2017 NPC Natural Product Communications Vol. 12

No. 12 Volatile Chemical Constituents of the Chilean Bryophytes 1929 - 1932

Jorge Cuvertino-Santonia,b*, Yoshinori Asakawab, Mohammed Nourc and Gloria Montenegrod aFaculty of Chemistry, Pontifical Catholic University of , Av. Vicuña Mackenna 4860, Santiago, Chile bFaculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan cLaboratoire Insulaire du Vivant et de l’Environnement, Université de la Nouvelle-Calédonie, France dFaculty of Agronomy and Forestry Engineering, Pontifical Catholic University of Chile, Av. Vicuña Mackenna 4860, Macul, Santiago, Chile [email protected]

Received: October 9th, 2017; Accepted: October 30th, 2017

The aim of this study is to increase the phytochemical knowledge of South American bryophytes, particularly from those of the southern tip of the continent, due to the uniqueness of its poorly known bryoflora. Thirty-two specimens were analyzed using GC-MS technique. Most of the molecules found in the present bryophyte species belong to sesquiterpenes. In general, liverworts resulted to be richer in terpenoid compounds, while mosses in n-alkanes. Oplopanone, trans- chrysanthenyl acetate and 6,7-secoeudesm-7(11)-en-6-al are compounds here newly reported to the bryophytes.-Ylangene and -herbertenol are new to hornworts, while -herbertenol and n-heneicosane are new to mosses.

Keywords: Mosses, Liverworts, Sesquiterpenes, Chemosystematics, Patagonia, Chile.

Chile counts for about 1500 bryophytes species, mostly distributed Chiloscyphus humilis (Hook. f. & Taylor) Hässel (loc.1): - in the southern part of the country, where richness and abundance of copaene; -herbertenol; -acoradiene; -elemene; bourbone-11- these plants are concentrated. For instance Chilean and Argentinian ene-like; cis-thujopsene; costunolide; cuparene; -maaliene; record 214 and 287 taxa of liverworts, isobazzanene; saussurea lactone-like. 2 respectively, in an area of 47,992 km . However, the central and the Juan Fernandez Archipelago are important hotspots Chiloscyphus humilis (Hook. f. & Taylor) Hässel (loc.6): - for bryophyte diversity that need to be better explored, particularly chamigrene; -copaene; -longipinene; aristolene; -barbatene; - due to the presence of endemic taxa in areas highly impacted by bazzanene; -chamigrene-like; -cubebene; -elemene; cis- man activities and/or biological invasions. thujopsene; costunolide; cuparene; -maaliene; isobazzanene;

saussurea lactone; selina-4(15),7-diene. Only 3.7% of the Chilean bryophytes have been studied chemically

[1]. Thus, Chilean and southern South American bryophytes Plagiochila hookeriana Lindenb. (loc.3): 1,2-herbertenediol; ar- become an interesting potential source of new molecules, molecular himachalene; ar-himachalen-2-ol; herbertene, longifolone. skeletons and related applications in pharmaceutical, pesticide and other industries. Within the main studies on the chemistry of Plagiochila hookeriana Lindenb. (loc.7): 1,2-herbertenediol; ar- Chilean bryophytes, Asakawa & Inoue [2,3] have elucidated the himachalene; herbertene; longifolene. chemical compositions of the crude extracts from 17 species of liverwort and 13 species of the genus Plagiochila. Further Riccardia spectabilis (Stephani) A. Evans (loc.5): -gurjunene; - information about chemical constituents and bioactivity of southern selinene; calarene. South American taxa are found in [1]. Nevertheless, most of the major secondary metabolites identified in Chilean bryophytes up to date belong to sesquiterpenes. Chiloscyphus horizontalis (Hook.) Nees (loc.1): -herbertenol; - longipinene-like; aristolene; -herbertenol; calarene; cis- Species analyzed and compounds detected are listed below. calamanene; cuparophenol; herbertene. Collecting sites are shown within brackets. Major compounds are in bold, while traces in italics. Lepidogyna menziesii (Hook.) R.M. Schust. (loc.1): 1-octen-3-yl acetate; alloaromadendrene; -ylangene; camphene; -3-carene; - Hornworts cadinene-like; -cadinene; limonene. Nothoceros endiviaefolius (Mont.) J. Haseg. ex J.C. Villarreal, Hässel & N. Salazar (loc.1): 1,5-di-epi--bourbonene; - Lepidogyna menziesii (Hook.) R.M. Schust. (loc.5): 1-octen-3-yl herbertenol; -ylangene; calarene; cuparene-like; dodecane; acetate; aristolene; 5-epi-aristolochene-like; -funebrene; - eicosane; peculiaroxide; phytol; undecane. ylangene-3-carene; -cedrene; -maaliene; -ylangene-like; gurjunene; limonene; maaliene-like; -amorphene. Liverworts Chiloscyphus humilis (Hook. f. & Taylor) Hässel (loc.2): - Blepharidophyllum densifolium (Hook.) Ångstr. ex C. Massal. barbatene; -elemene; costunolide; dihydroactinolide; (loc.5): longifolene; peculiaroxide; trans-calamenene. dihydrocostunolide; -herbertenol. 1930 Natural Product Communications Vol. 12 (12) 2017 Cuvertino-Santoni et al.

