Please wait a moment until all data is loaded. This message will disappear when all data is loaded.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
(+)-copalyl diphosphate
(+-)-13-hydroxy-8(14)-abietene + diphosphate
-
-
initial product of the reaction, thermally unstable. Dehydration of the alcohol products of (+)-copalyl diphosphate, yielding the well established diterpene products levopimaradiene, abietadiene, neoabietadiene, and palustradiene, may occurr due to three conditions of the GC-MS analysis typically used for identification of diterpene synthase products: a hot injector, a hot oven temperature necessary for eluting the compounds, and the high temperature and high energy of the MS and its interface
-
?
(+)-copalyl diphosphate
abieta-7,13-diene + diphosphate
(+)-copalyl-diphosphate
(-)-abietadiene + diphosphate
-
-
-
-
?
(+)-copalyl-diphosphate
(-)-abietadiene + levopimaradiene + neoabietadiene + palustradiene + diphosphate
(+)-copalyl-diphosphate
abieta-7,13-diene + abieta-8(14),13(15)-diene + abieta-8(14),12-diene + diphosphate
reaction intermediate is abieta-8(14)-en-13-yl cation
-
-
?
8alpha-hydroxy-17-nor copalyl diphosphate
17-normanoyl oxide + diphosphate
-
-
-
-
?
copalyl diphosphate
abietadienes + diphosphate
-
class I terpene synthase reaction
-
-
ir
geranylgeranyl diphosphate + diphosphate
(+)-copalyl diphosphate
-
-
-
?
(+)-copalyl diphosphate
abieta-7,13-diene + diphosphate
-
-
-
?
(+)-copalyl diphosphate
abieta-7,13-diene + diphosphate
-
-
products are levopimaradiene, abieta-7,13-diene, and sandaracopimaradiene
-
?
(+)-copalyl-diphosphate
(-)-abietadiene + levopimaradiene + neoabietadiene + palustradiene + diphosphate
reaction intermediate is C8-sandaracopimaradienyl cation
bifunctional levopimaradiene/abietadiene synthase produces a mixture of diterpenes
-
?
(+)-copalyl-diphosphate
(-)-abietadiene + levopimaradiene + neoabietadiene + palustradiene + diphosphate
reaction intermediate is C8-sandaracopimaradienyl cation
bifunctional levopimaradiene/abietadiene synthase, about 47% levopimaradiene, 27% abietadiene, 22% neoabietadiene, 3% palustradiene
-
?
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
A723S
product is switched from abietadienes to 75% isopimara-7,15-diene + 21% sandaracopimaradiene
D361A
-
lower turnover with geranylgeranyl diphosphate than wild-type
D402A
-
lower turnover with geranylgeranyl diphosphate than wild-type
D402E
-
lower turnover with geranylgeranyl diphosphate than wild-type
D402N
-
lower turnover with geranylgeranyl diphosphate than wild-type
D404E
-
lower turnover with geranylgeranyl diphosphate than wild-type
D404N
-
lower turnover with geranylgeranyl diphosphate than wild-type
D405A
-
lower turnover with geranylgeranyl diphosphate than wild-type
D405E
-
lower turnover with geranylgeranyl diphosphate than wild-type
D405N
-
lower turnover with geranylgeranyl diphosphate than wild-type
D625A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
D766A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
D845A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
DELTA:107-868
-
lower turnover with copalyl diphosphate than wild-type
DELTA:85-849
-
no turnover with copalyl diphosphate
E499A
-
lower turnover with geranylgeranyl diphosphate than wild-type
E589A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
E699A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
E773A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
E778A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
H348A/D621A
the mutant also produces 8alpha-hydroxy-copalyl diphosphate from geranylgeranyl diphosphate
N451A
this mutation reduces class II (protonation-initiated cyclization) activity about 100fold, with essentially no effect on class I (ionization-initiated cyclization) activity
N765A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
R365A
-
lower turnover with geranylgeranyl diphosphate than wild-type
R411A
-
lower turnover with geranylgeranyl diphosphate than wild-type
R454A
-
lower turnover with geranylgeranyl diphosphate than wild-type
R584A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
R586A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
R762A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
rAS:D96A
-
nearly the same turnover with copalyl diphosphate like wild-type
rAS:K86A/R87A
-
lower turnover with copalyl diphosphate than wild-type
S721A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
T617A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
