H. corriganiiis geographically widespread on North ... from Marlborough (MJB 721 and 1227). ...... River in Trounson Park, North Auckland (MJB 1451 ...... 60. 8. MeA OHA. L-4 -O-di glucoside. 18a le. 4 13 15 14 12a 23 16a 16d lb 4a 16 16c ...
New Zealand Journal of Botany
ISSN: 0028-825X (Print) 1175-8643 (Online) Journal homepage: http://www.tandfonline.com/loi/tnzb20
Composition and distribution of leaf flavonoids in Hebe and Leonohebe (Plantaginaceae) in New Zealand — 2. “Apertae”, “Occlusae”, and “Grandiflorae” Kevin A. Mitchell , Alison V. Kellow , Michael J. Bayly , Kenneth R. Markham , Patrick J. Brownsey & Phil J. Garnock‐Jones To cite this article: Kevin A. Mitchell , Alison V. Kellow , Michael J. Bayly , Kenneth R. Markham , Patrick J. Brownsey & Phil J. Garnock‐Jones (2007) Composition and distribution of leaf flavonoids in Hebe and Leonohebe (Plantaginaceae) in New Zealand — 2. “Apertae”, “Occlusae”, and “Grandiflorae”, New Zealand Journal of Botany, 45:2, 329-392, DOI: 10.1080/00288250709509721 To link to this article: http://dx.doi.org/10.1080/00288250709509721
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Date: 20 February 2017, At: 11:43
New Zealand Journal of Botany, 2007, Vol. 45: 329-392 0028-825X/07/4502-0329 © The Royal Society of New Zealand 2007
329
Composition and distribution of leaf flavonoids in Hebe and Leonohebe (Plantaginaceae) in New Zealand — 2. "Apertae", "Occlusae", and "Grandiflorae" KeviN A. M i T c h e l l industrial Research l t d PO Box 31310 lower hutt 5040, New Zealand AliSON v . K e l l O w * M i c h A e l J. BAyly † Museum of New Zealand Te Papa Tongarewa PO Box 467 wellington 6011, New Zealand
and "Grandiflorae" (informal infrageneric groups of Hebe). Presence/absence data are presented for 85 flavonoids from 377 samples of 42 species (as well as some samples of uncertain taxonomic placement). Flavonoid variation within and between species is illustrated using a series of ordination analyses. Most species in each of "Apertae" and "Grandiflorae" and many in "Occlusae" can be distinguished by their flavonoid profiles, generally through possession of unique combinations of compounds.
KeNNeTh R. MARKhAM industrial Research l t d PO Box 31310 lower hutt 5040, New Zealand
Keywords flavonoids; Hebe; Leonohebe; New Zealand flora; Plantaginaceae; Scrophulariaceae; numerical taxonomy; chemotaxonomy
PATRicK J. BROwNSey Museum of New Zealand Te Papa Tongarewa PO Box 467 wellington 6011, New Zealand
INTRODUCTION
P h i l J. GARNOcK-JONeS School of Biological Sciences victoria University of wellington PO Box 600 wellington 6140, New Zealand *Present address: Botany Department, l a Trobe University, victoria 3086, Australia. †School of Botany, The University of Melbourne, victoria 3010, Australia. Abstract A taxonomic revision of Hebe and Leonohebe in New Zealand has involved studies of plant morphology and flavonoid chemistry. This paper is the second in a series that summarises the composition and taxonomic distribution of leaf flavonoids in the two genera. it outlines the distribution of flavonoids in species of "Apertae", "Occlusae",
B06022; Online publication date 22 May 2007 Received 21 June 2006; accepted 5 January 2007
This paper is the second in an intended series of three papers providing an overview of the composition and taxonomic distribution of leaf flavonoids in Hebe and Leonohebe. it is part of a larger study toward a taxonomic revision of these genera, carried out jointly by the Museum of New Zealand, industrial Research ltd, and victoria University of wellington. The background to the project, together with an outline of the purpose of these papers and their format, are provided in the first paper (Markham et al. 2005). The aim of this second paper is to provide details of the distribution of flavonoids in three of the informal infrageneric groups in Hebe, i.e., "Apertae", "Occlusae", and "Grandiflorae" (see Moore, in Allan 1961). The groups discussed in this paper are included together for practical reasons, and not because they are closely related. These groups are also not strictly equivalent to the infrageneric groups used in a recent monograph of Hebe (Bayly & Kellow 2006), largely because the flavonoid comparisons presented here were prepared before the classification of Bayly & Kellow (2006) was finalised. These groups are, nonetheless, useful in providing a framework for comparison between morphologically similar species.
330 MATERIALS AND METHODS
New Zealand Journal of Botany, 2007, vol. 45 comprising H. angustissima, H. bishopiana, H. obtusata, and H. stricta; Subgroup 2, comprising H. acutiflora, H. adamsii1, H. bollonsii, H. breviracemosa1, H. ligustrifolia, H. perbella, and H. flavida; Subgroup 3, comprisingH. barkeri,H. chathamica, andH. dieffenbachii; Subgroup 4, comprisingH. adamsii1, H. corriganii1, H. macrocarpa, H. perbella, andH. tairawhiti. Ordinations were then performed separately for each subgroup. Hebe indet. (a), (b), (c), and (d) were not assigned to any of the subgroups. Hebe perbella was included in both subgroups 2 and 4, because it resembles some members of each of these groups in its morphology, i.e., having flowers with acute or subacute corolla lobes like members of subgroup 2, and having firm-textured leaves like most members of subgroup 4.
Flavonoids were analysed in a total of 377 leaf samples of "Apertae", "Occlusae", and "Grandiflorae" (details of voucher specimens are given in Appendix 1). Samples were collected, identified, and chemically analysed using the methods (including 2-dimensional paper chromatography (2D-PC), high performance liquid chromatography (HPLC), and mass spectrometry) described by Markham et al. (2005). The details of all flavonoids mentioned in this paper (including names, structures, and some physico-chemical properties) are listed, by flavonoid number, in Markham et al. (2005, table 1). Most samples were assigned to previously recognised species or infraspecific taxa (authorities are provided by Bayly & Kellow (2006)), but the identities of 15 samples from Northland (all belonging to "Occlusae") remain uncertain. These samples are referred to four informal entities, listed as: Hebe in- RESULTS det. (a), from Hikurangi Swamp (discussed by Bayly & Kellow (2006) in the notes under H. stricta); H. Flavonoid profiles of "Apertae" indet. (b), from Trounson Kauri Park, Northland Members of "Apertae" produce a wide range of (discussed by Bayly & Kellow (2006) in the notes flavonoids (Appendix 2), with O-glycosides of apiunder H. acutiflora); H. indet. (c), from Waipoua genin, luteolin, and 6-hydroxyluteolin being most Forest (discussed by Bayly & Kellow (2006) in the common. O-glycosides of 6-methoxyluteolin and notes under H. flavida); H. indet. (d), from Karikari 8-hydroxyluteolin also occur in many species, and Peninsula (discussed by Bayly & Kellow (2006) in those of quercetin also occur in approximately one the notes under H. ligustrifolia). quarter of species. Production of O-glycosides of Presence/absence of flavonoids 16c, 16g, and 6-hydroxyapigenin, 4 -methylapigenin, 4 -methyl16h, which co-chromatograph with 16 on 2D-Pcs, luteolin, kaempferol, and C-glycosides of apigenin was only recorded for H. bollonsii (large-leave "Oc- is more sporadic. An NMDS ordination is presented here for all clusae") and H. pubescens ("Apertae"). Because equivalent data are not available for other species, samples (Fig. 1), and details of species profiles are presence of these compounds is combined under presented in alphabetical order. included in this flavonoid 16 for the purpose of ordination analyses. analysis are 12 species and subspecies of "Apertae", As a result, the ordination (Fig. 1) presented here dif- along with: H. stricta var. stricta (for details see fers from that previously published for H. pubescens large-leaved "Occlusae"), included because of its (Bayly et al. 2003). In addition, flavonoids 16c, 16g, general similarity to H. salicifolia; and H. insularis and 16h are not mentioned in the text when listing ("Subdistichae"; details will be presented in the third paper of this series), included because its best placeunique compounds. 2 Multivariate (ordination) analyses of flavonoid ment is not clear . Of the species included, six (H. data employed Non-Metric Multidimensional Scal- paludosa, H. pubescens, H. salicifolia, H. speciosa, ing (NMDS; Kruskal 1964a,b) of matrices based on Manhattan distances (Sneath & Sokal 1973) as described by Markham et al. (2005). Analyses were performed separately for each of "Apertae", 1 Member of "Apertae", but included here for large-leaved "Occlusae", small-leaved "Occlusae", comparison. and "Grandiflorae" sensu Moore (in Allan 1961). 2 H. insularis was placed in "Subdistichae" by Moore For large-leaved "Occlusae", the large number of (in Allan 1961), presumably on the basis of its branched samples and taxa (22 species, varieties, and indeter- inflorescences, but it does not generally resemble most minate taxa) made ordinations difficult to interpret, other members of that group. it could equally be placed so the group was further divided into four subgroups in either "Apertae" or "Occlusae" because a leaf bud of morphologically similar species: Subgroup 1, sinus is variably present or absent.
