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Introduction
Geosmin, a sesquiterpene tertiary alcohol that
has lost an isopropyl group, is a major threat
of water industry worldwide. Its extremely low
threshold odour concentration of 15 ng/l (= 82 pM)
(Persson, 1980) and the ease to recognize the
muddy earthy odour are the primary causes of
consumer complaints against drinking water (Bru-
chet, 1999). Producers of geosmin in the source
water are planktonic and benthic cyanobacteria
and in the distribution pipes microorganisms of
unknown taxonomic position. In all so far investi-
gated geosmin-producing cyanobacteria, geosmin
was the major sesquiterpene accompanied by an
array of sesquiterpene hydrocarbons and alcohols.
But very few of these sesquiterpenes which may
also contribute to the musty odour bouquet of
cyanobacteria have been identified. Germacrene
D and Ȗ-cadinene were found as minor compo-
nents among nine unidentified sesquiterpenes in
Oscillatoria splendida (Tsuchiya et al., 1981). In
addition, several mass spectra were published,
but could not be attributed to any of the known
sesquiterpenes (Tsuchiya and Matsumoto, 1988).
The structure determination from mass spectro-
metric signals is unreliable because the epimers
described for higher plants must not also be typi-
cal products of lower plants. In general epimers
show only minor differences in their EI mass spec-
tra, and reference compounds that would allow
identification by retention time analysis are not
available. This is the reason why the structure elu-
cidation of sesquiterpenes is severely hampered.
The isolation of cyanobacterial biomass to ob-
tain sufficient material for NMR studies is rather
time-consuming, and essential oils in measurable
quantities have not yet been obtained for any of
these geosmin-producing cyanobacteria. Here we
describe sesquiterpenes of Calothrix which have
not yet been described for cyanobacteria. Since
the biogenesis of sesquiterpenes may be similar
in actinomycetes, these data will also be a contri-
bution to the knowledge of sesquiterpenes in this
group of microorganisms.
Sesquiterpenes of the Geosmin-Producing Cyanobacterium
Calothrix PCC 7507 and their Toxicity to Invertebrates
Claudia Höckelmann
a
, Paul G. Becher
a,b
, Stephan H. von Reuß
c
,
and Friedrich Jüttner
a,
*
a
Limnological Station, Institute of Plant Biology, University of Zürich, Seestrasse 187,
CH-8802 Kilchberg, Switzerland. E-mail: juttner@limnol.uzh.ch
b
Present address: Chemical Ecology Group, Swedish University of Agricultural Sciences
(SLU), Box 102, 23053 Alnarp, Sweden
c
University of Hamburg, Institute of Organic Chemistry, Martin-Luther-King-Platz 6,
D-20146 Hamburg, Germany
* Author for correspondence and reprint requests
Z. Naturforsch. 64 c, 49 – 55 (2009); received July 29/October 5, 2008
The occurrence of sesquiterpenes was investigated with the geosmin-producing cyanobac-
terium Calothrix PCC 7507. The essential oil obtained by vacuum destillation was studied in
more detail by GC-MS methods and superposition with authentic compounds. Geosmin was
the dominating compound while the other sesquiterpenes were minor components. Sesqui-
terpenes that have not been described before in cyanobacteria were isodihydroagarofuran,
eremophilone and 6,11-epoxyisodaucane. Closed-loop stripping analysis revealed that most
of the sesquiterpenes were found in the biomass of Calothrix, while eremophilone was main-
ly observed in the medium of the axenic culture. Eremophilone showed acute toxicity (LC
50
)
against Chironomus riparius (insecta) at 29 μM and against Thamnocephalus platyurus (crus-
tacea) at 22 μM. The compound was not toxic for Plectus cirratus (nematoda). 6,11-Epoxyiso-
daucane and isodihydroagarofuran exhibited no toxicity to invertebrates when applied in
concentrations up to 100 μM.
Key words: Sesquiterpenes, Isodihydroagarofuran, Cyanobacterium, Insecticide