Cryptolophocolea pallidovirens (Hook.f. et Taylor) L.Söderstr Sphagnum magellanicum Brid. (loc.4): ar-himachalene; (loc.5): -barbatene; -copaene; anastreptene; -acoradiene;- dihydroactinolide; eicosane; heneicosane; octadecane; chamigrene; cuparene; -cuprenene; -cuprenene; isobazzanene; peculiaroxide; pentacosane. longifolene. Dicranoloma robustum (Hook. f. & Wilson) Paris (loc.1): - Cryptolophocolea pallidovirens (Hook.f. et Taylor) L.Söderstr muurolene; -ylangene; -bourboene; cadalene; calarene; cis- (loc.1): -barbatene; -copaene; anastreptene; -acoradiene; - calamanene; copaene; cyclocolorenone; heneicosane; pentacosane; chamigrene; bicycloelemene; calarene; cuparene; -cuprenene; - rosifoliol. cuprenene; isobazzanene; longifolene; peculiaroxide. Dicranoloma robustum var. lagunicolum (Dus.) Card. (loc.1): 1- Schistochila lamellata (Hook.) Dumort. ex A. Evans (loc.1): - octen-3-ol; 2-octenal,2-butyl-; 2-octenoic acid; 2,4-decadienal; - barbatene; -barbatene-like; cembrene C-like; cembrene-like; ionone epoxide; dihydroactinidiolide; -undecalactone; dolabella-3,7-diene-18-ol; isobazzanene; valencene-like. heneicosane; heptanoic acid; hexanoic acid; n-hexadecanoic acid; neophytadiene isomer I; neophytadiene isomer III; nonanoic acid; Riccardia pallidevirens (Stephani) A. Evans (loc. 5): -barbatene; octacosane; octanoic acid. (E)-beta-farnesene; trans-farnesol; (Z, E)-farnesyl acetate. Racomitrium geronticum Müll. Hal. (loc.4): 2- Riccardia prehensilis (Hook. f. & Taylor) C. Massal. (loc. 1): (+)- Pentadecanone,6,10,14-trimethyl-; 5,9,13-Pentadecatrien-2-one, - himachala-2,4-diene; 5-epi-aristolochene-like; -ferulene; - herbertenol; arachinodonic acid; -calarene; -herbertenol; longipinene; -ylangene; ar-himachalene; -acoradiene; - dihydroactinidiolide; docosane; eicosane; heneicosane; ylangene; bicyclosesquiphellandrene; cedrene-like; cuparene; heptadecane; methyl dihydroepijasmonate; octadecane; phytol longifolene; maaliol; thujopsene; thujopsene-2-ol. acetate; supraene; tetracosane.

