2017 ISCE/APACE Kyoto, Japan (August 24, 2017) GC / FT-IR … · 2017. 11. 6. · Δ1 secretion...
Transcript of 2017 ISCE/APACE Kyoto, Japan (August 24, 2017) GC / FT-IR … · 2017. 11. 6. · Δ1 secretion...
* Tokyo University of Agricultureand Technology, JapanJapan
JICA, Can Tho University, VietnamE-mail: [email protected]
Yuta Muraki, Hideshi Naka, Atsushi Honma, Johanna Mappes, Kaisa Suisto, and Tetsu Ando*
Yuta Muraki, Hideshi Naka, Atsushi Honma, Johanna Mappes, Kaisa Suisto, and Tetsu Ando*
2017 ISCE/APACE2017 ISCE/APACEKyoto, Japan (August 24, 2017)Kyoto, Japan (August 24, 2017)
GC / FT-IR analysis of a novel 2,4,6,9-tetraene occurring in a female pheromone gland of
Parasemia plantaginis (Lepidoptera: Arctiidae)
GC / FT-IR analysis of a novel 2,4,6,9-tetraene occurring in a female pheromone gland of
Parasemia plantaginis (Lepidoptera: Arctiidae)
3000 2000 1000 (cm-1)
OHH
O
HOOAc
OAc
silkworm moth smaller tea tortrix rice stem borer
Milionia basalis giant geometrid moth
bombykol
Type I
Type IIO O
epo3,Z6,Z9-19:H Z3,epo6,Z9-19:H
Sex pheromones have been identified from more than 670 species.Male attractants have been reported for other 1300 species.
Unsaturated fatty alcohols, acetates and aldehydes with a C10 – C18 chain
Found most commonly (75%)
Polyunsaturated hydrocarbons and their epoxides with a C17 – C23 chain
Identified from evolved-insect groups (15%)
Representative lepidopteran sex pheromones
Z3,Z6,Z9-21:H
plum cankerworm moth
Photos from http://www.jpmoth.org/
plum cankerworm mothZ3,Z6,Z9-21:HZ3,Z6,Z9-23:H
satin moth Z3,epo6,epo9-21:H
Pyraloidea
TortricoideaCossoidea
GelechioideaZygaenoidea
Tineoidea
Ditrysia
Monotrysia
Dacnonypha
Paramecoptera
Nepticuloidea
Papillionoidea
Pterophoroidea
Hepialoidea
EriocranioideaZeugloptera
Geometroidea
NoctuoideaBombycoidea
Incurvarioidea
Yponomeutoidea Castnioidea
HesperioideaSesioidea
Type I pheromoneType II pheromone
Phylogenetic tree of Lepidoptera
yellow peach mothE10-16:AldZ3,Z6,Z9-23:H
Linoleic acidZ6,Z9-dienes
E4,Z6,Z9-trienesZ6,Z9,E11-trienesZ6,Z9,Z12-trienesdesaturation
mono-epoxides
OH
O
OH
OLinolenic acidZ3,Z6,Z9-trienes
1,Z3,Z6,Z9-tetraenesZ3,Z6,Z9,E11-tetraenesZ3,Z6,Z9,Z11-tetraenesdesaturation
mono- and di-epoxides
CnH2n+1
CnH2n+1Δ1
secretion
secretion
Δ11
Δ4 Δ11
Δ12
The known chemical diversity is still limited. Novel compounds must be found.
Chemical structures of Type II pheromones
emerald moth
Four subspecies are recorded in Japan.P. p. macromera P. p. melanissimaP. p. jezoensis P. p. melanomera
Noctuoidea species and their sex pheromones
Parasemia plantaqinis, wood tiger moth(Arctiidae; Arctiinae)
Noctuoidea
LithosiinaeSyntominaeArctiinae
Super-family Family Sub-family Taxonomy
*Erebidae
<Trifinae> <Quadritinae>*
NotodontidaeNolidaeNoctuidae
Lymantriidae*Arctiidae* II, others
IIII, others
IIIIII, othersII, others
Type ofpheromone
79 [4]4 [1]
51 [3]
124 [0]107 [0]787 [34]489 [4]59 [16]
Japanesespecies number
[ ] indicate number of species whose sex pheromone has been identified.
