NATURAL TOXINS 5:58–63 (1997)
Phlorotannins From the Brown
Algae Cystophora torulosa
and Sargassum spinuligerum
Karl-Werner Glombitza*, Sabine Hauperich, and Michael Keusgen
Institut für Pharmazeutische Biologie, Universität Bonn, Bonn, Germany
ABSTRACT Phlorotannins often have various toxic effects against a large number of organisms. From the
ethyl acetate fraction of the ethanolic extract of the brown alga Cystophora torulosa 33 phlorotannins were
obtained. Twenty of them are described in this report: phlorethols and fuhalols, and fucophlorethols and
hydroxyfucophlorethols. Seven of them were isolated for the first time. New phlorotannins bearing additional
hydroxy groups belong to the hydroxyfucophlorethols. NMR- and MS-data were used for structural
elucidation. Several of the substances described for C. torulosa occur in Sargassum spinuligerum as well. Nat.
Toxins 5:58–63, 1997. r 1997 Wiley-Liss, Inc.
Key Words: Cystophora torulosa; Sargassum spinuligerum; phaeophyceae; phlorotannins; phlorethols;
fuhalols; fucophlorethols; hydroxyfucophlorethols; structural elucidation
INTRODUCTION EXPERIMENTAL METHODS
Plant Materials
Phlorotannins are polymers occurring in many brown
Cystophora torulosa (R. Brown) I. Ag., collected at
algae; they all contain phloroglucinol as their monomeric
Whangaparoa, New Zealand, and Sargasssum spinuligerum
component. They are toxic to a variety of marine animals:
Sonder from Auckland harbour, New Zealand, were frozen
hydroids, various worms, pycnogonids, and copepods, as
as soon as possible and transported frozen to Germany.
well as larvae. They inhibit fertilization in echinoderms, Voucher specimens are deposited at the herbarium of the
settlement, and metamorphosis [Ragan and Glombitza, University of Auckland.
1986]. Phlorotannins containing extracts are toxic to mice
[Fusetani and Hashimoto, 1982]. They inhibit numerous Mass spectra
enzymes such as a-amylase, lipase, and trypsin [Barwell et Low resolution EIMS data were collected on a Kratos,
al., 1989], and some are effective antiplasmin inhibitors Manchester MS 50 spectrometer, ion source 200–300°C,
[Fukuyama et al., 1990]. The brown alga Cystophora ionization energy 70 eV; FABMS data were collected on a
torulosa contains such phenolic compounds. It is a typical Kratos concept 1 with Xe gun and a matrix of 3-nitro-
representative of Australasian algae. It grows on the rocky benzylalcohol in the positive mode.
coasts of New Zealand in the littoral and upper part of the 1H-NMR (300 MHz) and 13C NMR (75 MHz)
sublittoral [Lindauer et al., 1961]. Twenty of the 33 isolated
NMR data were collected on a Varian XL-300 (Bremen,
representatives of this class of substances from C. torulosa
Germany) using solvents as internal standards. The H NMR
are described in this report. They belong to different groups
spectra were recorded both in CDCl3 and d6-Me2CO; the 13C
of phlorotannins which differ from each other in the linkage
NMR spectra in CDCl3. For some signals, the chemical
of their individual phloroglucinol units. Whereas phlorethols shifts were estimated to the approximated third decimal
and fuhalols are only connected by phenylether bridges, the place. This is to distinguish between signals of very close
fucophlorethols have biaryl linkages as well. In every value but which could nevertheless be clearly differentiated
fucophlorethol mentioned in this article, the biaryl element by visual inspection of the spectra.
is substituted by a single phloroglucinol element or a chain
of phloroglucinol elements, with an ether bridge only on one
Contract grant sponsor: Ministerium für Wissenschaft und Forschung,
of the biphenyl elements. Nordrhein-Westfalen, Germany.
Because the free phlorotannins are sensitive against *Correspondence to: Karl-Werner Glombitza, Institut für Pharmazeuti-
oxidation, and in order to increase their lipophilic properties, sche Biologie, Universität Bonn, Nußallee 6, 53115 Bonn, Germany.
they were isolated as acetates. Received 30 August 1996; Accepted 23 December 1996
r 1997 Wiley-Liss, Inc.