Pachyschistochila splachnophylla (Hook. f. & Taylor) R.M. Schust. Polytrichastrum longisetum (Sw. ex Brid.) G.L. Sm. (loc.8): 2- & J.J. Engel (loc. 5): thunbergol-like. Pentadecanone,6,10,14-trimethyl-; 2,4,7,9-tetramethyl-5-decyn-4,7- diol; arachinodonic acid; dihydroactinolide; docosane; eicosane; Tylimanthus urvilleanus (Mont.) Hässel & Solari (loc. 3): heneicosane; heptadecane; hexadecanoic acid, ethyl ester; linoleic anastreptene; -bisabolene-like. acid, ethyl ester; nonadecane; octadecane; octadecanoic acid, ethyl ester; pentadecane; pentadecane,2,6,10,14-tetramethyl-; squalene. Tricholepidozia plumulosa (Lehm. & Lindenb.) E.D. Cooper (loc. 3): 1-octen-3-yl-acetate; 4,8a-dimethyl-1,2,3,4,6,7,8,8a-octalin; - Polytrichastrum longisetum (Sw. ex Brid.) G.L. Sm. (loc.4): muurolene; alloaromadendrene-like;; anastreptene-like; arachinodonic acid; dihydroactinolide; hexadecanoic acid, ethyl bicycloelemene; bicyclogermacrene; spathulenol; trans-4,8a- ester; hexadecanoic acid, z-11; nonadecane; pentadecane; dimethyl-4a,5-epoxydecaline. propanoic acid, 2 –methyl-,2-methylpropyl ester; squalene; tetratetracontane. Anastrophyllopsis involutifolia (Mont. ex Gottsche, Lindenb. & Nees) Váňa & L. Söderstr. (loc.5): (E)-ectocarpene; 6,7 Warnstorfia fluitans (Hedw.) Loeske (loc.1): 2- secoeudesm-7(11)-en-6-al; -herbertenol; -muurolene; Pentadecanone,6,10,14-trimethyl-; 6-dodecanone; -ionone; - alloaromadendrene; anastreptene; aristolene; -elemene; muurolene; -ylangene; -ionone epoxide-like; calarene; cadalene; bicyclogermacrene; calarene; cis-muurola-3,5-diene; copaene; cyclocolorenone-like; dihydroactinidiolide; -gurjunene- dictyopterene; eudesm-4(15)-ene-6-ol; fusicocca-3,5-diene; - like; heneicosane; heptadecane; heptanoic acid; hexadecanoic acid, elemene; heneicosane; ledol; peculiaroxide. ethyl ester; hexanoic acid; p-benzoquinone; pentadecane; phytol; vitamin E. Gackstroemia magellanica (Lam.) Trevis. (loc. 2): 1-octen-3-yl- acetate; alloaromadendrene; aristolene; bourbon-11-ene; calarene; Dendroligotrichum dendroides (Brid. ex Hedw.) Broth. (loc.7): - cis--santalene; -3-carene; trans-chrysanthenyl acetate; ionone; arachinodonic acid; dihydroactinolide; hexadecanoic acid, tritomarene. ethyl ester; squalene.

Marchantia berteroana Lehm. & Lindenb. (loc.4): -barbatene; - The commonest compounds found in the samples analyzed were: - cuprenene; -herbertenol; microbiotene-like- ylangene (1), -herbertenol (2), dihydroactinodiolide (3) and neocallitropsene; -chamigrene-like; -cubenene; -funebrene; cis- heneicosane (4) (Figure 1). thujopsene-like; cuparene; cuparophenol; isobazzanene. -Ylangene (1) has been detected in the liverwort genera Lepidozia, Mosses Marsupella and Scapania [4]. The presence of 1 in mosses and Dicranoloma chilense (De Not.) Ochyra & Matteri (loc.5): 10- hornworts has not been reported. However, -copaene, a related hydroxy-cis-calamenene; 6-epi-cubenol; -herbertenol; - chemical compound, is present in the moss genera Homalia and muurolene; -oplopenone-like; cadalene; calarene; cis-calamenene; Mnium [4]. In this study we report the presence of -ylangene (1) in cyclocolorenone; -muurolene; eicosane; guaia-6,9-diene; the hornwort Nothoceros endiviaefolius for the first time. - oplopanone; pentacosane; squalene; triacontane. Ylangene seems to be a marker compound in the Dicranoloma species analyzed, and is also present in Warnstorfia fluitans, and in Sphagnum fimbriatum Wilson (loc.4): -herbertenol; arachinodonic an unidentified Sphagnum species. The liverwort Lepidogyna acid; dihydroactinidiolide; heptadecane; hexadecane; n- menziesii shows traces of this compound, as well as Riccardia heneicosane; neophytadiene isomer III; octacosane; octadecane; prehensilis. peculiaroxide; pentacosane; phytol; phytol acetate; tetracosane. Volatile constituents of the Chilean bryophytes Natural Product Communications Vol. 12 (12) 2017 1931

Trans-chrysanthenyl acetate (8) is within the major volatile constituents of Gackstroemia magellanica, a common liverwort around boggy areas in Tierra del Fuego. Compound 8 has been isolated from species of the flowering genus Chrysanthemum. We report the first occurrence of this compound in bryophytes.