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2
331
A 1392 •
o •
WELT 83376
•
A
X V X
1536 PGJ 2346 A
AK 234626 O ^
A 1391
PJB H2
• 1534
* % 3
+ * • •
WELT 81598
X
A
A 504
WELT 81599 A 720
PJB 111
A H45
% 2
1293 A
WELT 80838O
A 1304
.PGJ 2335 A 508 A 578
WELT 83373/S:2
V PJB H6 |_+" 1142
1300A
A 1185
• •
A A.
* 9 7 8
• • *
H. adamsii H. breviracemosa H. corriganii H. elliptica H. insularis H. leiophylla H. paludosa H. pubescens subsp. pubescens H. pubescens subsp. rehuarum H. pubescens subsp. sejuncta - Little and Great Barrier Ids H. pubsecens subsp. sejuncta - Mokohinau Ids H. salicifolia H. speciosa H. stricta var. stricta H. townsonii
WELT 83373/S 1/S3
WELT 82046 I WELT 80844
I
WELT 81866AK 234625
1052#
PJB H7
II
^#j PGJ 2259 # WELT 82047
•I< 9 WELT 82048
•
^•670 *1387 500 b «1384 I *& 1385 499 V * PGJ 2324 V535 V543
WELT 82049
667 •
: : PJB H3
Ei 1393
V72I
V 1227 V990 V 515
1340 • V991
• 1339
Fig. 1 Two-dimensional NMDS of flavonoid data for "Apertae". Point labels without letter prefixes are MJB collecting numbers.
332
H. townsonii, and H. insularis) have distinct flavonoid profiles and do not overlap with any other in the ordination. The three subspecies of H. pubescens form a group with similar flavonoid profiles that overlap in the ordination. H. adamsii and H. breviracemosa cluster together and overlap with H. elliptica; H. leiophylla, H. corriganii, and H. stricta var. stricta also overlap in the ordination. hebe adamsii GENERAL: H. adamsii (1 sample) has a flavonoid profile similar to H. breviracemosa. it also overlaps in the ordination with some samples of H. elliptica, mostly because of shared absences of flavonoids. SUMMARY OF FLAVONOIDS: Flavones present are 10, 1c,
12, 22, 4,13, 23, and q. UNIQUE COMPOUNDS: q is unique within Hebe. NOTES ON VARIATION: Not applicable, only one sample
examined.
New Zealand Journal of Botany, 2007, vol. 45 One of the three most variable species in "Apertae". There is a partial correlation between geographic origin and flavonoid profile. Samples from the Kaweka Range, hawke's Bay (MJB 1339 and 1340), are more similar to each other than to other samples, all of which are from the hauhungaroa Range, and show some variation. H. corriganii is geographically widespread on North island, occurring in disjunct localities and in habitats ranging from near-coastal lowland scrub to montane forests close to altitudinal tree line; the sampling employed here might not adequately reflect the variation in this species. NOTES ON VARIATION:
DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o
flavonoid consistently distinguishes H. corriganii from H. leiophylla; individual samples are differentiated by their particular combination of flavonoids. Absence of 8c distinguishes it from H. stricta var. stricta, although 8b is present in both H. corriganii and H. stricta var. stricta3.
DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: P r e s -
ence of 12 and q and absence of 16a distinguish this species from H. breviracemosa. Presence of 1c, 12, and q and absence of 8b distinguish it from H. elliptica. hebe breviracemosa GENERAL: H. breviracemosa (1 sample) has a flavonoid profile similar to H. adamsii and also overlaps in the ordination with some samples of H. elliptica, mostly because of shared absences of flavonoids.
hebe elliptica GENERAL: H. elliptica (9 samples) has a flavonoid profile most similar to H. adamsii, H. breviracemosa, H. leiophylla, H. insularis, and samples of H. pubescens subsp. sejuncta from the Mokohinau islands, although these similarities may be partly due to shared absences. SUMMARY OF FLAVONOIDS: Flavones present in all
22, 4,13, 23, and 16a.
samples are 4 and 8b. Those present in five or more are 13,14,12a, 23, and 3. Flavonoids 10 (trace), 22, 1e, 15,16a, 1a, 22a, 9,14c, 13a, 5a (unconfirmed weak), and 2 occur more sporadically.
UNIQUE COMPOUNDS: None.
UNIQUE COMPOUNDS: 14C is unique to H. elliptica
SUMMARY OF FLAVONOIDS: Flavones present are 10, 1c,
NOTES ON VARIATION: Not applicable, only one sample
examined. Differences fromH. adamsii are discussed above. Presence of 1c and absence of 8b distinguish H. breviracemosa from H. elliptica. DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES:
hebe corriganii GENERAL: H. corriganii (6 samples) has a flavonoid profile similar to H. leiophylla and H. stricta var. stricta.
within "Apertae", but not within Hebe. One of the three most variable species in "Apertae". There is some correlation between geographic origin and flavonoid profile; samples from Snares Is (WELT 83373/S1, S2, and S3) are more similar to each other than to most other samples. In contrast, MJB 1391 (Normanby Rd, Taranaki) and PJB H2 (Charleston, Nelson) are more similar to each other than to other samples from the same locations, i.e., MJB 1392 (Normanby Rd) and PJB H1 (Charleston). NOTES ON VARIATION:
SUMMARY OF FLAVONOIDS: Flavones present in all
samples are 10,4, 1b, and 1a. Those in three or more samples are 1c, 17, 13, 15, 16, 3d, 14a, 8b, and 3 Note that the presence of 8c may be obscured on 2DPc (very weakly). Flavonoids 12,17a, 24,14e (trace), by 8b, and also that 8b is a biosynthetic derivative of 8c. 22a, 15a, 13a, 5a, and i occur more sporadically. consequently, a lack of 8c, where 8b is present, may not be significant. UNIQUE COMPOUNDS: None.
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2 DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Dif-
ferences from H. adamsii and H. breviracemosa are discussed under those species. Presence of 8b and absence of 14a and 15a distinguish H. elliptica from H. insularis. Absence of 4a and 16c distinguishes it from samples of H. pubescens subsp. sejuncta from the Mokohinau Islands. No flavonoid consistently distinguishes H. elliptica from H. leiophylla; individual samples are differentiated by particular combinations of flavonoids. It is noteworthy, however, that H. elliptica does not accumulate 1b, which occurs in all H. leiophylla samples except for PJB H6 and H7 (both from Bullock Creek, north of Punakaiki, Nelson). hebe leiophylla GENERAL: H. leiophylla (11 samples) has a variable flavonoid profile similar to H. corriganii, H. elliptica, H. paludosa, H. salicifolia, and H. stricta var. stricta. SUMMARY OF FLAVONOIDS: Only flavone 4 occurs in all samples. Other flavones and flavonols present in five or more samples are 10, 1c, 13, 1b, 16, 1a, and 18. Flavonoids 12, 17, 22, 6, 24, 1f, 14, 16a, 14e (unconfirmed in three samples), 8b, 9a (unconfirmed weak in one sample), 5a, 21, and 19 occur more sporadically. UNIQUE COMPOUNDS: 21 and 19 are unique to H. leio-
phylla within "Apertae", but not within Hebe. NOTES ON VARIATION: One of the three most variable species in "Apertae". Samples from the same locality are generally more similar to each other than to other samples, e.g., MJB 499 and 500 (Cobb Valley, Nelson), and MJB 535 and 543 (Gouland Downs, Nelson). however, all samples from north-west Nelson (MJB 499, 500, 515, 535, and 543) are not more similar to each other than they are to samples from Marlborough (MJB 721 and 1227). The two most distinctive samples are those from near the south-west limit of the species' range (PJB H6 and h7, Bullock creek, north of Punakaiki), which have profiles similar (particularly PJB H6) to some samples of H. elliptica (see notes under that species), H. salicifolia, and H. paludosa. DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Dif-
ferences from H. corriganii and H. elliptica are discussed under those species. Absence of 9 distinguishes H. leiophylla from H. paludosa, and several flavonoids present in almost all H. leiophylla samples are absent from H.paludosa (i.e., 10,13, 1b, 16, and 1a). Absence of 8c and 8a distinguishes it from
333 H. salicifolia. Absence of 8c may also distinguish it from H. stricta var. stricta, although 8b is present in three H. leiophylla and all H. stricta var. stricta3.