PHLOROTANNINS FROM C. TORULOSA AND S. SPINULIGERUM 59
Fig. 1. Compounds 2–12. Letters in rings are only valid for largest respective compounds. R 5 OAc.
Extraction and Isolation Diphlorethol pentaacetate (2); 5 mg, identical with Koch
Deep-frozen and crushed algae (9 kg) were extracted and Gregson [1984].
according to the published procedure [Glombitza et al., Triphlorethol-A- heptaacetate (3); 3 mg, identical with
1978]. The free phenols obtained were acetylated with Koch and Gregson [1984].
acetanhydride/pyridine for 12 hr. The high molecular mass Trifuhalol-A octaacetate (4); 3 mg, identical with Glom-
phlorotannin acetates dissolved in CHCl3 were precipitated bitza and Sattler [1973].
by a mixture of petrol/ether, boiling point (bp) 40–60°C Tetrafuhalol-A undecaacetate (5); 3 mg, identical with
(50 1 50). Yield of low molecular mass phlorotannin ac- Glombitza et al. [1982].
etates was 6 g. In 0.5-g quantities, they were preseparated Pentafuhalol-A tridecaacetate (6); 4 mg, identical with
using a low-pressure silica gel column with a stepwise Glombitza et al. [1982].
gradient of 200 ml CHCl3/n-hexane (50 1 50), 150 ml Hexafuhalol-A hexadecaacetate (7); 2 mg, identical with
CHCl3, 100 ml CHCl3/Me2CO (80 1 20), 100 ml CHCl3/ Glombitza et al. [1982].
MeCO (50 1 50), and 200 ml CHCl3/MeOH (80 1 20). Fucophlorethol-B octaacetate (8); 3 mg, identical with
Fine separation was performed using high performance Wegner-Hambloch, [1983].
liquid chromatography (HPLC) [pump: Knauer (Berlin, Fucodiphlorethol-D decaacetate (9); 5 mg, identical with
Germany) Fr-30 and 64; gradient programmer: Knauer 50; Glombitza et al. [1981].
detector: photodiodes-array-UV/Vis-detector, SPDM6 Shi- Fucotriphlorethol-B dodecaacetate (10); 3 mg, identical
madzu (Düsseldorf, Germany) at 270/250 nm; column: with Keusgen and Glombitza [1995].
250 3 8 mm LiChrosorb Si 60 Merck, (Darmstadt, Ger- Fucophlorethol-C octaacetate (11); 2 mg, identical with
many) 5 µm] with CHCl3/EtOH, CHCl3/EtOH/n-hexane, Glombitza and Große-Damhues [1985].
and CHCl3/EtOH/MeCN mixtures. Fucodiphlorethol-E decaacetate (12); 1 mg, identical with
Craigie et al. [1977].
Isolated Compounds Hydroxyfucophlorethol-A nonaacetate (13): 2,4,6,28,48,68-
Yields correspond to 18 kg frozen algae. hexaacetoxy-3-(3,4,5-triacetoxyphenoxy)-biphenyl; 4 mg,
Phloroglucinol triacetate (1); 6 mg, identical with Ragan EI-MS ketene elimination series: m/z 768 = 390,
and Glombitza [1986]. 666 = 372, 434 = 266, and 334 = 250.
60 GLOMBITZA ET AL.
Fig. 2. Compounds 13–20. Letters in rings are only valid for largest respective compound. R 5 OAc.
Hydroxyfucodiphlorethol-A undecaacetate (14); 4 mg, TABLE I. 13C-NMR Spectral Data of Compounds 13, 14, and 19*
identical with Glombitza and Li [1991].