The simple thalloid liverwort Riccardia prehensilis from Tierra del Fuego, shows the presence of thujopsene (9) as the major volatile compound. This is the first report of 9 from the genus Riccardia. Thujopsene has been identified in the foliose liverwort genera Bazzania, Frullania, Lepidozia, Marsupella, Radula and Trocholejeunea, and from the complex thallose Marchantia and simple thallose Symphyogyna [4].

Within the major components of the fuegian Riccardia Figure 1: Commonest compounds found and new findings in Chilean bryophytes. pallidevirens, here we report for the second time the finding of farnesol (10) and farnesyl acetate (11) in liverworts. In bryophytes, -Herbertenol (2) is one of the most frequently identified these two natural compounds were firstly reported from the herbertenoids in liverworts [4]. It has been detected in the genera Mexican Asterella echinella [4]. Interestingly, farnesol is a natural Asterella, Wettsteinia, Chandonanthus, Dendromastigophora, pesticide and pheromone for insects [11]. The trinorsesquiterpenoid Herbertus, Marchantia, Mastigophora, Plagiochila and 4,8a-dimethyl-1,2,3,4,6,7,8,8a-octalin, (12) previously reported Tylimanthus [4,5]. Recently, this compound has been identified in from the moss Plagiothecium undulatum, is here for the first time the Lophocoleaceae, Chiloscyphus horizontalis from Tierra del identified in the liverwort Tricholepidozia plumulosa. Oplopanone Fuego [6]. In this study, we firstly report -herbertenol （ 2） from (13) is here for the first time detected in bryophytes, as a major mosses and hornworts. -Herbertenol (2) is a major constituent in  constituent in the moss Dicranoloma chilense. the fuegian Racomitrium geronticum and Dicranoloma chilense (Bryophyta) and in Nothoceros endiviaefolius (Anthocerotophyta). Peculiaroxide (14) is a frequent drimane in the genus Plagiochila. It has also been detected in the liverworts Chiloscyphus humilis, Within the Chilean liverworts it has been previously found in Anastrophyllopsis involutifolia and Marchantia berteroana. Plagiochila dusenii and Lepicolea ochroleuca [4]. Only in one moss Possibly, the presence of this compound in the moss Sphagnum species, Homalia trichomanoides, compound 14 has been detected. fimbriatum is related to the adsorption process operated by moss Here we report the presence of this natural compound in the cell walls. Sphagnum cell walls are rich in polyuronic acids and liverworts Blepharidophyllum densifolium (major constituent), have an extraordinary cation exchange capacity [7]. Similar Anastrophyllopsis involutifolia and Cryptolophocolea pallidovirens. adsorption capacity of organic compound has been noticed in an It is also present in the moss Sphagnum magellanicum. A trace unpublished field experiment that used transplanted Sphagnum amount of 14 was detected in Sphagnum fimbriatum and the patches in a forest ecosystem in Poland [8]. hornwort Nothoceros endiviaefolius.

Dihydroactinodiolide (3) is a cat attractant and pheromone in red- For structures not reported here refer to [4] and [5]. fire ants [9]. We have recorded this compound exclusively in the mosses Sphagnum fimbriatum, Sphagnum magellanicum, In general, liverworts resulted to be richer in terpenoid compounds, Dicranoloma robustum var. lagunicolum, Racomitrium geronticum, while mosses in n-alkanes. This outcome has also been observed in Polytrichastrum longisetum, Warnstorfia fluitans and other studies that analyzed the secondary metabolite constituents of Dendroligotrichum dendroides. bryophytes [12,13].

