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Literature summary for 4.2.3.135 extracted from
- Moonlighting metals insights into regulation of cyclization pathways in fungal DELTA6-protoilludene sesquiterpene synthases (2015), ChemBioChem, 16, 2191-2199 .
Cloned(Commentary)
| Cloned (Comment) | Organism |
|---|---|
| recombinant expression of His6-tagged Stehi25180 enzyme in Escherichia coli | Stereum hirsutum |
| recombinant expression of His6-tagged Stehi64702 enzyme in Escherichia coli | Stereum hirsutum |
| recombinant expression of wild-type and mutant His6-tagged Omp6 enzymes in Escherichia coli | Omphalotus olearius |
| recombinant expression of wild-type and mutant His6-tagged Omp7 enzymes in Escherichia coli | Omphalotus olearius |
| recombinant expression of wild-type and mutant His6-tagged Stehi73029 enzymes in Escherichia coli | Stereum hirsutum |
Protein Variants
| Protein Variants | Comment | Organism |
|---|---|---|
| A159E | site-directed mutagenesis of Omp7, compared to wild-type, the mutant shows moderate reduction of activity with Mg2+ and Mn2+, slight to moderate reduction with Co2+, slightly reduced activity with Ni2+, and strong reduction of activity with Ca2+ | Omphalotus olearius |
| D111A | site-directed mutagenesis of Stehi73029, compared to wild-type, the mutant shows moderately reduced activity with Mg2+, slight to moderate reduction of activity with Mn2+, strong reduction of activity with Co2+, and no activity with Ca2+ and Ni2+ | Stereum hirsutum |
| E117A | site-directed mutagenesis of Stehi73029, compared to wild-type, the mutant shows slight to moderate reduction of activity with Mg2+, strongly reduced activity with Ca2+ and Mn2+, very strong reduction of activity with Co2+, and no activity with Ni2+ | Stereum hirsutum |
| E164A | site-directed mutagenesis of Stehi73029, compared to wild-type, the mutant shows moderate reduction of activity with Mg2+, strong reduction with Ca2+, Co2+, and Mn2+, and very strong reduction with Ni2+ | Stereum hirsutum |
| E187A | site-directed mutagenesis of Stehi73029, compared to wild-type, the mutant shows slight to moderate reduction of activity with Mg2+, and no activity with Ca2+, Mn2+, Ni2+, and Co2+ | Stereum hirsutum |
| E53A | site-directed mutagenesis of Stehi73029, compared to wild-type, the mutant shows slight reduction of activity with Mg2+, moderately reduced activity with Ca2+ and Mn2+, and no activity with Ni2+ and Co2+ | Stereum hirsutum |
| S93E/A159E | site-directed mutagenesis of Omp7, compared to wild-type, the mutant shows moderate reduction of activity with Co2+, Mg2+, and Mn2+, slightly reduced activity with Ni2+, and strong reduction of activity with Ca2+ | Omphalotus olearius |
| T165A | site-directed mutagenesis of Omp6, compared to wild-type, the mutant shows moderate reduction of activity with Mg2+ and Ni2+, slight to moderate reduction with Co2+, slightly reduced activity with Mn2+, and very strong reduction of activity with Ca2+ | Omphalotus olearius |
Metals/Ions
| Metals/Ions | Comment | Organism | Structure |
|---|---|---|---|
| Ca2+ | activates, about 50% activity as compared to Mn2+, Stehi25180 | Stereum hirsutum |  |
| Ca2+ | activates, about 60% activity as compared to Mg2+, Omp6 | Omphalotus olearius | |
| Ca2+ | activates, about 60% activity as compared to Mn2+, Stehi64702 | Stereum hirsutum | |
| Ca2+ | activates, about 80% activity as compared to Mn2+, Stehi73029 | Stereum hirsutum | |
| Ca2+ | activates, low activity with Ca2+ as compared to Mg2+, Omp7 | Omphalotus olearius | |
| Co2+ | activates, about 30-40% activity as compared to Mg2+, Omp6 | Omphalotus olearius | |
| Co2+ | activates, about 40% activity as compared to Mn2+, Stehi73029 | Stereum hirsutum | |
| Co2+ | activates, about 50% activity as compared to Mn2+, Stehi64702 | Stereum hirsutum | |
| Co2+ | activates, low activity with Co2+ as compared to Mg2+, Omp7 | Omphalotus olearius | |
| Co2+ | activates, low activity with Co2+ as compared to Mn2+, Stehi25180 | Stereum hirsutum | |
| Mg2+ | activates, about 50% activity as compared to Mn2+, Stehi25180 | Stereum hirsutum | |
