography-flame ionization detection (GC-FID) method in a recognized private laboratory.
Caffeic, chlorogenic, ferulic, and p-coumaric acids were obtained from Sigma-Aldrich Chemie GmbH (Taufkirchen, Germany). These phenolic acids (PAs) were selected because of their natural abundance in cereal grains and other plant foods. Stock solutions of PAs were daily prepared at 400 mM in 50% ethanol (Scharlab, Barcelona, Spain).

Sodium pyruvate,
citric acid, sodium citrate, thiamine pyrophosphate (TPP), and magnesium
chloride were obtained from Sigma Chemical Co. (St. Louis, USA) for
the determination of enzyme activity and reaction media. Ethanol,
potassium phosphate, sodium acetate, and sodium bicarbonate were obtained
from Scharlab, S.L. (Barcelona, Spain) for the determination of enzyme
activity and reaction media. Acetoin and lactic acid standards were
obtained from Sigma Chemical Co. (St. Louis, USA) and used as analytical
standards for gas chromatography and LC–MS analysis, respectively.
NADH and NAD⁺ were obtained from Bontac Bioengineering
Co. (Shenzhen, China) as reaction cofactors. Carbon dioxide gas as
well as gas mixture mimicking real blast furnace off-gases composition
[24.5% CO₂, 46.6% N₂, 23.9% CO, 1.2% O₂, and 3.8% H₂] was obtained from Carburos Metalicos (Barcelona,
Spain). PDC from Zymobacter palmae (ZpPDC) was produced
according to Alcover et al.^{27 (link)} PDC from Saccharomyces cerevisiae (ScPDC), ADH
from Saccharomyces cerevisiae (ScADH) and Thermotoga maritima LDH
(TmLDH) were produced according to Benito et al. (see Supporting Information).^{28 (link)}

Analytical standards were procured from Sigma Aldrich, Australia and included (+)-α-pinene (#80605), (-)-β-pinene (#80609), α-humulene (#12448), β-humulene (#53676), (-)-α-bisabolol (#95426), (-)-caryophyllene oxide (#91034) and (-)-trans-caryophyllene (#75541). Organic solvents n-hexane, methanol, ethanol, dichloromethane, diethyl ether and diethyl acetate were of HPLC grade and bought from Scharlau Australia.