Natural Product Research Formerly Natural Product Letters ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/gnpl20 Phytochemical analysis on the leaves of Agathis microstachya J.F. Bailey & C.T. White Claudio Frezza, Fabio Sciubba, Rita Petrucci & Mauro Serafini To cite this article: Claudio Frezza, Fabio Sciubba, Rita Petrucci & Mauro Serafini (2022) Phytochemical analysis on the leaves of Agathis�microstachya J.F. Bailey & C.T. White, Natural Product Research, 36:21, 5626-5630, DOI: 10.1080/14786419.2021.2018435 To link to this article: https://doi.org/10.1080/14786419.2021.2018435 View supplementary material Published online: 27 Dec 2021. Submit your article to this journal Article views: 88 View related articles View Crossmark data Full Terms & Conditions of access and use can be found at https://www.tandfonline.com/action/journalInformation?journalCode=gnpl20 NATURAL PRODUCT RESEARCH 2022, VOL. 36, NO. 21, 5626–5630 https://doi.org/10.1080/14786419.2021.2018435 SHORT COMMUNICATION Phytochemical analysis on the leaves of Agathis microstachya J.F. Bailey & C.T. White Claudio Frezzaa , Fabio Sciubbaa,b , Rita Petruccic and Mauro Serafinia a Dipartimento di Biologia Ambientale, Universita di Roma “La Sapienza”, Rome, Italy; bNMR-based metabolomics laboratory (NMLab), Sapienza University of Rome, Rome, Italy; cDipartimento di Scienze di Base e Applicate per l’Ingegneria, Universita di Roma “La Sapienza”, Rome, Italy ABSTRACT ARTICLE HISTORY The first phytochemical analysis on the leaves of Agathis microstachya J.F. Bailey & C.T. White collected in Rome was reported in this work. The study evidenced the presence of four compounds i.e., 7,4’’’-dimethoxy-agathisflavone (1), 7,7’’-dimethoxy-cupressuflavone (2), dactylifric acid (3) and shikimic acid (4) which were identified by means of spectroscopic techniques. Compounds (1, 2, 4) were reported in the species for the first time as well as this is the second report on the presence of dactylifric acid (3) in the whole Araucariaceae family. The absence of diterpenoids from the studied accession is also important. All these chemotaxonomic aspects were discussed. Received 2 December 2021 Accepted 4 December 2021 KEYWORDS Agathis microstachya J.F.Bailey & C.T.White; Araucariaceae; phytochemical analysis; chemotaxonomy 1. Introduction Agathis microstachya J.F.Bailey & C.T.White, also known with the common names of Bull Kauri, is a conifer tree belonging to the Araucariaceae family. This species is morphologically characterized by a coarse and flaky bark, an unbuttressed and straight trunk, leaves with numerous longitudinal, parallel veins and medium-sized cones (Boland et al., 1984). This species is native to Australia but, in the last twenty years, it was introduced in several botanical gardens of different countries of the world. Its CONTACT claudio.frezza@uniroma1.it Supplemental data for this article can be accessed online at https://doi.org/10.1080/14786419.2021.2018435. ß 2021 Informa UK Limited, trading as Taylor & Francis Group NATURAL PRODUCT RESEARCH 5627 Figure 1. Structures of the identified compounds in the leaves of A. microstachya. wood can be employed for house framing and flooring since it is soft and easy to work and to clean (Boland et al., 1984; Frezza et al., 2020). There are only a few works in the literature about the phytochemistry of A. microstachya, one focusing on the essential oil composition (Brophy et al., 2000) and three evidencing the presence of agathic, abietic and neo-abietic acids and their derivatives in the resin (Carman 1964; Carman and Marty 1966; Carman and Marty 1970). In this study, the first phytochemical analysis on the leaves of A. microstachya collected in Rome was carried out. The main aims of the work were to widen the phytochemical knowledge on this species and to draw more general chemotaxonomic conclusions. 