| Mg2+ | activates, about 70-80% activity as compared to Mn2+, Stehi64702 | Stereum hirsutum | |
| Mg2+ | activates, about 90% activity as compared to Mn2+, Stehi73029 | Stereum hirsutum | |
| Mg2+ | activates, preferred divalent metal ion | Omphalotus olearius | |
| Mg2+ | required, preferred divalent metal ion, Omp7 | Omphalotus olearius | |
| Mn2+ | activates, about 70% activity as compared to Mg2+, Omp6 | Omphalotus olearius | |
| Mn2+ | activates, preferred divalent metal ion, Stehi25180 | Stereum hirsutum | |
| Mn2+ | activates, preferred divalent metal ion, Stehi64702 | Stereum hirsutum | |
| Mn2+ | activates, preferred divalent metal ion, Stehi73029 | Stereum hirsutum | |
| Mn2+ | activates, results in about 70% of the activity compared to Mg2+, Omp7 | Omphalotus olearius | |
| additional information | DELTA6-protoilludene synthases are catalytically functional with a range of metal ions. Sesquiterpene synthases typically bind the divalent metal cations Mg2+ and Mn2+ to ionize the pyrophosphate of (2E,6E)-farnesyl diphosphate, exploration of metal ion dependencies of different DELTA6-protoilludene synthases, overview. Metal-dependent ionization results in the release of the diphosphate moiety from farnesyl diphosphate ((2E,6E)-FPP) leading to either a 1,11- or 1,10-cyclization of the primary carbocation. A 1,11 cyclization leads to the trans-humulyl cation, a 1,10-cyclization of the primary carbocation leads to the (E,E)-germacradienyl cation. Further hydride shifts and cyclizations results in final sesquiterpene products | Stereum hirsutum | |
| additional information | DELTA6-protoilludene synthases are catalytically functional with a range of metal ions. Sesquiterpene synthases typically bind the divalent metal cations Mg2+ and Mn2+ to ionize the pyrophosphate of (2E,6E)-farnesyl diphosphate, exploration of metal ion dependencies of different DELTA6-protoilludene synthases, overview. Metal-dependent ionization results in the release of the diphosphate moiety from farnesyl diphosphate ((2E,6E)-FPP) leading to either a 1,11- or 1,10-cyclization of the primary carbocation. A 1,11-cyclization leads to the trans-humulyl cation, a 1,10-cyclization of the primary carbocation leads to the (E,E)-germacradienyl cation. Further hydride shifts and cyclizations results in final sesquiterpene products | Omphalotus olearius | |
| additional information | DELTA6-protoilludene synthases are catalytically functional with a range of metal ions. Sesquiterpene synthases typically bind the divalent metal cations Mg2+ and Mn2+ to ionize the pyrophosphate of (2E,6E)-farnesyl diphosphate, exploration of metal ion dependencies of different DELTA6-protoilludene synthases, overview. Metal-dependent ionization results in the release of the diphosphate moiety from farnesyl diphosphate ((2E,6E)-FPP) leading to either a 1,11- or 1,10-cyclization of the primary carbocation. A 1,11-cyclization leads to the trans-humulyl cation, a 1,10-cyclization of the primary carbocation leads to the (E,E)-germacradienyl cation. Further hydride shifts and cyclizations results in final sesquiterpene products | Stereum hirsutum | |
| Ni2+ | activates, about 20% activity as compared to Mg2+, Omp6 | Omphalotus olearius | |
| Ni2+ | activates, low activity as compared to Mn2+, Stehi73029 | Stereum hirsutum | |
| Ni2+ | activates, low activity with Ni2+ as compared to Mg2+, Omp7 | Omphalotus olearius | |
| Ni2+ | activates, low activity with Ni2+ as compared to Mn2+, Stehi25180 | Stereum hirsutum | |
| Ni2+ | activates, low activity with Ni2+ as compared to Mn2+, Stehi64702 | Stereum hirsutum | |
Natural Substrates/ Products (Substrates)
| Natural Substrates | Organism | Comment (Nat. Sub.) | Natural Products | Comment (Nat. Pro.) | Rev. | Reac. |
|---|---|---|---|---|---|---|
| (2E,6E)-farnesyl diphosphate | Omphalotus olearius | - |
DELTA6-protoilludene + diphosphate | - |
? | |
| (2E,6E)-farnesyl diphosphate | Stereum hirsutum | - |
DELTA6-protoilludene + diphosphate | - |
? | |
Organism
| Organism | UniProt | Comment | Textmining |
|---|---|---|---|
| Omphalotus olearius | - |
- |
- |
| Stereum hirsutum | - |
- |
- |
Purification (Commentary)