hebe paludosa GENERAL: H. paludosa (2 samples), has a flavonoid profile most similar to H. leiophylla and H. salicifolia, although these similarities are partly due to shared absences. SUMMARY OF FLAVONOIDS: Flavones and flavonols
present in both samples are 6, 4, 1a, 8b, 9, and 18. Flavone 1d also occurs in MJB 1142. UNIQUE COMPOUNDS: None. NOTES ON VARIATION: The two samples, both from lake wahapo, westland, are similar. DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Dif-
ferences from H. leiophylla are discussed under that species. Presence of 1a and 18 and absence of 8c and 8a distinguish H. paludosa from H. salicifolia. hebe pubescens subsp. pubescens GENERAL: H. pubescens subsp. pubescens (4 samples) has a flavonoid profile similar to H. pubescens subsp. sejuncta. SUMMARY OF FLAVONOIDS: Flavones and flavonols
present in all samples are 10 (trace in two), 4,13, 12a (trace in two), 4a, 16c, 8b, 3,13a, and 25. Those in two or more samples are 1c (trace), 12 (trace in two of three), 15, 16 (trace), 16h (trace), 1a, 22a, 5a, and 18. Flavone 16g occurs at trace level in one sample. UNIQUE COMPOUNDS: 4a and 25 are unique to H.pubes-
cens (but not to subsp. pubescens) within "Apertae", but not within Hebe. NOTES ON VARIATION: Samples from Raukawa, coromandel Peninsula (MJB 962 and 963) are more similar to each other than they are to samples from Stony Bay, Coromandel Peninsula (MJB 978 and 979). DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o
single flavonoid distinguishes subsp. pubescens from subsp. sejuncta. however, presence of 3, which is absent in all subsp. sejuncta samples from Mokohinau islands and present at only trace levels in two of the other three samples of subsp. sejuncta, provides some distinction (trace levels being treated as absences in this analysis). Additionally, presence of 13a, which is absent in all samples of subsp. sejuncta from the Mokohinau islands and only weakly present in samples from little Barrier island, provides further differentiation.
334
hebe pubescens subsp. rehuarum GENERAL: H. pubescens subsp. rehuarum (6 samples) has a flavonoid profile similar to subsp. sejuncta.
New Zealand Journal of Botany, 2007, vol. 45 (unconfirmed in three of six samples), and 2 (unconfirmed) occur more sporadically. UNIQUE COMPOUNDS: 1 is unique to H. salicifolia
within "Apertae", but not within Hebe. samples are 10,12,4,13,15,12a, 16c, 16g (trace in NOTES ON VARIATION: Samples of H. salicifolia are two), 16h (trace in one), 1a, and 8b. Others present similar to each other, with the species forming a in three or more samples are 1c, 4a, 16,22a, 3,13a, tighter cluster than most others in the ordination. 5a, and 2. Flavone 23 occurs in one sample. There is no clear correlation between geographic UNIQUE COMPOUNDS: 4a is unique to H. pubescens origin and flavonoid profile. For instance, samples (but not to subsp. rehuarum) within "Apertae", but from southern South Island (MJB 578, Lake Marian, Southland; MJB 1304, Te Waewae Bay, Southland) not within Hebe. are more similar to samples from Nelson (e.g., MJB NOTES ON VARIATION: All samples are from Great Bar504,508, and 1185) than to samples from intermedirier island. MJB 1052 and 1053 are from the same ate localities (e.g., MJB 1145, Lake Wahapo, Westpopulation (Needle Rocks) and, although 1053 is similar to 1052, the latter is more similar to the land; PGJ 2335, Waihao Forks, Canterbury; MJB 1293, Otira valley, westland). There is also variation samples from other localities. among samples from the same locality (i.e., MJB DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: P r e s 1185, 504, and 508 from cobb valley, Nelson). ence of 12a distinguishes subsp. rehuarum from subsp. sejuncta. Presence of 12 further distinguishes DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Difit from all but one subsp. sejuncta sample (AK ferences from H. leiophylla and H. paludosa are discussed under those species. Presence of 8c, 8a, 234625, little Barrier island). and 8b and absence of 14,14a, and 15a distinguish H. salicifolia from H. insularis. hebe pubescens subsp. sejuncta SUMMARY OF FLAVONOIDS: Flavones present in all
GENERAL: H. pubescens subsp. sejuncta (7 samples) h . speciosa has a flavonoid profile similar to subsp. pubescens GENERAL: H. speciosa (2 samples) has a flavonoid and subsp. rehuarum. profile distinct from all other species in "Apertae" SUMMARY OF FLAVONOIDS: Flavonoids present in all but closest to some samples of H. elliptica and H. samples are 4,13,4a, 16c, and 22a. Others present insularis. in four or more samples are 10, 1c (trace level in four of six samples), 15, 1a, 8b, 18, and 25. compounds SUMMARY OF FLAVONOIDS: Flavones present in both 12,16g, 16h (trace), 3d, 3 (trace), 13a, 2, and i occur samples are 1c, 22, 29, 29a, and 16a. Those in one or other sample are 10, 12, 3d, and 16f (unconmore sporadically. firmed).