2. Results and discussion The phytochemical analysis on the leaves of A. microstachya evidenced the presence of four compounds, i.e., 7,4000 -dimethoxy-agathisflavone (1), 7,700 -dimethoxy-cupressuflavone (2), dactylifric acid (3) and shikimic acid (4) (Figure 1). Compounds (1, 2) are biflavonoids, compound (3) is an ester derivative of caffeic acid and compound (4) is an organic acid. To the best of our knowledge, all the compounds were evidenced in the species for the first time during this study. In fact, compound (1) has been already identified in the past in Agathis alba (Lam.) Foxw. (Khan et al., 1972), Agathis atropurpurea Hyland (Mashima et al., 1970), Agathis australis (D.Don) Lindl., Agathis ovata (C.Moore ex Vieill.) Warb., Agathis robusta (C.Moore ex F.Muell.) F.M.Bailey (Ofman et al., 1995) but also in chemotaxonomically correlated species such as Araucaria bidwillii Hook. (Khan et al., 1972), Araucaria columnaris (G.Forst.) Hook. (Ilyas et al., 1978), Araucaria cunninghamii Mudie, Araucaria rulei sk F.Muell. (Ilyas et al., 1977) and Wollemia nobilis W.G.Jones, K.D.Hill & J.M.Allen ( Glen et al., 2013; Venditti et al., 2017a, 2019a; Frezza et al., 2018). Compound (2) has been 5628 C. FREZZA ET AL. already reported in Agathis alba (Khan et al., 1972), Agathis atropurpurea (Mashima et al., 1970), Agathis australis, Agathis ovata, Agathis robusta (Ofman et al., 1995) but also in Araucaria araucana (Molina) K.Koch (Parveen et al., 1987), Araucaria columnaris (Ilyas et al., 1978), Araucaria cunninghamii, Araucaria rulei (Ilyas et al., 1977) and sk et al., 2013). Indeed, this is the second isolation of dactylifric Wollemia nobilis ( Glen acid (3) in the entire Araucariaceae family, having been previously identified in the family only in the unripe female cones of Wollemia nobilis (Venditti et al., 2021). Shikimic acid (4), which is the natural precursor for the biosynthesis of also flavonoids, has been previously identified in Agathis robusta (Venditti et al., 2017b) and Wollemia sk et al., 2013; Venditti et al., 2017a, 2019a, 2019b; Frezza et al., 2017, nobilis (Glen 2018). It is extremely important to underline that no diterpenoid was evidenced during this study. These compounds are considered to be other important chemotaxonomic markers of the Araucariaceae family (Frezza et al., 2020), and their absence in the studied accession may be likely due to climatic reasons. In fact, these leaves were collected in May 2021 which recorded colder temperatures and more rainy days. Major biosynthesis of terpenoids is correlated to higher temperatures and to more direct sunlight on the leaves (Chinnusamy et al., 2007). Nevertheless, it cannot be excluded from the beginning that this may actually be a genetic peculiarity of the species itself, and further phytochemical studies on the leaves of this accession and of the species itself, collected in different periods of the year and in different localities, are necessary in order to confirm this hypothesis. 3. Experimental See Supplementary material. 4. Conclusion The phytochemical analysis on the leaves of A. microstachya collected in Rome evidenced the presence of four compounds: 7,4000 -dimethoxy-agathisflavone (1), 7,700 dimethoxy-cupressuflavone (2), dactylifric acid (3) and shikimic acid (4). All these compounds were reported for the first time in the species. The presence of compounds (1, 2, 4) confirms the studied accession as a member of the Araucariaceae family under the phytochemical standpoint. Yet, the total absence of diterpenes in this species is an important and peculiar result which should be further verified by more in-depth phytochemical studies at any level. Acknowledgements The authors thank the Director of the Botanical Garden of Rome (Prof. Fabio Attorre) for providing us with the plant material and giving us the opportunity to study this species. Declaration interest The authors declare no conflict of interests in this work. NATURAL PRODUCT RESEARCH 5629 Funding The author(s) reported there is no funding associated with the work featured in this article. ORCID Claudio Frezza