1062 K.J. Siegert et al. Insect Biochemistry and Molecular Biology 30 2000 1061–1067
Table 1 Sequences of relevant AKH peptides including the novel AKH-III isolated in the present study. Molecular masses are given in brackets. Residues
identical with those in Phm-AKH-III are given in bold type-face, those similar are italicised, e.g. leucine and isoleucine. The sequencing results of deblocked Phm-3 and Dis-3 are also given
Pab-RPCH 929.4
pGlu Leu
Asn Phe
Ser Pro
Gly TrpNH
2
Lom-AKH-I 1158.5
pGlu Leu
Asn Phe
Thr Pro
Asn Trp
Gly ThrNH
2
Phm-AKH-I 1144.5
pGlu Leu
Asn Phe
Thr Pro
Asn Trp
Gly SerNH
2
Lom-AKH-II 903.4
pGlu Leu
Asn Phe
Ser Ala
Gly TrpNH
2
Scg-AKH-II 933.4
pGlu Leu
Asn Phe
Ser Thr
Gly TrpNH
2
Lom-AKH-III 1072.5
pGlu Leu
Asn Phe
Thr Pro
Trp TrpNH
2
Phm-AKH-III 1072.5
pGlu Ile
Asn Phe
Thr Pro
Trp TrpNH
2
Cycle Residue
Phm-3 Dis-3
pmol pmol
1 Ile
44.6l 35.7
2 Asn
44.2 32.9
3 Phe
42.3 31.4
4 Thr
27.2 19.8
5 Pro
19.1 13.8
6 Trp
5.2 4.5
7 Trp
3.4 2.7
8 void
— —
2. Materials and methods
2.1. Insects Insects were either taken from a colony at the Depart-
ment of Zoology, University of Cape Town, L. migratoria or were collected in the field ca. 100 km
north of Cape Town near the Langebaan lagoon and kept in a constant temperature room at 25
± 2
° C with bran and
oleander leaves ad libitum. 2.2. Extractions
CC were dissected and transferred into Eppendorf tubes which were kept on crushed ice and contained
either 50 µ
l 0.1 trifluoroacetic acid TFA or 50 µ
l 20 acetonitrile in 0.1 TFA. Tissues were then son-
icated for 30 s on ice with a Branson sonicator, spun for 10 min 13,000 rpm and immediately used for reversed-
phase high-performance liquid chromatography RP- HPLC. Other extracts were kept at 270
° C until they
were taken to Aberdeen for HPLC analysis. 2.3. RP-HPLC
At the University of Cape Town, a Gilson system was used as described elsewhere Ga¨de, 1985 with an Ultra-
sphere C-18 column 4.6 mm ×
250 mm, plus guard car- tridge; Altex at a flow rate of 0.8 mlmin; 0.1 TFA
pump A and acetonitrile pump B served as solvents. Peaks were detected in the ultraviolet range at l
= 206
nm and also with a Shimadzu Model RF 535 fluor- escence HPLC monitor excitation wavelength 276 nm,
emission wavelength 350 nm to identify tryptophan- containing peptides. The sensitivities of the spectropho-
tometer and fluorometer were selected in a way that pep- tides containing one tryptophan residue had approxi-
mately the same peak height in the two detection systems. The output was plotted on conventional chart
recorders. Peaks were collected by hand into Eppendorf tubes, dried in vacuo and used for further HPLC analy-
ses,
mass spectrometry,
bioassays or
sequencing. Initially, a gradient that started at 20 acetonitrile was
used; the percentage of B increased at a rate of 1 Bmin Gradient 1. AKHs were also separated with a
gradient that started at 20 B but increased at 0.5 Bmin Gradient 2. For the separation of deblocked pep-
tides the gradient started at 30 B and increased at 0.5 Bmin Gradient 3.
CC extracts and collected peptides were also analysed at the University of Aberdeen using identical HPLC
equipment. The same column was employed, however, a fluorometer was not available. Chromatograms were
stored by the UniPoint software Version 1.40 which also controlled the HPLC pumps. Data were exported as
text files, imported into Microsoft Excel Version 5.0a for the Power Macintosh and then copied into CA-
Cricket Graph software Version 1.5 and plotted.
2.4. Bioassays Adipokinetic effects of isolated RP-HPLC fractions
and synthetic peptides were determined by measuring changes in haemolymph lipid concentrations in adult
locusts and D. spumans with the vanillin reagent Zo¨llner and Kirsch, 1962 as described elsewhere
Ga¨de, 1980; changes in haemolymph carbohydrate
1063 K.J. Siegert et al. Insect Biochemistry and Molecular Biology 30 2000 1061–1067
concentrations were measured with the anthrone reagent Spik and Montreuil, 1964.
2.5. Deblocking of peptides Pyroglutamate
aminopeptidase from
Pyrococcus furiosus was used according to the manufacturer’s
instructions Takara Shuzo. Peptides were dissolved in 25
µ l of the buffer 5
× diluted supplied with the enzyme
and briefly sonicated. Enzyme 0.5 mU was added, the Eppendorf tube vortexed, spun and incubated for 2 h
at 70 °
C with occasional vigorous agitation. Twenty-five microlitres
of HPLC
starting solvent
30 acetonitrile0.1 TFA was added and the mixture kept
on ice until injection onto the RP-HPLC column Gradient 3.
2.6. Mass spectrometry Intact and deblocked peptides were analysed by mass
spectrometry using a Voyager Elite matrix-assisted laser desorptionionisation
time-of-flight instrument
PerSeptive Biosystems. Samples were prepared in α
- cyano-4-hydroxycinnamic acid and spectra acquired in
positive, linear mode. 2.7. Peptide sequencing
Deblocked peptides were subjected to automated Edman degradation using a model 477A sequencer con-
nected to an on-line model 120 phenylhydantoin amino acid analyser both from Applied Biosystems.
2.8. Synthetic peptides Lom–AKH-III and Phm–AKH-III were synthesised
by standard solid-phase chemistry, purified on RP- HPLC, and the identities verified by sequence determi-
nation and mass spectrometry.
3. Results