UNIQUE COMPOUNDS: 4a is unique to H.pubescens (but
not to subsp. sejuncta) within "Apertae", but is not unique within Hebe. NOTES ON VARIATION: Flavone 13a is absent in samples
from the Mokohinau Islands (AK 234626; WELT 80838, 81842, and 82046), but present in the other three samples. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r s p e c i e s :
See notes under subsp. pubescens and subsp. rehuarum. hebe salicifolia GENERAL: H. salicifolia (9 samples) has a flavonoid profile similar to H. insularis and H. paludosa and to some samples of H. leiophylla. SUMMARY OF FLAVONOIDS: Flavonoids present in all samples are 4,8c, 8a, and 8b. Those in five or more samples are 13, 1f, and 9. Flavonoids 10, 17, 5b (unconfirmed), 6 (trace), 16a, 1b, 1, 1d, 13a, 5a
UNIQUE COMPOUNDS: Flavones 29 and 29a are unique
to H. speciosa within Hebe and Leonohebe. NOTES ON VARIATION: The samples are from the same population. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: F l a -
vones 29 and 29a distinguish H. speciosa from all other species within Hebe and Leonohebe. Additionally, presence of 1c and absence of 4 and 8b distinguish H. speciosa from H. elliptica, while presence of 1c, 22, and 16a and absence of 4,14,14a, and 15a distinguish H. speciosa from H. insularis. hebe townsonii GENERAL: H. townsonii (3 samples) has a flavonoid profile distinct from all other members of "Apertae". it is most similar to H. stricta var. stricta. SUMMARY OF FLAVONOIDS: Flavonoids present in all samples are 10, 12, 5d, 6, 4, 15, 23a, 8c, 8b, and
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2
335
5a. Those present in one or two samples are 17, 1e, Subgroup 1 (Fig. 3) 22e, 24,14,12a, 16, and 1a. hebe angustissima UNIQUE COMPOUNDS: 5d, 22e, and 23a are unique to H. GENERAL: H. angustissima (10 samples) has a flavotownsonii within "Apertae", but not within Hebe. noid profile distinct from all other species but most NOTES ON VARIATION: The two samples from Nile similar to H. bishopiana, H. obtusata, and some River, south-west Nelson (PJB H3 and H4), are most samples of H. stricta var. stricta. similar, while the third, from Mt Burnett, northwest Nelson (MJB 1376), is more distinctive due to SUMMARY OF FLAVONOIDS: Flavones present in all samples are 6 (present in nine samples and possibly presence of 17, 1e, and 1a. also in tenth), 4,13, 1a, 8c, 8a, 8b, 9, and 3. Other DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: P r e s - flavones and flavonols present in four or more samence of 5d, 6, and 23a and absence of 13 and 1b ples are 1c, 13a, and 18. Flavonoids occurring more distinguish it from H. stricta var. stricta. sporadically are 10, 16a (unconfirmed), 1b, 4a, 2, 19 (unconfirmed), and l (unconfirmed). Flavonoid profiles of large-leaved "Occlusae" UNIQUE COMPOUNDS: None, but l (unconfirmed) is Flavonoid glycosides most common in members unique to large-leaved "Occlusae" within Hebe. of large-leaved "Occlusae" (Appendix 3) are Oglycosides of apigenin, luteolin, 6-hydroxyluteolin, NOTES ON VARIATION: Samples represent populations 6-methoxyluteolin, and 8-hydroxyluteolin. O-glyco- from two widely disjunct areas, but there is no clear sides of 4 -O-methylluteolin and quercetin are also distinction in flavonoid profile between them, e.g., common in many species, while those of 6-hydroxy- samples MJB 1177 and 1178 (from Wellington) apigenin occur in approximately one third of species. are similar to samples MJB 1199 and 1208 (from Production of O-glycosides of 4 -O-methylapigenin, Gisborne). Also, samples from the same locality are 6-methoxyapigenin and 8-hydroxyapigenin, and C- variable relative to other samples of this species, e.g., MJB 1198, 1199, 1201, and 1202 (Waioeka River, glycosides of apigenin, is more sporadic. NMDS ordinations are presented here for all sam- Gisborne). ples (Fig. 2), samples of Subgroup 1 only (Fig. 3), DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: H. samples of Subgroup 2 only (Fig. 4), samples of angustissima is distinguished from H. bishopiana Subgroup 3 only (Fig. 5), and samples of Subgroup by presence of 13,8c, and 8a, although 8b is present 4 only (Fig. 6). Details of species profiles are pre- in H. bishopiana3. H. angustissima differs from H. sented by subgroup and in alphabetical order. in obtusata by presence of 8c and 8a, and from all H. the ordination including all samples (Fig. 2), most stricta var. stricta samples apart from MJB 977, by species overlap with, or fall within, the widely vari- presence of 8a. however, MJB 977 produces a range able profiles of other species, with the exception of of other flavonoids that do not occur in H. angustisH. tairawhiti and H. indet. (a). H. insularis ("Sub- sima, i.e., 1e, 22a, 15,12a, 14d, and 3d. distichae", two samples), included here for comparison2, has two distinct profiles, each similar to hebe bishopiana other species in large-leaved "Occlusae". Likewise, GENERAL: H. bishopiana (1 sample) has a profile H. adamsii ("Apertae", one sample, included here distinct from all other species, but most similar to because it strongly resembles H. perbella (Bayly H. angustissima and H. obtusata. & Kellow 2006) and because some specimens re- SUMMARY OF FLAVONOIDS: Flavones and flavonols portedly lack a leaf bud sinus (Garnock-Jones & present are 10, 1c (unconfirmed), 6,18a (trace), 4, clarkson 1994)), H. breviracemosa ("Apertae", one 1a (trace), 8b, 9,3,13a, and l . sample, included here because it shows a general resemblance to large-leaved "Occlusae"), and H. UNIQUE COMPOUNDS: None, but l is unique to largecorriganii ("Apertae", six samples, included here leaved "Occlusae" within Hebe. because of its suggested relationship to H. macro- NOTES ON VARIATION: Not applicable, only one sample carpa (Bayly & Kellow 2006)) have been included examined. for comparison, and each is similar to species within DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Diflarge-leaved "Occlusae". Detailed notes for the spe- ferences from H. angustissima are discussed under cies of "Apertae" included here for comparison can that species. H. bishopiana differs from H. obtube found under that section, and for H. insularis, in sata by presence of 10 and 6 and absence of 13. it the third paper in this series. should be noted, however, that presence of 4, which
New Zealand Journal of Botany, 2007, vol. 45
336
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Mitchell et al.—Flavonoids in Hebe and Leonohebe 2
337
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New Zealand Journal of Botany, 2007, vol. 45
338
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occurs in H. obtusata, may obscure presence of 13 on 2DPc.
and other samples distinct, or most similar to H. angustissima. SUMMARY OF FLAVONOIDS: Flavones present in all
hebe obtusata GENERAL: H. obtusata (7 samples) has a variable flavonoid profile with one sample similar to some samples of H. stricta var. stricta and var. atkinsonii,
samples are 4, 13, 8b, 3, and 13a, while 5d, 16, 9, and 2 occur in three or more samples. Flavones present more sporadically are 12 (unconfirmed), 1b, and 1a.
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2
339
• 701
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Fig. 5 Two-dimensional NMDS of flavonoid data for Subgroup 3 of large-leaved "Occlusae". Point labels without letter prefixes are MJB collecting numbers.
New Zealand Journal of Botany, 2007, vol. 45
340
II
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Fig. 6 Two-dimensional NMDS of flavonoid data for Subgroup 4 of large-leaved "Occlusae". Point labels without letter prefixes are MJB collecting numbers.
5d within large-leaved "Occlusae". None is unique within Hebe. NOTES ON VARIATION: There is no clear relationship between geographic location and flavonoid profile, For example, w e l T 82066, from whatipu Beach, is UNIQUE COMPOUNDS:
more similar to MJB 1061, from Mercer Bay, than to w e l T 82067 also from whatipu Beach. DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Differences from H. angustissima and H. bishopiana are discussed under those species. H. obtusata differs
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2 from H. stricta var. stricta and var. atkinsonii by absence of 8c, although 8b is present in both species3.
