Ultrashield 600 spectrometer

Optical rotations were determined on a P-1030 digital polarimeter (JASCO, Tokyo, Japan). IR spectra were measured on a FT-710 Fourier transform infrared spectrophotometer (Horiba, Kyoto, Japan), while UV spectra were taken on a V-520 UV/Vis spectrophotometer (JASCO, Tokyo, Japan). NMR data were obtained by an Ultrashield 600 spectrometer (Bruker, Ettlingen, Germany) with tetramethylsilane (TMS) as an internal standard. Positive ion HR-ESI-MS measurement was performed with the LTQ Orbitrap XL mass spectrometer (Thermo Fisher Scientific, Waltham, MA, USA). Column chromatography (CC) was carried out on silica gel 60 (E. Merck, Darmstadt, Germany), and octadecyl silica (ODS) gel (Cosmosil 75C18-OPN (NacalaiTesque, Kyoto, Japan; Φ = 35 mm, L = 350 mm). HPLC was performed on ODS gel (Inertsil ODS-3, GL-science, Φ = 6 mm, 250 mm, flow rate = 1.6 mL/min, GL Sciences, Tokyo, Japan), and the eluate was observed by refractive index detector with the RI-930 intelligent detector (JASCO, Tokyo, Japan) and a PU-1580 intelligent pump (JASCO, Tokyo, Japan). All chemicals were purchased from Wako Pure Chemical Industries, Ltd. (Osaka, Japan) and TCI (Tokyo, Japan).

All chemicals and anhydrous solvents were supplied by Aldrich Chemicals and used under a nitrogen atmosphere. FTIR measurements were carried out using a Perkin−Elmer 2000 FTIR spectrometer. UV−Vis absorption/emission spectra were recorded on a Horiba Scientific Duetta spectrophotometer/spectrofluorimeter equipped with EZSpec software (Kyoto, Japan). All excitation and emission spectra and time−correlated single photon counting (TCSPC) lifetimes were carried out using an Edinburgh Instruments FLS1000 photoluminescence spectrometer (Edinburgh, Scotland). For steady−state measurements, an Xe Arc lamp and a visible PMT−900 detector were used. For lifetimes, a 375 nm variable pulse length diode laser (VPL−375) was employed. All data analyses were carried out using Floracle ® software version 2.15.2. CO TONs were quantified through headspace sampling using a Shimadzu GC−2010 Plus gas chromatograph equipped with LabSolutions Lite 5.5 software (Kyoto, Japan). All NMR spectra (Figures S18−S30, Supporting Information) were recorded on a Bruker Avance Ultrashield 600 spectrometer with TopSpin 3.6.1 software and were referenced to the deuterated solvent peak as an internal reference. Elemental analyses were carried out at London Metropolitan University.

Sampled oils were subjected to ¹H NMR analysis using a Bruker Ultrashield 600 spectrometer (Kingston University London, London, UK) operating at 600.13 MHz frequency and 298 K probe temperature. The acquisition parameters were: 65,536 fids; 256 scans; probe temperature 300 K; spectral width 20.573 ppm; relaxation delay 1.000 s; acquisition time 4.819 s; pulse width 90°C; and total acquisition time 16 min (3 (link)).
A 0.30 mL aliquot of each sampled oil was diluted with 0.60 mL of deuterated chloroform (C²HCl₃) (99.8% purity). A 0.50 mL aliquot of the resulting mixture was then thoroughly mixed with a 0.10 mL volume of the 1,3,5-tribromobenzene (TBB) quantitative internal standard (prepared by dissolving 4.14 mg TBB in 2.0 mL C²HCl₃) in a 5-mm diameter NMR tube (Norrell HT, GPE Scientific). All signal resonances were referenced to tetramethylsilane (TMS) (δ = 0.000 ppm), residual C²HCl₃ (δ = 7.283 ppm) and TBB (δ = 7.537 ppm). In addition, TBB served as an internal quantitative ¹H NMR standard that was employed for determining ¹H NMR-detectable LOPs in sampled sunflower oils (3 (link)).