N heptane

All chemicals were of analytical grade unless otherwise stated. More specifically, tetra-methyl-ammonium-hydroxide (TMAH) 25%, sodium hydroxide, o-phtaldialdehyde and butylated hydroxyToluene were purchased from Sigma-Aldrich (Steinheim, Germany). Toluene, hydrogen chloride, methanol, chloroform, sodium chloride, and 20% boron trifluoride were purchased from Merck (Darmstadt, Germany). n-Heptane was purchased from VWR (Radnor, Pennsylvania, USA). The purified C23:0 was purchased from Nu Chek Prep (Elysian, MN, USA).

CBN (1 mg/mL in methanol, certified reference material), CBN-d₃ (100 μg/mL in methanol, certified reference material), CBD (1 mg/mL in methanol, certified reference material), and CBD-d₃ (100 μg/mL in methanol, certified reference material) were bought from Cerilliant; acetonitrile (HPLC gradient grade), methanol (HPLC gradient grade), n-hexane (HPLC grade), n-heptane (HPLC grade), and formic acid (98–100%) were obtained from VWR Chemicals; dichloromethane (HPLC grade) from Carl Roth, triethylamine from ACROS Organics, Fast Blue Salt B (FBS, dye content ~ 95%) from Sigma-Aldrich, Chromabond SiOH (1 ml/100 mg), Chromabond C₁₈ ec (1 ml/ 100 mg) as well as TLC (thin-layer chromatography) plates (silica gel 60, ALUGRAM Xtra SIL G UV₂₅₄ and octadecyl-modified silica, ALUGRAM RP-18 W/UV₂₅₄) from Macherey-Nagel, TLC plates (silica gel 60 without fluorescent indicator on aluminum sheets), and HPTLC (high-performance thin-layer chromatography) plates (silica gel 60 F₂₅₄ MS-grade for matrix-assisted laser desorption/ionization (MALDI) and silica gel 60 F₂₅₄ on glass plates) were purchased from Merck KGaA and analytical sea sand from Grüssig GmbH. Distilled diethyl ether and acetone were produced with a rotary evaporator from BÜCHI.

All chemicals were used as received. Caffeine, formic acid, Pirkle’s alcohol, hexobarbital, anthracene, and pyrene were purchased from Sigma-Aldrich GmbH (Taufkirchen, BY, DEU). HPLC grade chloroform (CHCl₃, purity: 99.8%) and n-heptane (purity: 97%) were acquired from VWR International GmbH (Darmstadt, HE, DEU). Photoresist AZ 1518, Developer AZ 351B, and chromium etchant AZ® ECI 3000 were bought from Microchemicals GmbH (Ulm, BW, DEU). High-purity water was obtained from a Smart2Pure purifying system (0,055 μS/cm, TKA Wasseraufarbeitungssysteme GmbH, Niederelbert, RP, DEU). Starting materials and product of the model reaction N-phenyl-1,2,3,4-tetrahydroisoquinoline were provided by the Zeitler research group (Institute for Organic Chemistry, Leipzig University, Leipzig, SN, DEU) and synthesized as previously reported [68 (link)]. The following solutions were prepared: Pirkle’s alcohol, hexobarbital, pyrene in n-heptane with the concentrations 0.18 mM, 0.05 mM, 5 mM, and 5.6 mM, respectively. pyrene, anthracene, N-phenyl-1,2,3,4-tetrahydroisoquinoline, and CBrCl₃ in CHCl₃ have the concentrations 5 mM, 5.6 mM, 1 mM, and 1 mM respectively. Caffeine in CHCl₃ have concentrations of 1.5, 3.0, 10, 20, and 50 μM. pyrene in n-heptane have concentrations of 0.05, 0.25, 0.5, and 1 mM.

Substances of different origin and purity (determined by gas chromatography–mass spectrometry) were used in these experiments, as listed in Table S1. Descriptions of the syntheses of E8,Z10-12:OAc and C25 pentaene are provided in Appendices 1 and 2, respectively. Transparent plastic delta traps with sticky inserts, purchased from CSalomon (Plant Protection Institute, Hungarian Academy of Science, Budapest, Hungary), were used. Red rubber septa (11 × 5 mm, #224100–020) from Wheaton Science Products (Millville, NJ, USA) were used as lures in traps for experiments on both moth species. Compound solutions were prepared in n-hexane (> 99%, Merck, Darmstadt, Germany) or n-heptane (> 99%, VWR, Fontenay-sous-Bois, France), and baits were produced by applying 100 µl of a solution on the septum. Baits for C. strobilella monitoring traps were loaded with 0.15 µg each of E8,E10-12:OAc and E8,Z10-12:OAc (amounts of stock solution adjusted for differences in isomeric purity of compounds), whereas baits for D. abietella assessment traps were loaded with 0.1 mg of Z9,E11-14:OAc and 10 mg of C25 pentaene.

All solvents were either purified by distillation or used in LC-MS grade. Dichloromethane (DCM), ethanol, ethyl acetate, n-heptane, n-hexane, methanol, and sodium sulfate (anhydrous) were purchased from VWR (VWR International, Radnor, PA, USA). Acetonitrile, toluene, and the series of n-alkanes (C₆-C₂₆) were purchased from Sigma-Aldrich (Sigma-Aldrich Corporation, St. Louis, MO, USA). tert-Butyl methyl ether was obtained from Thermo Fisher (Thermo Fisher Scientific, Waltham, MA, USA), and trichloromethane D1 (0.03% v/v) from Carl Roth (Carl Roth GmbH + Co. KG, Karlsruhe, Germany). Ultrapure water was used for the experiments (Thermo Fisher Scientific, Waltham, MA, USA). For the CCC and CPC experiments, the solvents n-heptane, ethyl acetate, and methanol of the biphasic solvent system n-heptane/ethyl acetate/methanol/water (Arizona S) were all from Merck (Merck KGaA, Darmstadt, Germany) in analytical grade (purity ≥99%). Milli-Q water was obtained from a Milli-Q Direct Water Purification System (Merck Millipore, Billerica, MA, USA).

High-performance liquid chromatography (HPLC)-grade solvents such as acetonitrile, n-heptane, and ethanol (EtOH), as well as menthol, eucalyptol, thymol, choline chloride, and citric acid were purchased from VWR Chemicals (Spain). Standards of 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), sodium carbonate (Na₂CO₃), aluminum chloride (AlCl₃), potassium persulfate (K₂S₂O₈), disodium phosphate (Na₂HPO₄), monopotassium phosphate (KH₂PO₄), fluorescein sodium salt, gallic acid, ascorbic acid, and quercetin were obtained from Sigma-Aldrich (Spain). Folin–Ciocalteu phenol reagent was acquired from Merck (Germany). 2,2-azobis (2-amidinopropane) dihydrochloride (AAPH) was purchased from TCI Chemicals (Japan). Ultrapure water was obtained from a Millipore system (Billerica, United States).