Four subspecies are recorded in Japan.P. p. macromera P. p. melanissimaP. p. jezoensis P. p. melanomera
EAD
GC-EAD analysis of the pheromone extract
FID
0.1 mV
Comp. IComp. II
Mixing ratioI : II : III : IV ≑ 30:3:5:1
Comp. III
Comp. IV
GC column: DB-23 (0.25 mm X 30 m)
Temperature program:80ºC (1 min) →
210ºC (10ºC/min)
20.0 22.018.0 Rt (min)
Comp. IZ3,Z6,Z9-21:H
Crude pheromoneextract (1.0 FE)
Parasemia plantaqinis, wood tiger moth(Arctiidae; Arctiinae)
Comp. II100
0
121135
149107
93
79
GC / MS analysis of the pheromone extract
247194
GC column: DB-23(0.25 mm X 30 m)
Temperature program:80ºC (1 min) →
210ºC (8ºC/min)
I
IIIII
IV
TIC
E4,Z6,Z9-21:H
135121
79
247 194
290M+
Crude pheromoneextract (1.0 FE)
20.018.0 Rt (min)
25020015010050 300 m/z
234
25020015010050 300
79 91
106 119133147 288
m/z
M+
Comp. III100
0
1,Z3,Z6,Z9-21:H
234
133
79
10691
100
025020015010050 300
220
79
94
105119133
147 288
m/z
M+
91
Comp. IV 133105
94 220
912,4,6,9-tetraene ?
No information on the configurationsGC / FT-IR
OH
Functional group OH Carbon chain length 16
Double bond Number 2Position 10, 12Configuration E, Z
Determined by the IR spectrum,if a large amount of the pure pheromone is available.
IR analysis is not utilized, becausethe species-specific pheromones are composed of multiple components, which are produced at μg level, at most.
O-Htrans
cis
Merits of IR analysis
Lq. N2GC / FT-IR
<Spectra Analysis, Inc.>
Capillary GC High separation
FT-IR (solid phase) High sensitivity
Familiarized spectrum
® Discover IR
IR beamGCcapillary
Detector
ZnSe diskcooled at −30ºC
Comp. I3007
29652918
2851 14721396 935
728
30132958
2919
2852 1473
30102954
2919
2853899
IR spectra of four EAG-active components
Comp. II
Comp. III
Measured by GC / FT-IR Disk temperature: −30ºCDisk speed: 2 mm/minCrude extract (4 FE)
Comp. IV includes E,Z conjugated systems, and no Z,Z conjugation.
983951
1000
E4,Z6,Z9-21:H
30202957
2921
2853
3000 2000 1000 (cm-1)
Comp. IV 1470 765992
941
Z2,E4,Z6,Z9-21:H
3040
ConjugatedZ,Z-diene
970Z3,Z6,Z9-21:H
1,Z3,Z6,Z9-21:H
H
O
H
O
_Br Ph3
+P P+Ph3 Br_
••
Ph3P PPh3
H
O
Synthesis of 2,4,6,9-tetraene
Br Br
Poor yield (< 5%), but a very simple route
GC / FT-IR analyses of natural and synthetic 2,4,6,9-tetraene
20.0 22.0Rt (min)
20.0 22.0
[Peak chromatogram]
I
IIIII
IV
Synthetic
E2,E43020
2921
Comp. IV
3020
2921
993942766
993942766
Crude extract
Synthetic
3000 2000 1000 (cm-1)
3017
2921
752996
SyntheticE2,E4,Z6,Z9-21:H
good coincident
Z2,E4,Z6,Z9-21:H
Crude extract(4 FE)
Z2,E4
Column: HP-5(0.25 mm X 30 m)
Summary & discussion
1) Four EAG-active components were found in the pheromone grand of P. p. melanomera and a Finnish subspecies.
2) GC/MS and GC/FT-IR analyses showed the following structures.Comp. I Z3,Z6,Z9-21:H ( ← linolenic acid)Comp. II E4.Z6,Z9-21:H ( ← linoleic acid)Comp. III 1,Z3,Z6,Z9-21:H ( ← linolenic acid)Comp. IV Z2,E4,Z6,Z9-21:H ( ← linoleic acid)
Mixing ratio; I : II : III : IV ≑ 30 : 3 : 5 : 1
3) An IR spectrum of the minor Comp. IV measured by a high-sensitive GC/FT-IR instrument indicated its 2Z,4E configuration.
4) The structure of Comp. IV was confirmed by synthesis utilizing the double Wittig reaction.
5) Male attraction by synthetic lures in the field has not succeeded, indicating necessity of additional pheromone component(s).
Thank you for attention !! Thank you for attention !!
I retired Tokyo University of Agriculture and Technology (TUAT) in 2015.
I am grateful to all member of Chemical Ecology Laboratory of TUAT, who studied lepidopteran sex pheromones together.
I retired Tokyo University of Agriculture and Technology (TUAT) in 2015.
I am grateful to all member of Chemical Ecology Laboratory of TUAT for study of lepidopteran sex pheromones.
Present address: Can Tho University (CTU) in Can Tho City, Vietnam Chief advisor of JICA’s project for “Building Capacity for CTU”
https://lepipheromone.sakura.ne.jp/index_eng.html