The n-alkane heneicosane (4) has been found in liverwort genus It is possible that 1,5-di-epi--bourbonene in the terrestrial Frullania, but not reported from mosses. Here we report the Nothoceros endiviafolius and -bourbonene in Dicranoloma presence of 4 as a major compound in the mosses Sphagnum robustum, come from the upper forest vegetation beneath these magellanicum and in one unidentified Sphagnum. It is also reported bryophytes species grow. In these forests, canopy is mainly from Sphagnum fimbriatum, Dicranoloma robustum, an dominated by Nothofagus betuloides tree. Indeed, Keble-Williams unidentified Dicranoloma, and from a Racomitrium sp. A trace of 4 has been detected in the mosses Warnstorfia fluitans, [14] reports the presence of - and -bourbonene in the Tasmanian Polytrichastrum longisetum, Racomitrium geronticum, Nothofagus cunninghamii. However, the chemical composition of Dicranoloma robustum var. lagunicola and in the liverwort foliage and bark of N. betuloides remains unstudied. Further studies Anastrophyllopsis involutifolia. on the secondary metabolite chemistry of southern South American bryophytes may offer new insights into the discussion of the origin Within the new findings from the analyzed fuegian bryophytes, we and evolution of the different linages of plants, as well as useful highlight the presence of the brown-algae pheromones (E)- information regarding the chemical ecology of the ecosystems ectocarpene (5) and dictyopterene (6) in the liverwort where bryophytes are abundant (i.e. Patagonian forests). Anastrophyllopsis involutifolia. These acetogenins have been also reported from the liverworts Fossombronia angulosa and GC/MS analysis of the ether extract of Marchantiophyta species Chandonanthus hirtellus [4]. Anastrophyllopsis involutifolia also collected in Tierra del Fuego indicates that each liverwort species, exhibits 6,7-secoeudesm-7(11)-en-6-al (7) as a major compound. genus or family produce own characteristic major compounds that This is the first time that this compound is found in bryophytes. could be used as taxonomic markers. The present liverworts are rich Related chemical compounds have been found in the higher plant sources of sesquiterpenoids, whereas only a few monoterpenoids, Inula viscosa [10]. diterpenoids and aromatic compounds have been found.

1932 Natural Product Communications Vol. 12 (12) 2017 Cuvertino-Santoni et al.

As the production of some bryophyte compounds is doubtful, it is Samples were devoid of debris and rinsed with distilled water three necessary to analyze the rest of the accompanying flora where the times prior to air-drying in paper bags. All preparatory steps were bryophyte species grow, including vascular plants, with the aim of performed aboard the Stella Australis. Samples were collected and distinguishing the origin of some molecules that might be produced identified by Jorge Cuvertino-Santoni. by other organisms and adsorbed by bryophytes. To reach this goal, comparative studies using in vitro or green house cultured Extraction: All samples were ground in a mill prior to extraction bryophytes may provide further insights and useful background for 7 days at room temperature with diethyl ether (Merck 100921 information on the chemical ecology of these environments (i.e. EMSURE® ACS, ISO, Reag. Ph Eur). The filtrate was reduced in a peatland ecosystems from Tierra del Fuego). rotary evaporator (Büchi R-210) at 24ºC. The crude extracts obtained were conserved in 20 mL glass vials at 4ºC. We conclude that southern South American taxa of bryophytes, particularly liverworts from peatlands, represent an interesting TLC: Each crude extract was checked by TLC in order to determine reservoir of new findings and molecules, consequently bryophytes the presence of major components and constituent patterns. TLC should be further studied and protected. was carried out on glass-plates coated with a thin layer of silica gel 60 F254 (0.25 mm) and eluted with a solvent mixture of n-hexane: Experimental ethyl acetate (4:1). The running distance was 8 cm and running time was approx. 14 min. Plates were sprayed with 30% HSO and Plant material: 32 bryophyte samples; 16 species of liverwort, 9 of 2 4 heated at 120ºC for visualizing the spots. moss and 1 hornwort, were collected in the Chilean territory of

Tierra del Fuego in January-February 2012. The mosses GC-MS: Gas chromatography-mass spectrometry analyses were Dendroligotrichum dendroides and Polytrichastrum longisetum and performed using an Agilent Technologies 6890N gas the liverwort Plagiochila hookeriana were also collected in Chiloé chromatograph coupled with a mass selective detector (Agilent Island (Chile). Collection sites were located in boggy areas along technologies 5973) on a HP-5MS capillary column (30 m x 0.25 the fjords and channels of Tierra del Fuego and mainland of Chiloé mm, 0.25 mm film thickness). The initial oven temperature was Island and are detailed as follows: 50ºC, with a 3 min holding time, and then increased to 250ºC at 5ºC