| Purification (Comment) | Organism |
|---|---|
| recombinant His6-tagged Stehi25180 enzyme from Escherichia coli by affinity chromatography and dialysis against EDTA to eliminate metal ions | Stereum hirsutum |
| recombinant His6-tagged Stehi64702 enzyme from Escherichia coli by affinity chromatography and dialysis against EDTA to eliminate metal ions | Stereum hirsutum |
| recombinant wild-type and mutant His6-tagged Omp6 enzymes from Escherichia coli by affinity chromatography and dialysis against EDTA to eliminate metal ions | Omphalotus olearius |
| recombinant wild-type and mutant His6-tagged Omp7 enzymes from Escherichia coli by affinity chromatography and dialysis against EDTA to eliminate metal ions | Omphalotus olearius |
| recombinant wild-type and mutant His6-tagged Stehi73029 enzymes from Escherichia coli by affinity chromatography and dialysis against EDTA to eliminate metal ions | Stereum hirsutum |
Reaction
| Reaction | Comment | Organism | Reaction ID |
|---|---|---|---|
| (2E,6E)-farnesyl diphosphate = DELTA6-protoilludene + diphosphate | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-farnesyl diphosphate following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Proposed mechanisms for sesquiterpene production by DELTA6-protoilludene synthases, overview | Stereum hirsutum | |
| (2E,6E)-farnesyl diphosphate = DELTA6-protoilludene + diphosphate | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-FPP following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Proposed mechanisms for sesquiterpene production by DELTA6-protoilludene synthases, overview | Omphalotus olearius | |
| (2E,6E)-farnesyl diphosphate = DELTA6-protoilludene + diphosphate | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11-cyclization of (2E,6E)-farnesyl diphosphate following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Proposed mechanisms for sesquiterpene production by DELTA6-protoilludene synthases, overview | Stereum hirsutum |
Substrates and Products (Substrate)
| Substrates | Comment Substrates | Organism | Products | Comment (Products) | Rev. | Reac. |
|---|---|---|---|---|---|---|
| (2E,6E)-farnesyl diphosphate | - |
Omphalotus olearius | DELTA6-protoilludene + diphosphate | - |
? | |
| (2E,6E)-farnesyl diphosphate | - |
Stereum hirsutum | DELTA6-protoilludene + diphosphate | - |
? | |
| additional information | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-farnesyl diphosphate following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Diphosphate enzyme-coupled spectrophotometric assay | Stereum hirsutum | ? | - |
? | |
| additional information | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-FPP following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Diphosphate enzyme-coupled spectrophotometric assay | Omphalotus olearius | ? | - |
? | |
| additional information | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11-cyclization of (2E,6E)-farnesyl diphosphate following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene Diphosphate enzyme-coupled spectrophotometric assay | Stereum hirsutum | ? | - |
? | |
Synonyms
| Synonyms | Comment | Organism |
|---|---|---|
| DELTA6-protoilludene sesquiterpene synthase | - |
Omphalotus olearius |
| DELTA6-protoilludene sesquiterpene synthase | - |
Stereum hirsutum |
| Omp6 | - |
Omphalotus olearius |
| OMP7 | - |
Omphalotus olearius |
| Stehi25180 | - |
Stereum hirsutum |
| Stehi64702 | - |
Stereum hirsutum |
| Stehi73029 | - |
Stereum hirsutum |
Temperature Optimum [°C]
| Temperature Optimum [°C] | Temperature Optimum Maximum [°C] | Comment | Organism |
|---|---|---|---|
| 22 | - |
assay at room temperature | Omphalotus olearius |
| 22 | - |
assay at room temperature | Stereum hirsutum |
pH Optimum
| pH Optimum Minimum | pH Optimum Maximum | Comment | Organism |
|---|---|---|---|
| 7.5 | - |
assay at | Omphalotus olearius |
| 7.5 | - |
assay at | Stereum hirsutum |
General Information
| General Information | Comment | Organism |
|---|---|---|