T848A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
W358A
-
lower turnover with geranylgeranyl diphosphate than wild-type
Y520A
-
lower turnover with geranylgeranyl diphosphate than wild-type
Y841F
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
A620T
-
130% of wild-type productivity. Products are 87% levopimaradiene, 11% abieta-7,13-diene, and 2% sandaracopimaradiene
A729G
-
2% of wild-type productivity. Product is 100% sandaracopimaradiene
C618N
-
20% of wild-type productivity. Products are 91% levopimaradiene, 9% abieta-7,13-diene, and traces of sandaracopimaradiene
G854T
-
140% of wild-type productivity. Products are 79% levopimaradiene, 14% abieta-7,13-diene, and 7% sandaracopimaradiene
I855L
-
70% of wild-type productivity. Products are 90% levopimaradiene, 7% abieta-7,13-diene, and 3% sandaracopimaradiene
K723S
-
180% of wild-type productivity. Products are 90% levopimaradiene, 7% abieta-7,13-diene, and 3% sandaracopimaradiene
L619F
-
150% of wild-type productivity. Products are 94% levopimaradiene, 6% abieta-7,13-diene, and traces of sandaracopimaradiene
L696Q
-
160% of wild-type productivity. Products are 86% levopimaradiene, 7% abieta-7,13-diene, and 7% sandaracopimaradiene
M593I
-
370% of wild-type productivity. Products are 83% levopimaradiene, 12% abieta-7,13-diene, and 5% sandaracopimaradiene
N838E
-
220% of wild-type productivity. Products are 92% levopimaradiene, 6% abieta-7,13-diene, and 2% sandaracopimaradiene
V731L
-
8% of wild-type productivity. Product is 100% levopimaradiene
Y700F
-
500% of wild-type productivity. Products are 80% levopimaradiene, 15% abieta-7,13-diene, and 5% sandaracopimaradiene
Y700H
-
40% of wild-type productivity. Products are 71% levopimaradiene, traces of abieta-7,13-diene, and 29% sandaracopimaradiene
Y700M
-
500% of wild-type productivity. Products are 80% levopimaradiene, 13% abieta-7,13-diene, and 7% sandaracopimaradiene
Y700W
-
400% of wild-type productivity. Products are 85% levopimaradiene, 7% abieta-7,13-diene, and 8% sandaracopimaradiene
A713S
products are isopimaradiene and sandaracopimaradiene
G651V
no change in product
V717L
no change in product
W679L/Y686H/A713S/V717L
products are isopimaradiene and sandaracopimaradiene
Y686H
no change in product
Y686H/A713S
main products are isopimaradiene and sandaracopimaradiene
Y686H/A713S A713S
main products are isopimaradiene and sandaracopimaradiene
Y686H/A713S/V717L
products are isopimaradiene and sandaracopimaradiene
additional information
swapping of residues 568640 of isopimaradiene synhase to corresponding residues 560-632 of levopimaradiene/abietadiene synthase results in complete reversion of the product profiles of the two enzymes
D404A
-
-
D404A
-
unreactive with geranylgeranyl diphosphate
D621A
-
-
D621A
-
unreactive with (+)-copalyl diphosphate
D621A
-
eliminates class I activity
D621A
this substitution eliminates the subsequently acting class I activity
T769A
-
no effect on geranylgeranyl diphosphate reaction, but lower turnover with copalyl diphosphate than wild-type
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Please wait a moment until the data is sorted. This message will disappear when the data is sorted.
Ravn, M.M.; Coates, R.M.; Flory, J.E.; Peters, R.J.; Croteau, R.
Stereochemistry of the cyclization-rearrangement of (+)-copalyl diphosphate to (-)-abietadiene catalyzed by recombinant abietadiene synthase from Abies grandis
Org. Lett.
2
573-576
2000
Abies grandis
brenda
Peters, R.J.; Flory, J.E.; Jetter, R.; Ravn, M.M.; Lee, H.J.; Coates, R.M.; Croteau, R.B.
Abietadiene synthase from grand fir (Abies grandis): characterization and mechanism of action of the "pseudomature" recombinant enzyme
Biochemistry
39
15592-15602
2000
Abies grandis
brenda
Peters, R.J.; Ravn, M.M.; Coates, R.M.; Croteau, R.B.
Bifunctional abietadiene synthase: Free diffusive transfer of the (+)-copalyl diphosphate intermediate between two distinct active sites
J. Am. Chem. Soc.
123
8974-8978
2001
Abies grandis
brenda
Peters, R.J.; Croteau, R.B.
Abietadiene synthase catalysis: conserved residues involved in protonation-initiated cyclization of geranylgeranyl diphosphate to (+)-copalyl diphosphate
Biochemistry
41
1836-1842
2002
Abies grandis
brenda
Peters, R.J.; Croteau, R.B.
Abietadiene synthase catalysis: mutational analysis of a prenyl diphosphate ionization-initiated cyclization and rearrangement
Proc. Natl. Acad. Sci. USA
99
580-584
2002
Abies grandis
brenda
Ravn, M.M.; Peters, R.J.; Coates, R.M.; Croteau, R.
