Figure 2: Genetic evidence supportive of the proposed biosynthetic pathways of dalesconols A–C (1–3).

(a) Exemplified by 1, the catalytic reaction was mediated by an iterative PKS and necessary proteins whose sequence scales were represented approximately. Lac, laccase; SD, scytalone dehydratase. (b, c) Comparisons of LC–MS/MS profiles in an EIC (extracted ion chromatogram) mode of wild-type (WT), pksTL gene knockout (pksTLKO) and lacTL gene knockout (lacTLKO) strains of D. eschscholzii, the latter two being unable to produce 1–3 and dihydrosphaerolone (a naphthol dimer). In the on-line electrospray ionization interface (ESI)–MS spectra of 1–3 and dihydrosphaerolone recorded in negative-ion mode, the chosen characteristic parent/daughter ion pairs were: 461.0>443.0 (1), 477.0>435.0 (2), 493.0>346 (3) and 349>277 (dihydrosphaerolone), which were acquired in MRM (multiple reaction monitoring) mode.