Hydroxyfucotriphlorethol-A tridecaacetate (15): 2,6,38,58- Chemical shift
tetraacetoxy-28-(3,4,5-triacetoxyphenoxy-4-(2,4,6,28,48,68- Measured
Calculated
hexaacetoxybiphenylyl-3-oxy)-diphenylether; 1 mg, EI-MS- Ring type C-No. 13 14 19 [14]
ketene elimination series: m/z 1142 = 638, 1082 = 914,
918 = 498, 934 = 514, 710 = 374, 726 = 390, 502 = 250, Ring F C-4 150.7 150.7 150.7
C-2,6 149.2 149.1 149.2
and 518 = 266; FAB-MS: m/z [M 1 K]1 1224, [M 1 Na]1
C-1 114.9 114.9 114.9
1207; ketene elimination series: m/z 1185 = 639. C-3,5 113.8 113.8 113.8
Hydroxyfucotetraphlorethol-A pentadecaacetate (16): 3,5- Ring G C-6 145.0 145.2 145.1 144.2
diacetoxy-1-[2,6-diacetoxy-4-(2,4,6,28,48,68-hexaacetoxybi- C-2 143.0 143.1 143.2 142.9
phenylyl-3-oxy) [phenoxy]-2-[3,5-diacetoxy-4-(3,4,5-triac- C-4 142.7 (2) 142.8 141.6
etoxyphenoxy)-phenoxy]benzene; 1 mg, EI-MS-ketene C-3 137.0 (2) 137.0 137.8
elimination series: m/z 1056 = 762, 1122 = 870, C-1 118.2 (2) 118.2 116.5
1126 = 622, 1142 = 638, 918 = 498, 934 = 514, C-5 116.1 116.1 116.2 114.8
710 = 374, 726 = 390, 502 = 250, and 518 = 266; FAB- C1/C2
MS: m/z [M 1 K]1 1431, [M 1 Na]1 1415; ketene elimina- Ring C C-1 153.4 153.4/154.1 153.1
tion series: m/z 1393 = 805. C-3,5 143.7 143.7 140.0
C-4 (2) 134.3 (7)/134.4 (4) 134.7
Hydroxyfucopentaphlorethol-A heptadecaacetate (17):
C-2,6 109.8 109.5 108.3
4,6,38,58-tetraacetoxy-2-[2,6-diacetoxy-4-(2,4,6,28,48,68- Ring E C-1 147.7 147.5
hexaacetoxybiphenylyl-3-oxy)phenoxy]-48-[3,5-diacetoxy- C-5 140.1 139.2
2-(3,4,5- triacetoxyphenoxy)phenoxy]diphenylether; ,1 mg, C-3 136.9 136.6
FAB-MS: m/z, [M 1 K]1 1639, [M 1 Na]1 1623; ketene C-2 134.7 134.4
elimination series: m/z 1601 = 1307. C-4 131.4 131.2
Dihydroxyfucotriphlorethol-A tetradecaacetate (18): C-6 109.6 109.0
2,6,38,48,58-pentaacetoxy-28-(3,4,5-triacetoxyphenoxy)-4- Ring D C-1 154.2 154.2 154.6 155.2
(2,4,6,28,48,68- hexaacetoxybiphenylyl-3-oxy)-diphenylether; C-3,5 143.7 143.7 143.9 144.3
3 mg, EI-MS-ketene elimination series: m/z 1158 = 654, C-4 130.4 130.3 130.2 130.2
1198 = 720, 892 = 514, 950 = 530, 626 = 374, C-2,6 109.2 109.0 109.0 108.0
684 = 390, 376 = 250, and 476 = 266; FAB-MS: m/z *Three hundred MHz, d in ppm, in CDCl 3 . (2), signal not detectable, not
[M 1 K]1 1281, [M 1 Na]1 1265; ketene elimination se- enough substance.
ries: m/z 1243 = 949.
Dihydroxyfucotetraphlorethol-A hexadecaacetate (19): ketene elimination series: m/z 862 = 778, 932 = 638,
3,4,5-triacetoxy-1-[2,6-diacetoxy-4-(2,4,6,28,48,68-hexa- 864 = 654, 934 = 514, 656 = 530, 626 = 374, 684 = 390,
acetoxybiphenylyl- 3-oxy)phenoxy]-2-[3,5-diacetoxy-4- 418 = 250, and 434 = 266; FAB-MS: m/z [M 1 K]1 (1489),
(3,4,5-triacetoxyphenoxy)phenoxy]benzene; 6 mg, EI-MS- [M 1 Na]1 1473; ketene elimination series: m/z 1451 = 905.