| metabolism | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-farnesyl diphosphate ((2E,6E)-FPP) following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Alternatively, a direct 2,10 cyclization of the trans-humulyl cation leads to (E)-beta-caryophyllene. On the other hand, beta-elemene, 4,11-selinadiene, beta-selinene and alpha-selinene are derived from a 1,10 cyclization of (2E,6E)-FPP. A direct deprotonation of the intermediate (E,E)-germacradienyl cation results in germacrene A. beta-Elemene is the heat-induced Cope rearrangement product. A 2,7 cyclization of the (E,E)-germacradienyl cation is followed by deprotonation yields 4,11-selinadiene. Finally, a hydride shift, followed by a 2,7 cyclization of the (E,E)-germacradienyl cation and deprotonation leads to beta-selinene and alpha-selinene. Therefore DELTA6-protoilludene synthases are capable of catalyzing simultaneously a 1,10 and a 1,11 cyclization in the presence of an alternative metal ion | Omphalotus olearius |
| metabolism | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-farnesyl diphosphate ((2E,6E)-FPP) following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Alternatively, a direct 2,10 cyclization of the trans-humulyl cation leads to (E)-beta-caryophyllene. On the other hand, beta-elemene, 4,11-selinadiene, beta-selinene and alpha-selinene are derived from a 1,10 cyclization of (2E,6E)-FPP. A direct deprotonation of the intermediate (E,E)-germacradienyl cation results in germacrene A. beta-Elemene is the heat-induced Cope rearrangement product. A 2,7 cyclization of the (E,E)-germacradienyl cation is followed by deprotonation yields 4,11-selinadiene. Finally, a hydride shift, followed by a 2,7 cyclization of the (E,E)-germacradienyl cation and deprotonation leads to beta-selinene and alpha-selinene. Therefore DELTA6-protoilludene synthases are capable of catalyzing simultaneously a 1,10 and a 1,11 cyclization in the presence of an alternative metal ion | Stereum hirsutum |
| metabolism | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-farnesyl diphosphate ((2E,6E)-FPP) following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Alternatively, a direct 2,10 cyclization of the trans-humulyl cation leads to (E)-beta-caryophyllene. On the other hand, beta-elemene, 4,11-selinadiene, beta-selinene and alpha-selinene are derived from a 1,10 cyclization of (2E,6E)-FPP. A direct deprotonation of the intermediate (E,E)-germacradienyl cation results in germacrene A. beta-Elemene is the heat-induced Cope rearrangement product. A 2,7 cyclization of the (E,E)-germacradienyl cation is followed by deprotonation yields 4,11-selinadiene. Finally, a hydride shift, followed by a 2,7 cyclization of the (E,E)-germacradienyl cation and deprotonation leads to beta-selinene and alpha-selinene. Therefore DELTA6-protoilludene synthases are capable of catalyzing simultaneously a 1,10- and a 1,11-cyclization in the presence of an alternative metal ion | Stereum hirsutum |
| metabolism | in the presence of Ca2+, DELTA6-protoilludene synthases catalyze diverse cyclization reactions. DELTA6-Protoilludene and (E)-beta-caryophyllene result from a 1,11 cyclization of (2E,6E)-farnesyl diphosphate ((2E,6E)-FPP) following metal ion mediated ionization. The intermediate trans-humulyl cation may undergo a hydride shift followed by two cyclizations and a deprotonation to yield DELTA6-protoilludene. Alternatively, a direct 2,10-cyclization of the trans-humulyl cation leads to (E)-beta-caryophyllene. On the other hand, beta-elemene, 4,11-selinadiene, beta-selinene and alpha-selinene are derived from a 1,10 cyclization of (2E,6E)-FPP. A direct deprotonation of the intermediate (E,E)-germacradienyl cation results in germacrene A. beta-Elemene is the heat-induced Cope rearrangement product. A 2,7 cyclization of the (E,E)-germacradienyl cation is followed by deprotonation yields 4,11-selinadiene. Finally, a hydride shift, followed by a 2,7 cyclization of the (E,E)-germacradienyl cation and deprotonation leads to beta-selinene and alpha-selinene. Therefore DELTA6-protoilludene synthases are capable of catalyzing simultaneously a 1,10- and a 1,11-cyclization in the presence of an alternative metal ion | Stereum hirsutum |
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