min-1, and held for 15 min at 250ºC. An injection temperature of 1. CHILE. Tierra del Fuego. Agostini Sound. Aguila Glacier. 280ºC was maintained, and helium (1mL min-1) was used as a Coastal Bog. Coord.: 402838 E - 3965989 N; 2. CHILE. Tierra del carrier gas. The detector was operated in electron impact mode (70 Fuego. Agostini Sound. Aguila Glacier. Coastal Bog. Coord.: eV with 3 scans/s, and mass range m/z 40-500) at 230ºC. Retention 403088 E - 3966380 N; 3. CHILE. Tierra del Fuego. Almirantazgo indices for all compounds were calculated relative to C8-C27 n- Sound. Ainsworth Bay. Forest. Coord.: 459074 E - 3971003 N; 4. alkanes. Compounds were identified using a computer-supported CHILE. Tierra del Fuego. Almirantazgo Sound. Ainsworth Bay. spectral library, mass spectra of reference compounds, MS data Peatland. Coord.: 459219 E – 39711867 N; 5. CHILE. Tierra del from the literature, and the library database of the Faculty of Fuego. Beagle Channel. Pía Sound. Pía Glacier. Periglacial Pharmaceutical Sciences, Tokushima Bunri University. vegetation. Coord.: 461444 E – 3930528 N; 6. CHILE. Tierra del

Fuego. . Hornos Island. Pond. Coord.: 610886 E – Acknowledgments - This research was funded by Conicyt grant 3796481 N; 7. CHILE. Chiloé Island. Ancud. Fundo Tantauco Lote folio nº 21100800 and Fondecyt grant folio nº 3160509. We thank 3. Forest. Coord.: 597710 E – 5338773 N; 8. CHILE. Chiloé Island. the Asakawa’s Laboratory team for assistance during chemical Ancud. Fundo Coquiao. Open grass area. Coord.: 599556 E– analysis of samples and the Cruceros Australis for logistic support 5350170 N in Tierra del Fuego.

References [1] Cuvertino-Santoni J, Montenegro G. (2013) Bioprospecting, a tool to conserve Chilean bryophytes. Gayana Botánica, 70, 16–25. [2] Asakawa Y, Inoue H. (1984) Chemical constituents of selected Chilean liverworts. In Studies on Cryptogams in Southern Chile. Inoue H (Ed.). Kenseisha, Tokyo, Japan. 109-115. [3] Asakawa Y, Inoue H. (1984) Chemical constituents of Chilean Plagiochila Species. In Studies on Cryptogams in Southern Chile. Inoue H (Ed.). Kenseisha, Tokyo, Japan, 117-124. [4] Asakawa Y, Ludwiczuk A., Nagashima F. (2013) Chemical constituents of bryophytes: bio- and chemical diversity, biological activity, and chemosystematics. Progress in the Chemistry of Organic Natural Products. 95, Springer, Vienna, 1-796. [5] Asakawa Y. (1995) Chemical constituents of the bryophytes. Progress in the Chemistry of Organic Natural Products. 65, Springer, Vienna, 1-618. [6] Cuvertino-Santoni J, Asakawa Y, Peralta DF, Montenegro G. (2014) Chemical evidence for the liverwort complex, Chiloscyphus concavus and C. horizontalis. Natural Product Communications, 9, 899-902. [7] Clymo RS. (1963) Ion exchange in Sphagnum and its relation to bog ecology. Annals of Botany, 27, 309-324. [8] Asakawa Y, Ludwiczuk A, Cuvertino-Santoni J, unpublished results. [9] Tucker A, Tucker S. (1988) Catnip and the catnip response. Economic Botany, 42, 214-231. [10] Andolfi A, Zermane N, Cimmino A, Avolio F, Boari A, Vurro M. (2013) Inuloxins A-D, phytotoxic bi-and tri-cyclic sesquiterpene lactones produced by Inula viscosa: potential for broomrapes and field dodder management. Phytochemistry, 86, 112–120. [11] Dancewicz K, Gliszczyńska A, Halarewicz A, Wawrzeńczyk C, Gabryś B. (2010) Effect of farnesol and its synthetic derivatives on the settling behaviour of the peach potato aphid Myzus persicae (Sulz.). Pestycydy/Pesticides, 1-4, 51-57. [12] Saritas Y, Sonwa MM, Iznaguen H, König WA, Muhle H, Mues R. (2001)Volatile constituents in mosses (Musci). Phytochemistry, 57, 443-457. [13] Huang X, Wang C, Xue J, Meyers PA, Zhang Z, Tan K, Zhang Z, Xie S. (2010) Occurrence of diploptene in moss species from the Dajiuhu Peatland in southern China. Organic Geochemistry, 41, 321–324. [14] Keble-Williams PJ. (2012) Canopy arthropods and herbivory on the Tasmanian southern beeches, Nothofagus cunninghamii and Nothofagus gunnii. PhD thesis, University of Tasmania, 1-346.