PHLOROTANNINS FROM C. TORULOSA AND S. SPINULIGERUM 61
TABLE II. Correlation of 1HNMR Data of Compounds 13 and 15–17*
Chemical shift measured
13 15 16 17
Ring type (CDCl3 /d6-Me2CO) (CDCl3 /d6-Me2CO) (CDCl3 /d6-Me2CO) (CDCl3 /d6-Me2CO)
Ring F
C-3,5 7.002/7.039 6.999/7.043 6.999/7.043 7.001/7.043
C-4 (Ac) 2.294/2.281 2.294/2.283 2.295/2.284 2.298/2.284
C-2.6 (Ac) 2.056/2.001 2.048/2.002 2.073/2.007 2.048/2.008
Ring G
C-5 7.111/7.221 7.113/7.235 7.105/7.233 7.110/7.236
C-6 (Ac) 2.068/2.083 2.120/2.125 2.117/2.140 2.111/2.125
C-4 (Ac) 2.023/1.978 2.021/1.979 2.025/1.982 2.025/1.982
C-2 (Ac) 1.905/1.838 1.912/1.847 1.912/1.848 1.912/1.849
Ring C1
C-2,6 6.673/6.750 6.672/6.785 6.674/6.772
C-3,5 (Ac) 2.014/2.036 2.038/2.064 2.007/2.078
Ring C2
C-2,6 6.679/6.785 6.652/6.741
C-3,5 (Ac) 2.049/2.052 2.021/2.060
Ring H1
C-4 6.743/6.865d 6.743/6.872d 6.728/6.848d
C-6 6.500/6.481d 6.475/6.453d 6.475/6.477d
C-5 (Ac) 2.226/2.209d 2.229/2.211d 2.207/2.187d
C-3 (Ac) 2.152/2.138d 2.195/2.166d 2.159/2.139d
Ring H2
C-4 6.736/6.870d
C-6 6.531/6.532d
C-5 (Ac) 2.224/2.208d
C-3 (Ac) 2.186/2.157d
Ring D
C-2,6 6.722/6.760 6.692/6.780 6.698/6.728 6.691/6.785
C-4 (Ac) 2.258/2.256 2.251/2.250 2.255/2.250 2.250/2.248
C-3,5 (Ac) 2.240/2.238 2.240/2.230 2.229/2.218 2.239/2.229
*Three hundred MHz, d in ppm. d, coupling constant J 5 2.9/2.7 Hz. Last decimal place shows only a tendency.
Trihydroxyfucopentaphlorethol-A nonadecaacetate (20): rated using a low-pressure silica gel column. Final separa-
4,5,6,38,58-pentaacetoxy-2-[2,6-diacetoxy-4-(2,4,6,28,48,68- tion was carried out by high performance liquid chromatog-
hexaacetoxybiphenylyl-3-oxy)phenoxy]-48-[3,5-diacetoxy- raphy (HPLC) on silica gel 60 columns using chloroform/
2-(3,4,5- triacetoxyphenoxy)phenoxy]diphenylether; 2 mg, ethanol or chloroform/ethanol/n-hexane or chloroform/
FAB-MS: m/z [M 1 K]1 1755, [M 1 Na]1 1739; ketene ethanol/methyl cyanide mixtures. The structures were
elimination series: m/z 1717 = 1255. elucidated using nuclear magnetic resonance (NMR) and
mass spectrometry (MS).
