Choline chloride

The DES ionic liquid was prepared by mixing urea (Merck KGaA, Darmstadt, Germany) and choline chloride (ChCl) (Merck KGaA, Darmstadt, Germany) in a 2:1 molar ratio at a temperature of 80 °C with continuous vigorous magnetic stirring until a homogeneous colorless liquid was formed. After this step, the incorporation of the cerium and zinc species to the electrolyte was made by the addition of the ZnCl₂ and CeCl₃·7H₂O salts separately (0.3 M in each case) and together (Zn:Ce ratio 3:1). In all cases, the solution was dried overnight at 80 °C under vacuum and stored under moisture-free conditions before electrodeposition. Remaining moisture was measured by Karl Fisher titration showing a volumetric water content between 0.16 ± 0.09% in ChCl–urea–ZnCl₂ and 1.07 ± 0.03% in the ChCl–urea–ZnCl₂–CeCl₃ liquid.

Ibf (pure) was procured from PubChem. The sunflower–canola oil blend was purchased from LOTUS supermarket. Sodium hydroxide (NaOH), Span 80, tetramethylammonium acetate [TMAm][Ac] (≥99%), tetramethylammonium chloride [TMAm][Cl] (≥99%), 1-butyl-3-methylimidazolium acetate [EMIm][Ac] (≥99%), 1-Butyl-1-methylpyrrolidinium chloride [BMPyrro][Cl] (≥99%), 1-butyl-1-methylpyrrolidinium bromide [BMPyrro][Br] (≥99%), choline chloride [Ch][Cl] (≥99%), and tributylmethylammonium chloride [TBMAm][Cl] (≥99%) were supplied by Merck, Darmstadt, (Germany). All chemicals used were of analytical grade and were used without further purification. A list of the chemicals used and their properties is present in Table S2.

Fresh C. longa was purchased at Tangerang (Banten, Indonesia) local market. Fresh C. mangga was commercially purchased from a local business at Garut (West Java, Indonesia). Fresh C. xanthorriza was purchased at local market in Jakarta Selatan (DKI Jakarta, Indonesia).
Pure curcuminoids standard was commercially purchased from a retailer at Bantul (Yogyakarta, Indonesia). Choline chloride (95%), lactic acid (90%), analytical grade ethanol (>99%), hexane (>98.5%), and isopropanol (>99.8%) were obtained from Merck (Darmstadt, Germany). A nylon membrane filter with a pore size of 0.45 µm was obtained from Merck Millipore (Carrigtwohill, Ireland). Whatman filter paper (No. 42) with 90 mm pore size was obtained from Whatman (Dassel, Germany).

Acetone and methanol were obtained from Valente and Ribeiro (Lisbon, Portugal). Ethanol (96%) was purchased from “AGA-Álcool e Géneros Alimentares”, S.A. (Lisbon, Portugal). Monobasic potassium phosphate was from Merck (Darmstadt, Germany), while dibasic potassium phosphate, iron (II) chloride (FeCl₂), ferrozine, ethylenediaminetetraacetic acid (EDTA), pyrocatechol violet (PV), copper sulfate (CuSO₄), sodium acetate, choline chloride, glucose, fructose, sucrose, and xylose were provided by VWR International (Leuven, Belgium). Panreack AppliChem ITW Reagents (Barcelona, Spain) supplied fluorescein and Acros Organics (Geel, Belgium) provided 2,2′-azobis (2-amidinopropane) dihydrochloride (AAPH) and Trolox. Sigma-Aldrich (Lisbon, Portugal) delivered DPPH and butylated hydroxytoluene (BHT).

Desisopropylatrazine (DIA), desethylatrazine (DEA), simazine (SIM), atrazine (ATZ), and propazine (PPZ), isoproturon (IPN), methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), and 2,2′-azobis-2-isobutyronitrile (AIBN) were supplied by Sigma-Aldrich (Madrid, Spain). AIBN was recrystallized in methanol, and EGDMA and MAA were freed from the stabilizers by distillation under reduced pressure prior to use. Formic acid (FA), L-menthol, thymol, camphor, choline chloride (ChCl), and betaine hydrochloride (BetCl) were purchased from Merck (Madrid, Spain). High-performance liquid chromatography (HPLC)-grade acetonitrile (ACN), toluene, and acetone were obtained from Honeywell (Seelze, Germany). Purified water was obtained from a Milli-Q purification unit supplied by Millipore (Madrid, Spain). All other chemicals were of analytical reagent grade and were used as received. Stock standard solutions of triazines (1 g/L) were prepared in acetonitrile and kept at −22 °C. The chemical structures of the triazines and isoproturon are shown in Fig. S1.

The basis set for LCModel was simulated using the NMRScope-B plugin, which is implemented in jMRUI (Version 6.0 beta) [65 ]. MR spectra for each metabolite were calculated based on a priori knowledge of scalar coupling, chemical shifts, and vendor specific hardware parameters for data acquisition. The metabolites simulated and included in the data evaluation were: sodium-3-hydroxybutyrate (βOHB), acetone natural (Acn), lithium acetoacetate (AcAc), sodium l-lactate (Lac), N-acetyl-l-aspartic acid (NAA), creatine anhydrous (Cr), choline chloride (Cho), l-glutamine (Gln), l-glutamic acid (Glu), and myo-inositol (mI) (all Merck KGaA, Darmstadt, Germany). A line broadening of 3 Hz was applied to each basis spectrum.
Following simulation, the basis set was tested on phantom data, including signals for the respective metabolites at expected in vivo concentrations (Lac 2 mmol/L, NAA 8 mmol/L, Cr 6 mmol/L, Cho 2 mmol/L, Gln 2 mmol/L, Glu 7 mmol/L, mI 4 mmol/L). Concentrations of βOHB, Acn and AcAc were at 1 mM. The frequency, phases and linewidths of the peaks were all constrained relative to the creatine singlet at 3.03 ppm (Figure 3a).

The Brookfield DV-II + Pro EXTRA viscometer was used to measure solvent viscosity, and the G LAB melting point apparatus was used to measure the melting point of solvent and derivatives. The ¹H, and ¹³C NMR spectra, CHNS/O elemental analyzer, and mass analysis of compounds were prepared using the Varian Inova 500MHz, the EMA 502, and the Agilent technologies 5975C. The Thermo biomate 5 Spectrophotometer was used to prepare the suspension of bacteria. The suspension of bacteria was obtained from the American Type Culture Collection (ATCC). All the reagent materials used for the synthesis of deep eutectic solvent and the synthesis of pyrazole derivatives and pyrano[2,3-c] pyrazole derivatives such as choline chloride, urea, malononitrile, aldehyde derivatives, and hydrazine derivatives were obtained from Merck and Sigma.