Dmso d6

Both dimethyl sulfoxide (DMSO) and deuterated DMSO (d₆-DMSO) solutions were used in these experiments. The 15% (w/v) DMSO solution was prepared by dissolving DMSO (Fisher Scientific, Fair Lawn, NJ, USA) in distilled water. In addition, 5, 10, 15, and 20% (w/v) d₆-DMSO solutions for calibrations were prepared by dissolving d₆-DMSO (MilliporeSigma, St. Louis, MO, USA) in distilled water.

The PIM-EA-TB polymer
(Sigma-Aldrich 918784; molecular weight approximately 70 KD; monomer
weight for C₂₁H₂₀N₂ 300 g mol^–1; density approximately 1.1–1.3 g cm^–3 or 3.7–4.3 mmol cm^–3;^{21 (link)} pore volume typically 30–26% (FFV),^{22 (link)} therefore wet density approximately 1.4–1.7 g cm^–3) was synthesized following a previously reported
method.^{23 (link)} Iodomethane (99%), NaClO₄ (≥98.0%), D₂O (99.9% atom D, contains 0.05
wt % 3-(trimethylsilyl)propionic-2,2,3,3-d₄ acid, sodium
salt as the internal standard), dimethyl sulfoxide, DMSO-d₆ (99.9 atom % D), and chloroform were purchased from
Sigma-Aldrich. NaCl (99.5%) was purchased from Fisher Scientific Ltd.
Methanol (HPLC) was purchased from VWR Chemicals BDH. Agarose powder
was purchased from Melford Ltd. All reagents were applied and used
as received without further purification. All aqueous solutions were
prepared with ultrapure water with a resistivity not less than 18.2
MΩ·cm (20 °C), from a CE Instruments water purification
system.

Lyophilized hCA I and HSA were purchased from Sigma-Aldrich and used without further purification or manipulation. Auoxo6, Au₂phen, Aubipyc, and AuL12, as well as the dodecapeptide of thioredoxin reductase (dTrxR), were synthetized in the MetMed Laboratories at the Department of Chemistry, University of Florence, following already established procedures (Pratesi et al., 2010 (link), 2014 (link)).
DTT and dimethyl sulfoxide (DMSO) were purchased from Fluka. Liquid chromatography (LC)–MS materials (water, methanol, and ammonium acetate) were purchased from Sigma-Aldrich. Deuterated solvents (D₂O and DMSO-d₆) were purchased from Sigma-Aldrich.

The extract was prepared using a well-known extraction methodology applied to the commercially available matrix, which is widely accepted by the scientific community and is useful for other different complex plant matrices [43 (link),44 (link),45 ].
Three replicates of PEF were prepared for high-resolution ¹H NMR analysis. Spectra were recorded in hexadeutero dimethyl sulfoxide (DMSO-d6; 600 μL for sample) purchased from Sigma-Aldrich (Milan, Italy) at 298 K, on a Bruker Avance Ultrashielded 300 MHz spectrometer equipped with a 5 mm multinuclear Z-axis gradient inverse probe head and at a proton frequency of 300.08 MHz. Relaxation times T1, pulse sequences, and acquisition and elaboration parameters were applied according to the literature [60 (link),61 (link),62 (link)].

The dried seeds of P. armeniaca L. (1.0 kg) were extracted three times with EtOH (1 L × 3 h) under reflux. After concentrating under reduced pressure, the EtOH extract (89.7 g) was suspended in distilled water and partitioned with n-hexane, CH₂Cl₂, EtOAc, and n-butanol to yield an n-hexane extract (50 g), a CH₂Cl₂ extract (8.8 g), an EtOAc extract (9.6 g), an n-butanol extract (6.5 g), and a water layer. The n-butanol extract was chromatographed with column chromatography (CC) on silica gel using stepwise eluent of CH₂Cl₂–acetone (gradient 10:1–1:1, v/v) and then CH₂Cl₂–MeOH–H₂O (gradient 6:1:0.1–1:1:0, v/v) to obtain 6 fractions (A–F). Compound 1 (35 mg) was isolated from fraction F (177.5 mg) by reserved phase C18 (RP-18) CC using MeOH–H₂O (3:1, v/v) as an eluent, followed by preparative high-performance liquid chromatography (HPLC) with an isocratic mixture solvent, 60% MeOH in H₂O, at 5 mL/min for 60 min. The nuclear magnetic resonance (NMR) spectra of compound 1 (¹H and ¹³C) were conducted using a 500 MHz NMR spectrometer (JEOL, JNM-ECA 500) with tetramethylsilane (TMS) as an internal standard. NMR solvent DMSO-d₆ was purchased from Sigma-Aldrich (MO, USA). The structure of compound 1 was confirmed as amygdalin using spectroscopic analysis of the NMR data and by comparison with other studies [24 (link),25 ] (Table S1, Figures S1 and S2).