RESULTS AND DISCUSSION The following 13 compounds already isolated from other
The native phlorotannins were extracted from the deep- algae were isolated from C. torulosa, and their structures
frozen and crushed algae using ethanol (end concentration were elucidated by comparison spectra: phloroglucinol
50–60%). To remove interfering lipophilic accompanying triacetate (1) [Ragan and Glombitza, 1986]; phlorethols
substances, the residue obtained after gentle evaporation (Fig. 1): diphlorethol pentaacetate (2) [Koch and Gregson,
was extracted with petrol and chloroform. Subsequently, the 1984], triphlorethol-A heptaacetate (3) [Koch and Gregson,
phenols were transferred to ethyl acetate. After removal of 1984] (for phlorethols from Sargassum spinuligerum see
the solvent, the phenols were acetylated immediately with a Keusgen and Glombitza [1995]); fuhalols (Fig. 1): trifuha-
mixture of acetic anhydride and pyridine. With an ether/ lol-A octaacetate (4) [Glombitza and Sattler, 1973], tetrafu-
petrol mixture, the high molecular mass phlorotannin acetate halol-A undecaacetate (5) [Glombitza et al., 1982], pentafu-
fraction was separated from that of the low molecular mass halol-A tridecaacetate (6) [Glombitza et al., 1982],
fraction by precipitation from CHCl3 solution. The low hexafuhalol-A hexadecaacetate (7) [Glombitza et al., 1982]
molecular mass phlorotannin acetates were partially sepa- (for fuhalols from S. spinuligerum see Keusgen and Glom-
62 GLOMBITZA ET AL.
bitza [1995] and Glombitza and Keusgen [1995]); fucophlor- TABLE III. Correlation of 1HNMR-data of Compounds 18–20*
ethols: fucophlorethol-B octaacetate (8) [Wiedenfeld, 1977],
fucodiphlorethol-D decaacetate (9) [Glombitza et al., 1981], Chemical shift measured
fucotriphlorethol-B dodecaacetate (10) [Glombitza and Keus- 18 19 20
gen, 1995], fucophlorethol-C octaacetate (11) [Glombitza (CDCl3 / (CDCl3 / (CDCl3 /
Ring type d6-Me2CO) d6-Me2CO) d6-Me2CO)
and Große-Damhues, 1985], fucodiphlorethol-E decaacetate
(12) [Craigie et al., 1977], and hydroxyfucodiphlorethol-A Ring F
(14) undecaacetate [Glombitza and Li, 1991] (Figs. 1 and 2) C-3.5 6.999/7.040 7.000/7.041 6.998/7.042
(for fucophlorethols from S. spinuligerum see also Keusgen C-4 (Ac) 2.295/2.281 2.290/2.283 2.296/2.282
et al. [1997]). C-2.6 (Ac) 2.047/2.001 2.060/2.002 2.041/2.001
Ring G
Substance 14 is a fucophlorethol with an additional
C-5 7.110/7.230 7.108/7.230 7.106/7.228
acetoxy group. Hitherto it was the only hydroxyfucophlor-
C-6 (Ac) 2.118/2.130 2.105/2.132 2.100/2.128
ethol isolated, and it was found first in Carpophyllum C-4 (Ac) 2.020/1.980 2.020/1.982 2.025/1.980
maschalocarpum [Glombitza and Li, 1991]. In this paper we C-2 (Ac) 1.906/1.842 1.905/1.840 1.903/1.838
report on the isolation of this substance from both C. Ring C1
torulosa and S. spinuligerum. C-2,6 6.662/6.766 6.661/6.732 6.658/6.769
This paper describes further representatives of this phloro- C-3,5 (Ac) 2.030/# 2.040/# 2.025/#
tannin group isolated from C. torulosa or from S. spinu- Ring C2
ligerum (substances 13 and 18) at the same time. (Fig. 2). C-2,6 6.701/6.775 6.679/6.756
This group is characterized by a 2,4,6,28,48,68-hexaacetoxy- C-3,5 (Ac) 2.050/# 2.025/#
Ring E1
biphenyl on one end of the molecule (ring F–G), which is
C-6 6.658/6.650 6.625/6.642 6.619/6.638
linked at C-3 by ether bridges with additional phloroglucinol
C-4 (Ac) 2.250/2.248 2.255/2.250 2.244/2.245
units. Each terminal phloroglucinol element is substituted by C-5 (Ac) 2.220/2.221 2.215/2.200 2.215/2.218
an additional acetoxy group, resulting in a 3,4,5-triacetoxy- C-3 (Ac) 2.167/2.158 2.210/2.221 2.195/2.187
phenoxyl (ring D). The smallest compound isolated was Ring E2
hydroxyfucophlorethol-A nonaacetate (substance 13). The C-6 6.698/6.698
electron-impact mass spectrum (EI-MS) shows an µ1 at C-4 (Ac) 2.256/2.258
mass per charge (m/z) 768. From this, nine ketenes split off C-5 (Ac) 2.200/2.187
which are derived from the acetoxy groups. The simulta- C-3 (Ac) 2.171/2.161
neous appearance of a ketene elimination series from m/z Ring D
C-2,6 6.719/6.771 6.710/6.805 6.719/6.782
666–372 is traced back to the formation of a furanoid ring
C-4 (Ac) 2.255/2.263 2.260/2.271 2.258/2.267
between ring F and ring G and is typical for two phloroglu-
C-3,5 (Ac) 2.241/2.235 2.225/2.218 2.239/2.233
cinols linked by a biaryl bond (the next higher homologue is
substance 14). *Three hundred MHz, d in ppm. (#), signal hidden by solvent. Last decimal
place shows only a tendency.