341 Subgroup 2 (Fig. 4)
Hebe acutiflora GENERAL: H. acutiflora (9 samples) is only moderately variable in flavonoid profile, and is similar to H. ligustrifolia. SUMMARY OF FLAVONOIDS: Flavonoids present in all samples are 13, 16a, 16d, and 18. Other flavones and flavonols present in five or more samples are 4, 12a, and 8b. Flavonoids 10,16 (trace), 1a, 9,3,13a, 19, and 25 occur more sporadically. UNIQUE COMPOUNDS: None within large-leaved "Occlusae", but 16d is unique, within Hebe, to largeleaved "Occlusae". NOTES ON VARIATION: There is a partial relationship between geographic location and flavonoid profile, SUMMARY OF FLAVONOIDS: Flavone 8b occurs in all with samples collected from the same location gensamples. Flavones present in 45 or more samples are erally being similar, and placed near each other in 10,4,13,16, 1a, and 8c. Flavones 1b, 14d, 9,3,5a, the ordination, e.g., MJB 1540 and 1541 (Waipoua and 2 occur in 14 or more samples. Other flavonoids Forest, North Auckland), 1544 and 1545 (Puketi present more sporadically are 1c, 12,6, 1e, 15,12a, Forest, North Auckland), and MJB 445 and 446 4a, 14e, 22a, 3d, 14a (unconfirmed), 15a (trace), (Rainbow Falls, North Auckland). However, WELT 81878 (Puketi Forest) is more similar to samples 8a, 13a, 18, c, and i. from Rainbow Falls than to others from the same UNIQUE COMPOUNDS: None. location. NOTES ON VARIATION: There is some relationship between geographic location and flavonoid profile. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o Each variety has a well-defined geographic distri- flavonoid consistently distinguishes it from H. bution. with the exception of var. stricta, all other ligustrifolia; individual samples are differentiated varieties are less variable than the species as a whole, by their particular combinations of flavonoids. with varieties occupying overlapping sub-regions of that covered by H. stricta in the ordination. Samples hebe bollonsii of var. stricta show little relationship between geo- GENERAL: H. bollonsii (5 samples) has a flavonoid graphic origin and flavonoid profile. For example, profile similar to H. ligustrifolia. samples fromNorthland (MJB 417,418,449,1409, SUMMARY OF FLAVONOIDS: Flavonoids present in all and 1410) are highly variable, as are samples from samples are 10, 1c, 22,22b, 13,16a, 16d, 16f (trace East Cape (MJB 1344, 1351,1363, and 1365). The in one), and 8b. Others present in four samples are tetraploid Northland sample, MJB 1639, is not simi- 4 and 5a. lar to other Northland samples, but falls within var. UNIQUE COMPOUNDS: 22b and 16f are unique within stricta in the ordination. large-leaved "Occlusae" but not within Hebe. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r s p e c i e s / v a r i e TIES: No single flavonoid clearly distinguishes var. NOTES ON VARIATION: There are few samples for comatkinsonii, var. egmontiana, var. lata, or var. mac- parison, but there is probably no correlation between roura from var. stricta. The tetraploid sample MJB flavonoid profile and geographic location, e.g., MJB 1639 differs from all other H. stricta by the absence 1414 (Matapouri Bay, North Auckland) and AK of 8c, but it does produce 8b3. No other flavonoid 252128 (cult. ex Aorangi Island) are more similar glycoside clearly separates one variety from another; to each other than to other samples of the same (or individual samples are separated in the ordination similar) provenance. by their particular combinations of compounds. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: H. Differences from H. obtusata are discussed under bollonsii differs from H. ligustrifolia by presence that species. of 22b. hebe stricta GENERAL: H. stricta (62 samples) is the most widely sampled species of large-leaved "Occlusae". Most samples have similar flavonoid profiles, but a few are more distinctive. H. stricta var. stricta (38 samples) overlaps all other varieties in the ordination. H. stricta var. atkinsonii (9 samples) partly overlaps var. stricta, var. egmontiana (6 samples), and var. lata (4 samples). variety lata overlaps var. stricta and var. atkinsonii, and is similar to var. egmontiana. variety macroura (5 samples) is as similar to some samples of var. egmontiana as it is to var. stricta, overlapping both varieties. The only species which overlaps H. stricta in the ordination is H. obtusata.
342
Hebe flavida GENERAL: H. flavida (12 samples) has a relatively variable flavonoid profile. Ten of the samples have profiles similar to H. breviracemosa, H. ligustrifolia, and H.perbella, but two, MJB 1419 and w e l T 81843, are more distinct. SUMMARY OF FLAVONOIDS: Flavones and flavonols
present in all samples are 13, 1a, and 18, while 10, 1c, 22, 4,16a, and 19 occur in six or more. Those occurring more sporadically are 1e, 23, 4a (trace), 16, 22a, 3d (trace), 8b, 3, 5a, 25, and c. UNIQUE COMPOUNDS: None, but 19 is limited to Subgroup 2 within large-leaved "Occlusae", apart from an unconfirmed presence in one H. angustissima sample. NOTES ON VARIATION: There is a partial relationship between geographic location and flavonoid profile. For example, MJB 1407 and 1408 (Kerr Road, North Auckland) are almost identical, and MJB 1553 and 1554 (Horokaka, North Auckland) are also very similar to each other. Samples MJB 1560 and 1561 (Maunganui Bluff, North Auckland), however, are more distinct from each, as are MJB 1419 and 1420 (Waima Range, North Auckland). DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Dif-
ferences from H. ligustrifolia and H. perbella are discussed under those species. Presence of 1a and 18 distinguishes it from H. breviracemosa. hebe ligustrifolia GENERAL: H. ligustrifolia (15 samples) has a highly variable flavonoid profile with samples overlapping all other species in subgroup 2, except possibly H. adamsii ("Apertae", only included for comparison).
New Zealand Journal of Botany, 2007, vol. 45 Bream Head (MJB 430 and 432), Cape Reinga (MJB 1551 and 1552), and Whangaruru (MJB 1436 and 1437). Also, samples from Tutukaka Harbour (MJB 1433 and 1550) collected eight months apart have very distinct flavonoid profiles, being placed some distance from each other in the Subgroup 2 ordination. This pattern of variation has not been correlated with any obvious morphological characters. DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Dif-
ferences from H. acutiflora and H. bollonsii are discussed under those species. Although no single flavonoid glycoside distinguishes it from all H. flavida samples, most H. ligustrifolia samples have 16d, which is absent from H. flavida, and only 4 out of 15 have 1a, which is present in all H. flavida samples. it is distinguished from H. adamsii by presence of 8b and absence of 12 and q. hebe perbella GENERAL: The two samples of H. perbella have substantially different flavonoid profiles. One, MJB 407, is most similar to H. breviracemosa, H. flavida, and some samples of H. ligustrifolia, while MJB 1538 is distinct from all other species included in Subgroup 2. SUMMARY OF FLAVONOIDS: Flavones present in both samples are 10, 1c (trace in one sample), 4,13, and 16 (unconfirmed in one sample). Other flavonoids present in MJB 1538 are 1b, 16b, 1a, 22a, 3d, 8c, 8b, 3, and a. UNIQUE COMPOUNDS: a is unique within Hebe. NOTES ON VARIATION: MJB 1538 (cult. ex Maungaraho
Rock, North Auckland) produces flavonoid glycosides not present in MJB 407 (cult. ex Waima Forest, North Auckland).
SUMMARY OF FLAVONOIDS: Flavones 4,13, and 8b are
DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: B o t h
present in all samples and 16a in all but two. Other flavonoids present in 8 or more samples are 1c, 22, 16d, 16 (trace in 6 of 10 samples), and 5a. Flavones and flavonols occurring more sporadically are 10, 6, 18a, 1e (trace), 12a, 23, 1b, 16b, 1a, 22a, 14a (trace), 8c, 8a, 9,3,13a, 2 (trace), 18,19, and 25. UNIQUE COMPOUNDS: None, but presence of 1a is limited to Subgroup 2 within large-leaved "Occlusae". NOTES ON VARIATION: There is no apparent relationship between geographic location and flavonoid profile. Pairs of samples collected from the same location on the same day have distinct flavonoid profiles and are, in most cases, more similar to samples from other locations than to each other, e.g., samples from
samples differ from H. flavida by absence of 18, and from H. breviracemosa by absence of 22 and 23. H. perbella differs from the morphologically similar (Bayly & Kellow 2006) H. adamsii by absence of 12, 22, 23, and q. Subgroup 3 (Fig. 5) hebe barkeri GENERAL: H. barkeri (4 samples) has a variable flavonoid profile that is distinct from other members of Subgroup 3, but is most similar to H. dieffenbachii. SUMMARY OF FLAVONOIDS: Flavonoids present in all samples are 4, 15, 12a, 16a, 8a, and 8b. Others
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2 present in two or three are 22 and 1e, while 10,17, 5b, 6 (trace), and 5a only occur in MJB 699. UNIQUE COMPOUNDS: Flavone 5b is unique within
large-leaved "Occlusae" but not within Hebe. NOTES ON VARIATION: There is no clear relationship between geographic origin and flavonoid profile. MJB 692 (Rangaika Scenic Reserve, Chatham Island) is less similar to MJB 699, from the same location, than it is to both MJB 717 and MJB 718 (Tuku Nature Reserve, chatham island). DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: H.
barkeri differs from H. dieffenbachii by presence of 8a and absence of 8c, and from H. chathamica by absence of 13 and 8c, but 8b is present in H. barkeri3. hebe chathamica GENERAL: H. chathamica (4 samples) has a flavonoid profile most similar to H. dieffenbachii.