http://orcid.org/0000-0002-2968-5264 Fabio Sciubba http://orcid.org/0000-0002-1982-2712 Rita Petrucci http://orcid.org/0000-0003-2411-825X References Boland DJ, Brooker MIH, Chippendale GM, Hall N, Hyland BPM, Johnston RD, Kleinig DA, Turner JD. 1984. Forest Trees of Australia (4th ed). Melbourne, Australia; CSIRO.. Brophy JJ, Goldsack RJ, Wu MZ, Fookes CJR, Forster PI. 2000. The steam volatile oil of Wollemia nobilis and its comparison with other members of the Araucariaceae (Agathis and Araucaria). Biochem Syst Ecol. 28(6):563–578. Carman RM. 1964. Agathis microstachya oleoresin. Aust J Chem. 17(3):393–394. Carman RM, Marty RA. 1970. Diterpenoids. XXIV. A survey of the Agathis species of North Queensland. Two new resin acids. Aust J Chem. 23(7):1457–1464. Carman RM, Marty RA. 1966. Diterpenoids. IX. Agathis microstachya oleoresin Aust. Aust J Chem. 19(12):2403–2406. Chinnusamy C, Zhu J, Zhu J-K. 2007. Cold stress regulation of gene expression in plants. Trend Plant Sci. 12(10):444–451. la A, Foddai S, Bianco A, Serafini M. 2017. Frezza C, Venditti A, Rossi G, Serafini I, Pitorri M, Cicco Phytochemical study on the leaves of Wollemia nobilis. Biochem Syst Ecol. 74:63–66. la A, Serafini I, Sciubba F, Foddai S, Franceschin M, Frezza C, Venditti A, Scandurra C, Cicco Bianco A, Serafini M. 2018. Phytochemical profile of Wollemia nobilis half-matured female cones and their potential ethnopharmacological and nutraceutical activities. J Agric Sci Technol A. 8:162–170. Frezza C, Venditti A, De Vita D, Toniolo C, Franceschin M, Ventrone A, Tomassini L, Foddai S, Guiso M, Nicoletti M, et al. 2020. Phytochemistry, chemotaxonomy, and biological activities of the Araucariaceae family—a review. Plants. 9(7):888–873. sk M, Włodarczyk M, Stefanowicz P, Kucharska A. 2013. Biflavonoids from the Wollemi Pine, Glen Wollemia nobilis (Araucariaceae). Biochem Syst Ecol. 46:18–21. Ilyas M, Seligmann O, Wagner H. 1977. Biflavones from the leaves of Araucaria rulei F. Muell. and a survey on biflavanoids of the Araucaria genus. Z Naturforsch C. 32(3–4):206–209. Ilyas N, Ilyas M, Rahman W, Okigawa M, Kawano N. 1978. Biflavones from the leaves of Araucaria excelsa. Phytochemistry. 17(5):987–990. Khan NU, Ilyas M, Rahman W, Mashima T, Okigawa M, Kawano N. 1972. Biflavones from the leaves of Araucaria bidwillii Hooker and Agathis alba Foxworthy (Araucariaceae). Tetrahedron. 28(23):5689–5695. Mashima T, Okigawa M, Kawano N, Khan NU, Ilyas M, Rahman W. 1970. On the bisflavones in the leaves of Agathis alba Foxworthy [A. dammara]. Tetrahedr Lett. 11(33):2937–2940. Ofman DJ, Markham KR, Vilain C, Molly BPJ. 1995. Flavonoid profiles of New Zealand kauri and other species of Agathis. Phytochemistry. 38(5):1223–1228. Parveen N, Taufeeq HM, Khan NU. 1987. Biflavones from the Leaves of Araucaria Araucana. J Nat Prod. 50(2):332–333. Venditti A, Frezza C, Sciubba F, Foddai S, Serafini M, Bianco A. 2017a. Terpenoids and more polar compounds from the male cones of Wollemia nobilis. Chem. Biodivers. 14:1–7. Venditti A, Frezza C, Campanelli C, Foddai S, Bianco A, Serafini M. 2017b. Phytochemical analysis of the ethanolic extract of Agathis robusta (C. Moore ex F. Muell.) FM Bailey. Nat Prod Res. 31(14):1604–1611. 5630 C. FREZZA ET AL. la A, Sciubba F, Foddai S, Tomassini L, Bianco A, Venditti A, Frezza C, Rossi G, Serafini I, Cicco Serafini M. 2019a. A new byciclic monoterpene glucoside and a new biflavone from the male reproduction organs of Wollemia nobilis. Fitoterapia. 133:62–69. Venditti A, Frezza C, Vincenti F, Brodella A, Sciubba F, Montesano C, Franceschin M, Sergi M, Foddai S, Di Cocco ME, et al. 2019b. A syn-ent-labdadiene derivative with a rare spiro-b-lactone function from the male cones of Wollemia nobilis. Phytochemistry. 158:91–95. Venditti A, Frezza C, Rossi G, Sciubba F, Ornano L, De Vita D, Toniolo C, Tomassini L, Foddai S, Nicoletti M, et al. 2021. A new diterpene and other compounds from the unripe female cones of Wollemia nobilis. Nat Prod Res. 35(21):3839–3849.