The higher homologues have either only one additional
acetoxy group on the last phloroglucinol ring (substances
15–17), or they have additional acetoxy groups on the rings AB2-system of ring B at 6.66–6.64 ppm and 6.58–6.54 ppm
labelled E1 and E2 (substances 18–20). disappears and is replaced by a singlet for 2 H in the range of
The molecular ions in fast atom bombardement mass 6.72–6.69. Simultaneously, a singlet appears at 2.26–2.25
spectrometry (FAB-MS) (1184, 1392, and 1600) of sub- ppm for 3 H for the additional acetoxy group. The AB-
stances 15–17 are at the beginning of a ketene elimination system of ring type H at 6.77–6.74 ppm and 6.55–6.49 ppm
series, in which each ends after loss of 13, 15, or 17 ketenes present in substances 16 and 17 disappears in substances
at the ions of the free five-, six-, or seven-ringed homo- 18–20. Instead, a singlet for 1 H at 6.70–6.62 ppm appears,
logues. along with a singlet for 3 H at 2.26–2.24 ppm forming the
The masses determined for substances 18 and 19 are 58 rings E1 and E2.
atomic mass units (a.m.u.) higher than those of substances To determine the exact position of ring elements of type C
15 and 16 because they possess an additional acetoxy group. within the molecule, the resonances of the aromatic protons
Compound 20 exhibits 116 a.m.u. more than substance 17 from substances 13–17 were graphically brought into corre-
because the ring E occurs twice (instead of H in substance lation with those of substances 8–10 and of fucotetraphlor-
17). Accordingly, the ketene elimination series could be ethol-A-tetradecaacetate (six-ringed) as well as of fucopen-
identified with 14, 16, and 19 elements. EIMS indicates a taphlorethol-A-hexadecaacetate (seven-ringed) [Wegner-
furanoid ring formation between ring F and G. Hambloch, 1983] by fixing the signal of the aromatic
The 1H-NMR-spectra of compounds 13–20 (Tables I and protons of ring F, usually found between 7.00–6.98 ppm, to
II) show great similarity with those of the fucophlorethols exactly 6.98 ppm and relating all other signals to this.
8–10. Due to the additional acetoxy group on ring D, the Substances 18–20 and their comparison spectra 4–7 were
PHLOROTANNINS FROM C. TORULOSA AND S. SPINULIGERUM 63
treated analogously. The graphic representation shows the Glombitza K-W, Große-Damhues J (1985): Antibiotics from algae. XXXIII:
close relationship of substances 8–10 with 13–17 on one Phlorotannins of the brown alga Himanthalia elongata. Planta Med
50:42–46.
side, and of substances 4–7 with 14 and 18–20 on the other
Glombitza K-W, Keusgen M (1995): Fuhalols and deshydroxyfuhalols
(diagrams may be requested from the authors). from the brown alga Sargassum spinuligerum. Phytochemistry 38:987–
Sufficient quantities of substances 13, 14, and 19 could be 995.
isolated to obtain 13C-NMR spectra (Table III). A compari- Glombitza K-W, Li S-M (1991): Fucophlorethols from the brown alga
son of the measured chemical shifts displayed good confor- Carpophyllum maschalocarpum. Phytochemistry 30:3423–3427.
mity with the values calculated by Wegner-Hambloch and Glombitza K-W, Sattler E (1973): Trifuhalol, ein neuer Triphenylether aus
Halidrys siliquosa. Tetrahedron 14:4277–4280.