343 NOTES ON VARIATION: There is no clear relationship be-
tween geographic origin and flavonoid profile. MJB 697 and 698 (Rangaika Scenic Reserve, Chatham island) are similar relative to other samples, but MJB 696 from the same location is more distinct. MJB 713 and 714 (Matarakau, Chatham Island) are variable relative to the species as a whole. All other samples are from separate locations on chatham island. DIFFERENCES FROM CHEMICALLY SIMILAR SPECIES: Dif-
ferences from H. barkeri and H. chathamica are discussed under those species. Subgroup 4 (Fig. 6) hebe macrocarpa GENERAL: H. macrocarpa (14 samples) has a variable flavonoid profile that is distinct from other members of Subgroup 4. it is most similar to H. corriganii. SUMMARY OF FLAVONOIDS: Flavones present in all sam-
SUMMARY OF FLAVONOIDS: Flavones present in all
ples are 10, 1c, 4,13, 1b, 16, and 1a. Others present samples are 4, 13, 15, 12a, 16a, 8c, 8a, and 8b. in seven or more samples are 12, 3, 13a, 8a, and Others present in two or more are 3,19c, and 5a; 14 possibly 5a. Flavones and flavonols occurring more (unconfirmed), 13a, and 2 are more sporadic. sporadically are 22,6,18a, 24,12a, 14e (trace), 22a, UNIQUE COMPOUNDS: 19C, in two samples, and 14, 3d, 14a (unconfirmed), 8a, 9, 2, and 18. possibly in one sample, are unique in large-leaved UNIQUE COMPOUNDS: None; however, 24 is limited to "Occlusae" but not within Hebe. Also, 13a (in one Subgroup 4 within large-leaved "Occlusae", but not sample) is unique within Subgroup 3 but not within to large-leaved "Occlusae" within Hebe. large-leaved "Occlusae". NOTES ON VARIATION: There is some relationship beNOTES ON VARIATION: There is no clear relationship be- tween geographic origin and flavonoid profile. Samtween geographic origin and flavonoid profile, e.g., ples from the west coast of Auckland (MJB 1439, MJB 712 (Kaiangaroa, Chatham Island) is at least 1445, and 1446) are generally similar to each other, as similar to MJB 715 (Point Gap, Chatham Island) as are samples from Coromandel Peninsula (MJB as it is to other samples from Kaiangaroa. 959,960,981, and 982), Great Barrier Island (MJB 1054 and 1055, and w e l T 81557 and 82580), and DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: H. Bream Head (MJB 419 and 421). Together, specichathamica differs from H. dieffenbachii by presmens from islands of Hauraki Gulf (Great Barrier ence of 8a. Differences from H. barkeri are disand little Barrier) and Bream head are generally cussed under that species. distinct from those of Auckland and the coromandel Peninsula. hebe dieffenbachii GENERAL: H. dieffenbachii (9 samples) has a variable flavonoid profile similar to both H. barkeri and H. chathamica.
SUMMARY OF FLAVONOIDS: Flavones present in all
samples are 4,12a, 16a, 8c, 8b, and possibly 13 (unconfirmed in six samples); 15 and 3 are each present in seven samples. Flavonoids 1b (unconfirmed), 9 (unconfirmed), 5a, 2 (trace), and m all occur more sporadically. UNIQUE COMPOUNDS: m is unique within large-leaved "Occlusae", but not within Hebe.
DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o
flavonoid consistently distinguishes it from H. corriganii; individual samples are differentiated by their particular combinations of flavonoids. hebe perbella GENERAL: H. perbella (2 samples) has a variable flavonoid profile most similar to H. corriganii. SUMMARY OF FLAVONOIDS: See Subgroup 2 for de-
tails. UNIQUE COMPOUNDS: See Subgroup 2 for details.
344
New Zealand Journal of Botany, 2007, vol. 45
DIFFERENCES from chemically similar species: H. indet. (a) differs from all H. stricta samples by absence flavonoid consistently distinguishes it from H. cor- of 8b, and from all H. stricta varieties apart from var. riganii; individual samples are differentiated by their stricta by absence of both 4 and 13 (one or other of 4 or 13 also being present in all var. stricta samples). particular combinations of flavonoids. it differs from H. macrocarpa by presence of 15 and hebe tairawhiti 15a and by absence of 10, 1c, 4,13, and 1b. GENERAL: H. tairawhiti (6 samples) has a flavonoid hebe indet. (b) profile distinct from all other species of Subgroup 4, among which it is most similar to H. macrocarpa GENERAL: H. indet. (b) (4 samples) has a flavonoid profile distinct from all other members of largeand H. perbella. leaved "Occlusae". It is chemically most similar SUMMARY OF FLAVONOIDS: Flavones present in all to H. corriganii (but shows a greater morphologisamples are 10,4, 1b, 16, 1a, 14e, 8c, 8b, 9, and 5a. cal resemblance to other members of large-leaved Others present in four or more samples are 22a and "Occlusae). 2. Flavones and flavonols present more sporadically SUMMARY OF FLAVONOIDS: Flavones present in all samare 1c, 24, 6,12a (trace), 14d, and 18. ples are 10,12, 4,13,15, 1b, 16, 1a, 22a, and 15a; UNIQUE COMPOUNDS: 14d is unique within Subgroup 3d is present in two samples, while 1c, 16b (trace), 4, but not within large-leaved "Occlusae". 2 (trace), and i each occur in one. NOTES ON VARIATION: There is some relationship UNIQUE COMPOUNDS: None within large-leaved "Ocbetween geographic origin and flavonoid profile. clusae", but i only occurs within members of largeSpecimens from Gisborne (MJB 1355, 1360, and leaved "Occlusae". PGJ 2313) are similar to each other, but less so to those from Hawke's Bay (MJB 1347, 1348, and NOTES ON VARIATION: All samples are from the waima River in Trounson Park, North Auckland (MJB 1451 1349) which are also more variable. was from a plant cultivated in wellington, but of the DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: H. same original provenance). tairawhiti differs from H. macrocarpa by presence of 8c and absence of 13, but H. macrocarpa contains DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o 8b3. H. tairawhiti differs from H. perbella by pres- flavonoid consistently distinguishes it from H. corence of 14e, 9, and 5a, and absence of 13. it should riganii; individual samples differ by their particular be noted that 4 is present in H. tairawhiti, and this combinations of flavonoids. may obscure 13 on a 2DPc. For this reason, absence of 13 in H. tairawhiti may not be good distinguish- hebe indet. (c) GENERAL: H. indet. (c) (2 samples) is most similar to ing character. one sample each of H. ligustrifolia, H. acutiflora, Indeterminate/unidentified samples of large-leaved and H. flavida (all of which it resembles morpho"Occlusae" logically). Samples included here are labelled on Fig. 2. SUMMARY OFFLAVONOIDS: Flavones and flavonols present in both samples are 10, 1c, 22, 4,13,16a, hebe indet. (a) 16d, 1a, 8b, 5a, 18, and 19. Others present in one GENERAL: H. indet. (a) (1 sample) has aflavonoidpro- or other sample are 1b, 16 (trace), 22a (trace), 9 file distinct from all other members of large-leaved (trace), 3,13a, and 2. "Occlusae", but most similar to H. macrocarpa and UNIQUE COMPOUNDS: None within large-leaved "Ocsome sample of H. stricta (to which it is morpho- clusae" or Hebe. logically closest). NOTES ON VARIATION: Both samples are from the same SUMMARY OF FLAVONOIDS: Flavonoids present are location (Ohae Stream, Waipoua Forest, North Auck15, 16, 1a, 14d (unconfirmed), 22a, 3d, and 15a land). They have most flavonoids in common, with (trace). separation being caused by a few flavonoids present UNIQUE COMPOUNDS: None within large-leaved "Ocin one or other sample. clusae" or Hebe. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: H. NOTES ON VARIATION: Not applicable, only one sample indet. (c) is distinguished from H. acutiflora by examined. presence of 1c, 22, and 5a, and from H. flavida NOTES ON VARIATION: See Subgroup 2 for details.
DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2
345
by presence of 16d (although this is only weakly present in H. indet. (c)). No flavonoid distinguishes H. indet. (c) from H. ligustrifolia, individual samples being distinguished by their particular combination of flavonoids.
apigenin and/or 6-hydroxyapigenin-7-O-glycosides is common in H. calcicola, H. decumbens, H. stenophylla, H. strictissima, and H. subalpina. Production of the biosynthetically distinct apigenin-6,8-di-Cglucoside occurs in H. rakaiensis, H. strictissima, and H. subalpina. hebe indet. (d) NMDS ordination of all samples (Fig. 7) shows GENERAL: H. indet. (d) (7 samples) has a variable that all 16 species overlap with, or fall within, the flavonoid profile. It is most similar to H.flavida, and widely variable profiles of other species. Details of less so to H. acutiflora and H. ligustrifolia (one of species profiles are presented in alphabetical order. the species to which it is morphologically closest). Some samples are also similar to some samples of hebe albicans GENERAL: H. albicans (20 samples) has a flavonoid H. angustissima and H. obtusata. profile similar to H. evenosa, H. topiaria, and H. SUMMARY OF FLAVONOIDS: Flavones present in all samples are 13,16a, and 8b. Others present in four traversii. or more samples are 6, 4, 1a, and 9. Flavones and SUMMARY OF FLAVONOIDS: Flavones and flavonols flavonols occurring more sporadically are 10, 1c, 22 present in all samples are 4, 8b, 5a (unconfirmed in one), 18, and 19. Other flavonoids present in 10 (unconfirmed), 1b, 16 (trace), 3,13a, 5a, and 18. or more samples are 1a, 8c (trace in 15 of 19 ocUNIQUE COMPOUNDS: None. currences), 8a, 9, and 3. Flavonoids 10, 3e (trace), NOTES ON VARIATION: All samples are from a small 5b (trace), 6 (trace), 1e, 3b, 13 (trace), 16a (uncongeographic area, on or near Karikari Peninsula, firmed), 4a (trace), 16 (trace), 13a, 2,12b (unconNorthland (WELT 81844 is from a plant cultivated in firmed weak), 25 (unconfirmed), y, and z all occur wellington, but of the same original provenance). more sporadically. DIFFERENCES from c h e m i c a l l y s i m i l a r species: N o fla-
vonoid consistently distinguishes H. indet. (d) from H. ligustrifolia; individual samples are distinguished by their particular combination of flavonoids. H. indet. (d) differs from: H.flavida by absence of 1a; H. acutiflora by absence of 16d; H. angustissima by absence of 8c and 8a; H. obtusata by presence of 16a and absence of 5d. Flavonoid profiles of small-leaved "Occlusae" The flavonoid chemistry of small-leaved "Occlusae" (Appendix 4) is dominated by the production of O-glycosides of luteolin, 6-hydroxyluteolin, and 8-hydroxyluteolin. Apigenin, 6-hydroxyapigenin, kaempferol, and quercetin O-glycosides are also produced, but to a lesser extent. H. stenophylla, H. brockiei, H. treadwellii, and H. decumbens possess very active flavone 6- and 8-hydroxylating enzymes, producing almost exclusively the 6- and 8-hydroxyluteolin and 8-hydroxyapigenin glycosides. in contrast, several species, including H. parviflora, H. strictissima, and H. calcicola, accumulate significant amounts of the luteolin-O-glycosides, as well as the 6- and 8-hydroxyflavone glycosides. Approximately one third of the taxa, including H. albicans, H. calcicola, H. evenosa, H. parviflora, H. strictissima, H. topiaria, and H. traversii accumulate significant amounts of 3-O-glycosides of the flavonols kaempferol and/or quercetin. The production of either
UNIQUE COMPOUNDS: y and z are unique to H. albicans
within small-leaved "Occlusae" and within Hebe. NOTES ON VARIATION: There is no clear relationship between geographic origin of samples and flavonoid profile. Samples from the same location are generally no more similar to each other than to those from other locations. For example, variation among samples from Peel Range, Nelson (MJB 477, 478, 552, 1190, and 1191) represents a large proportion of flavonoid variation of the species. Also, samples from "Harwoods Lookout" (Takaka Hill), Nelson (MJB 1195 and 1196), are less similar to each other than to samples from other localities. DIFFERENCES f r o m c h e m i c a l l y s i m i l a r species: N o
flavonoid consistently distinguishes H. albicans from H. evenosa orH. traversii; individual samples are distinguished by their particular combination of flavonoids. Absence of 18d distinguishes H. albicans from H. topiaria. hebe brockiei GENERAL: H. brockiei (2 samples) has a flavonoid profile similar to H. decumbens, H. traversii, and H. treadwellii. SUMMARY OF FLAVONOIDS: Flavones present in both samples are 4,8c, 8a, 8b, 9, and 5a. Others present in MJB 1281 are 5b (trace), 6 (trace), 3d, 15h, 3, and 2 (trace).
New Zealand Journal of Botany, 2007, vol. 45
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MJB1353 MJB1357 MJB1364 MJB1386 PGJ2314
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00
Appendix 4 Presence/absence of flavonoids in samples of small-leaved "Occlusae". +, conspicuous presence; w, weak presence; tr, compounds evident by HPLC only, i.e., not visible as spots on paper chromatograms; ?, unconfirmed identity; L, luteolin; A, apigenin; K, kaempferol; Q, quercetin; Me/OMe, methyl/methoxy; OH, hydroxy. Compounds are grouped into aglycone classes, and number/letter codes follow those given in Markham et al. (2005, table 1). Apigenin glycosides
6OHA side
6OHA
60 MeA
8OHA
Luteolin glycosides
10 lc 12 17 22 22e 24
de
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18a
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4 13 15 14 12a 23 16a 26 lb 4a 16 16b 1 la 22a23a
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% % *
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60HA like
60HA
60 MeA
80HA
Luteolin glycosides
10 lc 12 17 22 22e 24
3e
5b 6
18a
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4 13 15 14 12a 23 16a 26 lb 4a 16 16b 1 la 22a23a
MJB 1327 MJB 1329 MJB 1330
+ + +
H. brockiei MJB 1281 MJB 1282 H. calcicola MJB 548 MJB 549 MJB 1180 MJB 1181 MJB 1186 MJB 1187 MJB 1188 MJB 1192 MJB 1193 MJB 1194
+ ?
?
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H. decumbens MJB 752 MJB 753 MJB 774 MJB 775
H. parviflora MJB 423 MJB 426
I
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+ +
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+ + +
+ +
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+ +
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w w?
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H. evenosa MJB 455 MJB 456 H. glaucophylla MJB 785 MJB 1279 MJB 1280
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60HA
20 MeA
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Samples
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3e
5b 6
18a
le 3b
MJB529 MJB530 MJB652 MJB653 MJB655 MJB654 MJB665 MJB883 MJB986 MJB987 MJB 1016 MJB 1017 PGJ2258 PGJ 2325
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+ +
+ + +
w
+
w
+
w
+
w
+
w tr ?
? ? ?
+ ? +? w tr tr
H. stenophylla var. hesperia PGJ 2344 PGJ 2350 PGJ 2352
4
13 15 14 12a 23 16a 26 lb 4a 16 16b 1 la 22a23a
+ + + + + + + + + + + + + +
w +
+ + + + + + + + + +
tr + w
H. stenophylla var. oliveri WELT 81504 WELT 81505 ?
+ +
H. stenophylla var. stenophylla MJB 645 MJB 647
w +
00
Luteolin glycosides
+ + + + + + + + + +
? ? + + + + + + +
+ + + + + + + +
+ + + + + +
+ w + + + +
+ + w? +? w w w w +? +
w?
+ + w
w w w w + w w
+
w
+
w
+ +
w w
+ +? +
2 % N
+
o ? ?
^ to o o $
+ +
+ +
w w
• & >
Samples
Apigenin glycosides
60HA like
60HA
60 MeA
80HA
Luteolin glycosides
10 lc 12 17 22 22e 24
3e
5b 6
18a
le 3b
4 13 15 14 12a 23 16a 26 lb 4a 16 16b 1 la 22a23a
MJB651 MJB687 MJB688 MJB689 MJB863 MJB864 MJB983 MJB 1033 MJB 1034 MJB 1040 MJB 1041 MJB 1174 PJBH8 PJBH9 H. strictissima MJB 998 MJB 999 MJB 1001 MJB 1008 H. subalpina MJB 576 MJB 577 MJB 610 MJB 777 MJB 779 MJB 786 MJB 946 MJB 949 MJB 1133 MJB 1139 MJB 1140 MJB 1266 MJB 1270 MJB 1283 MJB 1285 MJB 1336
tr
+ + w
w + + w
w w
w w
+ +
+ +
+ +
+ + + + + + + +
w w w w + w w + + + + + + +
+ + + + + + + + + + + + + +
+ + + + + + + + + + + + + +
+ + + +
tr + + w + + + + + + + ?