Mechanism of abietadiene synthase catalysis: stereochemistry and stabilization of the cryptic pimarenyl carbocation intermediates
J. Am. Chem. Soc.
124
6998-7006
2002
Abies grandis
brenda
Peters, R.J.; Carter, O.A.; Zhang, Y.; Matthews, B.W.; Croteau, R.B.
Bifunctional abietadiene synthase: mutual structural dependence of the active sites for protonation-initiated and ionization-initiated cyclizations
Biochemistry
42
2700-2707
2003
Abies grandis
brenda
Vogel, B.S.; Wildung, M.R.; Vogel, G.; Croteau, R.
Abietadiene synthase from grand fir (Abies grandis). cDNA isolation, characterization, and bacterial expression of a bifunctional diterpene cyclase involved in resin acid biosynthesis
J. Biol. Chem.
271
23262-23268
1996
Abies grandis
brenda
Ro, D.K.; Bohlmann, J.
Diterpene resin acid biosynthesis in loblolly pine (Pinus taeda): Functional characterization of abietadiene/levopimaradiene synthase (PtTPS-LAS) cDNA and subcellular targeting of PtTPS-LAS and abietadienol/abietadienal oxidase (PtAO, CYP720B1)
Phytochemistry
67
1572-1578
2006
Pinus taeda, Pinus taeda (Q50EK2)
brenda
Wilderman, P.R.; Peters, R.J.
A single residue switch converts abietadiene synthase into a pimaradiene specific cyclase
J. Am. Chem. Soc.
129
15736-15737
2007
Abies grandis (Q38710)
brenda
Keeling, C.I.; Weisshaar, S.; Lin, r.P.C.; Bohlmann, J.
Functional plasticity of paralogous diterpene synthases involved in conifer defense
Proc. Natl. Acad. Sci. USA
105
1085-1090
2008
Picea abies (Q675L4)
brenda
Zhou, K.; Peters, R.J.
Investigating the conservation pattern of a putative second terpene synthase divalent metal binding motif in plants
Phytochemistry
70
366-369
2009
Abies grandis
brenda
Kim, Y.B.; Kim, S.M.; Kang, M.K.; Kuzuyama, T.; Lee, J.K.; Park, S.C.; Shin, S.C.; Kim, S.U.
Regulation of resin acid synthesis in Pinus densiflora by differential transcription of genes encoding multiple 1-deoxy-D-xylulose 5-phosphate synthase and 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate reductase genes
Tree Physiol.
29
737-749
2009
Pinus densiflora (B9U4U8), Pinus densiflora
brenda
Siebert, M.R.; Zhang, J.; Addepalli, S.V.; Tantillo, D.J.; Hase, W.L.
The need for enzymatic steering in abietic acid biosynthesis: gas-phase chemical dynamics simulations of carbocation rearrangements on a bifurcating potential energy surface
J. Am. Chem. Soc.
133
8335-8343
2011
synthetic construct
brenda
Keeling, C.I.; Madilao, L.L.; Zerbe, P.; Dullat, H.K.; Bohlmann, J.
The primary diterpene synthase products of Picea abies levopimaradiene/abietadiene synthase (PaLAS) are epimers of a thermally unstable diterpenol
J. Biol. Chem.
286
21145-21153
2011
Picea abies
brenda
Zulak, K.G.; Dullat, H.K.; Keeling, C.I.; Lippert, D.; Bohlmann, J.
Immunofluorescence localization of levopimaradiene/abietadiene synthase in methyl jasmonate treated stems of Sitka spruce (Picea sitchensis) shows activation of diterpenoid biosynthesis in cortical and developing traumatic resin ducts
Phytochemistry
71
1695-1699
2010
Picea sitchensis
brenda
Leonard, E.; Ajikumar, P.K.; Thayer, K.; Xiao, W.H.; Mo, J.D.; Tidor, B.; Stephanopoulos, G.; Prather, K.L.
Combining metabolic and protein engineering of a terpenoid biosynthetic pathway for overproduction and selectivity control
Proc. Natl. Acad. Sci. USA
107
13654-13659
2010
Ginkgo biloba
brenda
Zhou, K.; Gao, Y.; Hoy, J.A.; Mann, F.M.; Honzatko, R.B.; Peters, R.J.
Insights into diterpene cyclization from structure of bifunctional abietadiene synthase from Abies grandis
J. Biol. Chem.
287
6840-6850
2012
Abies grandis (Q38710)
brenda
Criswell, J.; Potter, K.; Shephard, F.; Beale, M.H.; Peters, R.J.
A single residue change leads to a hydroxylated product from the class II diterpene cyclization catalyzed by abietadiene synthase
Org. Lett.
14
5828-5831
2012
Abies grandis (Q38710)
brenda