Glombitza [1985].
Glombitza K-W, Wiedenfeld G, Eckhardt G (1978): Antibiotica aus Algen,
ACKNOWLEDGMENTS XX. Niedermolekulare Phlorotannine aus Cystoseira baccata. Arch
Pharm (Weinheim) 311:393–399.
We thank Dr. F. I. Dromgoole (University of Auckland) Glombitza K-W, Schnabel C, Koch M (1981): Antibiotica aus Algen. 27.
for introducing us to the New Zealand algae and their Mitt. Niedermolekulare Phlorotannine der Braunalge Cystoseira baccata
identification, the Central Analytical Department of the Teil II. Arch Pharm (Weinheim) 314:602–608.
Glombitza K-W, Forster M, Farnham WF (1982): Antibiotics from algae—
Institute of Chemistry and the NMR Department of the
Part 25. Polyhydroxyphenyl ethers from the brown alga Sargassum
Pharmaceutical Institute, University of Bonn, for mass and muticum (Yendo) Fensholt part II. Bot Mar 25:449–453.
NMR spectra, and Mrs. R. Lodder for translating the Keusgen M, Glombitza K-W (1995): Phlorethols, fuhalols and their
manuscript. This research was supported by the Ministerium derivatives from the brown alga Sargassum spinuligerum. Phytochemis-
für Wissenschaft und Forschung, NW. try 38:975–985.
Keusgen M, Glombitza K-W (1997) submitted.
REFERENCES Koch M, Gregson RP (1984): Brominated phlorethols and non-halogenated
phlorotannins from the brown alga Cystophora congesta. Phytochemis-
Barwell CJ, Blunden G, Manandhar PD (1989): Isolation and characteriza-
tion of brown algal polyphenols as inhibitors of a-amylase, lipase and try 23:2633–2637.
trypsin. J Appl Phycol 1:319–323. Lindauer VW, Chapmann VJ, Aiken M (1961): In: ‘‘The Marine Algae of
Craigie JT, McInnes AG, Ragan MA, Walter JA (1977): Chemical New Zealand, II. Phaeophyceae’’. Nova Hedwigia III, Weinheim: J.
constituents of the physodes of brown algae. Characterization by 1H and Cramer 2:298–299.
13C nuclear magnetic resonance spectroscopy of oligomers of phloroglu- Ogino C, Taki Y (1957): Studies on the tannins of brown algae; Sargassum
cinol from Fucus versiculosus (L.). Can J Chem 55:1575–1582. ringgoldianum Harv. J Tokyo Univ Fish 43:1–5.
Fukuyama Y, Kodama M, Miura I, Kinzyo Z, Mori H, Nakayama Y, Ragan MA, Glombitza K-W (1986): Phlorotannins, brown algal polyphe-
Takahashi M (1990): Anti-plasmin inhibitors VI. Structure of phlorofuco- nols. Prog Phycol Res 4:129–241.
furoeckol A, a novel phlorotannin with both dibenzo-1,4-dioxin and Wegner-Hambloch S (1983): Polyphenole aus der Phaeophycee Cystoseira
dibenzofuran elements, from Ecklonia kurome Okamura. Chem Pharm granulata sowie Untersuchungen über das Flavonoidvorkommen in
Bull 38:133–13. Chara contraria und Nitella flexilis. Dissertation, Universität Bonn.
Fusetani N, Hashimoto K (1981): Isolation of a tannin-like substance lethal Wegner-Hambloch S, Glombitza K-W (1985): Increments for calculation of
to mice from the marine brown alga Analipus japonicus. Bull Jpn Soc Sci the 13C NMR shifts of acetylated polyphenols considering steric interac-
Fish 47:293–294. tions. Magn Reson Chem 23:358–360.