+ + + + + + + + + + +
w + + + + + + + + + + + + w
% r>
w w w
E.
I
w ?
I
w w
TO
a. § + + + +
+ + + w
+
+ +
+ + + +
+ + + +
+ +
+ w
+ w +
+ + w 00
Samples
Apigenin glycosides
60HA like
60HA
60 MeA
80HA
Luteolin glycosides
10 lc 12 17 22 22e 24
3e
5b 6
18a
le 3b
4 13 15 14 12a 23 16a 26 lb 4a 16 16b 1 la 22a23a
MJB1482 MJB1564
+
+ +
? +
+
H. topiaria MJB465 MJB468 MJB494 MJB554 MJB819 MJB820 MJB1466
tr + tr +?
+ +
+
tr + + +
tr tr tr tr + +
tr + + + + +
w w + w +
+ + tr
+ +
tr tr
tr
+
+ + + w
tr + + + tr +
2
%
H. treadwellii MJB951 MJB952 MJB1212 WELT 82632
H. urvilleana MJB1250 MJB1253 MJB1255
+ +
+ ? + ? + tr + ? + ? + + + +
H. traversii MJB837 MJB838 MJB995 MJB996 MJB1010 MJB1012 MJB1263
H. truncatula MJB525 MJB526
+ +
00
+ +
+ + +
N
+ tr + + +
+ + + +
w
+ +
+ +
+ +
+
w
w
+ +
a o
+ + +
+ ? ?
+ + +
to
o
Mitchell et al.—Flavonoids in Hebe and Leonohebe 2
387
Unidentified flavonoids Q-7-O-glucuronide-3-O-glucoside Q-3-O-[6-O-rhamnoglucoside]
+ + + + + + + + + + + + + + + + + + + +
Q-3-O-xyloside
a
Q-3-O-glucoside O
o
2z
CN CM
&
O
00
t3 ^O
8Ohl-7-O-[6-O-rhamnoglucoside]
CN
8Ohl-8-O-glucoside
e«
8Ohl-7-O-glucoside
en ^H
6OMel-7-O-[6-O-xyloglucoside]
t3
en
6OMe-l-7-O-glucuronide
en
6OMel-7-O-glucoside
15h
CN ^H
>n
4 Me6OHL-7-O-[rhamnodixyloside]?
2
+ + + + + + + + + + + + + + + + + + + +
%
&
+ +
£ + c--+ ^ + + + + + ^ ^+ + + + + £ + + +
+ +
+ + + +
+ + + + +
£+ + + + + + + +
'$•++'$•
+ + + + + + + + + + + + + + +
6Ohl-7-O-[6-O-xyloglucoside] 6Ohl-7-O-[2-O-glucoglucoside]
00
e« 00
6Ohl-7-O-[2-O-xyloglucoside]
6Ohl-7-O-[2-O-rhamnoglucoside] ?
"O O\
6Ohl-7-O-triglycoside?
o ea
V ^^ t3
"O
en
+ + + + + + + + + + + + + + + + + + + +
6Ohl-7-O-[2-O-xyloxyloside]
o V
00
s
+
4 Me6OHL-7-O-[2-O-xyloglucoside] O\
2
+
U &
6Ohl-7-O-glucoside
UUUUU££UUUU£UU£!£!£!
4 MeL-7-O-[6-O-xyloglucoside] 4 MeL-7-O-[6-O-rhamnoglucoside] 4 MeL-7-O-glucoside
85 A
OrHin^^oi^o^om^^oi^^o ^^
^^
ass:
W~i W~i V°i
V") ^H
^H
^H
^H
^H
^H
^H
^H
^H
^H
^H
^H
^H
^H
4TVIeL Samples
4'Me 6OHL
6OHL
3d 14a 15a
8c 9d 15c 8a 8b
+
w w
8OHL
K-glycs
Q-glycs
5a
2
21 20
18 18d 19 25
+
+ +
tr
+
+ +
+ + + + + + + + + +
+ + + +
w w w w
9
9a
9b 15h
6OMeL 3
3a 13a
6a 12b
00 00
H. brockiei
MJB1281 MJB1282
+ +
+ +
? ?
? ?
+ +
+
H. calcicola + + + + + + + + + +
MJB548 MJB549 MJB1180 MJB1181 MJB1186 MJB1187 MJB1188 MJB1192 MJB1193 MJB1194
+ + +
+ + + + + + + + + +
? + + + + ? +
H. decumbens
MJB752 MJB753 MJB774 MJB775
+ + + +
tr
+ + + +
w
N H. evenosa
MJB455 MJB456
+
+
+ +
w?
+ +
tr
+ +
+ +
w
+ +
+ +
a
o1
1
H. glaucophylla
H. parviflora MJB 423 MJB 426 MJB 529 MJB 530 MJB 652
+ + +
+?
+ w +
w w
+ + +
w + +
+?
w
+
+
w + +
w + w
w
o 1
«}
B01
MJB785 MJB1279 MJB 1280
B + +
+ + +
to
o o
4'MeL Samples
3d 14a 15a
8c 9d 15c 8a 8b
9
+ w w w w +?
MJB653 MJB655 MJB654 MJB665 MJB883 MJB986 MJB987 MJB 1016 MJB1017 PGJ2258 PGJ2325 H. rakaiensis MJB 611 MJB 612 MJB 797 MJB 938 MJB 941 MJB 1120 MJB 1121 MJB 1128 MJB 1277 MJB 1278
4TV[e 6OHL
6OHL 9a
9b 15h
6OMeL 3
3a 13a
+ w w +
+
K-glycs
Q-glycs
2
21 20
18 18d 19 25
+ + + + + +
+ + + + + w +
+ + + +
w w +
+
8OHL 5a
6a 12b
I a &
w w
+ + +
+
+
+
h
+ + + +
3
§-
+
B. tr tr
H. stenophylla var. hesperia PGJ2344 PGJ2350 PGJ2352 H. stenophylla var. oliveri WELT 81504 WELT 81505 H. stenophylla var. stenophylla MJB 645 MJB 647 MJB 651
? ?
+ + +
+ + +
+ + +
+ + + ? ? + + +
w + + + + +
w + + + +
w + + + + +
w w +
+ + +
+ + +
+ + +
w w
+ + +
+ +
+ +
+ +
+ +
+ +
+ +
+ +
+ + +
+ + +
+ + +
+ + +
+ + +
+ + +
+ tr +? w? +?
w
w
+ + + + + + + + + +
+ + + + + +
+ + + + + + + + + +
+
m 1 1
TO
©
§ TO
8to" ? ?
w +
00
4TV[eL
Samples
3d 14a 15a
MJB687 MJB688 MJB689 MJB863 MJB864 MJB983 MJB1033 MJB 1034 MJB 1040 MJB 1041 MJB 1174 PJBH8 PJBH9
?
8c 9d 15c 8a 8b
9
+ + + + + + + + + + + + +
+ + + + + + + + + + + + +
+ + + + + + + + + + + + +
H. strictissima MJB 998 MJB 999 MJB 1001 MJB 1008 H. subalpina MJB 576 MJB 577 MJB 610 MJB 777 MJB 779 MJB 786 MJB 946 MJB 949 MJB 1133 MJB 1139 MJB 1140 MJB 1266 MJB 1270 MJB 1283 MJB 1285 MJB 1336
4TV[e 6OHL
6OHL
+ + + + + + + + + + + + +
+
+
? + + + + + + +
+ w + +
+ + + + + + + + + + + + + + + +
+ + + + + + + + + + + + + + + +
9b 15h
3
+ + ? +
+ + + +
+? w w +
+ + + + + + + +
9a
*•©
6OMeL
5a
2
21
+ + + + + + + + + + + + +
w w w + + + + + +
6a 12b
20
Q-glycs
+ +
w
+
w
?
+ + + w
+
!
+ + w + + + + + + + + + + + +
o
18 18d 19 25
+ w w
tr
+
+
K-glycs
+
+ + + + + + + + + + + + + + +
3a 13a
8OHL
N
8
o1 ?
E. o
+
o + + + +
o o
¥
"oo
6 O-
OO
O-
9 CTQ
o
9 CTQ
o
6 O-
F 9
|
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