FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W1991465229> ?p ?o ?g. }

• W1991465229 endingPage "136" @default.
• W1991465229 startingPage "123" @default.
• W1991465229 abstract "The tightly coupled nature of the reaction sequence catalyzed by monoterpene synthases has prevented direct observation of the topologically required isomerization step leading from geranyl diphosphate to the presumptive, enzyme-bound, tertiary allylic intermediate linalyl diphosphate, which ultimately cyclizes to the various monoterpene skeletons. Previous experimental approaches using the noncyclizable substrate analogs 6,7-dihydrogeranyl diphosphate and racemic methanogeranyl diphosphate, in attempts to dissect the cryptic isomerization step from the normally coupled reaction sequence, were thwarted by the limited product available from native monoterpene synthases and by the inability to resolve chiral monoterpene products at the microscale. These approaches were revisited using three recombinant monoterpene synthases and chiral phase capillary gas chromatographic methods to separate antipodal products of the substrate analogs. The recombinant monoterpene olefin synthases, (-)-limonene synthase from spearmint and (-)-pinene synthase from grand fir, yielded essentially only achiral, olefin products (corresponding to the respective analogs and homologs of myrcene, trans-ocimene and cis-ocimene) from 6,7-dihydrogeranyl diphosphate and (2S,3R)-methanogeranyl diphosphate; no significant amounts of terpenols or homoterpenols were formed, nor was direct evidence obtained for the formation of the anticipated analog and homolog of the tertiary intermediate linalyl diphosphate (i.e., 6,7-dihydrolinalyl diphosphate and homolinalyl diphosphate, respectively). In the case of recombinant (+)-bornyl diphosphate synthase from common sage, the achiral olefins were generated, as before, from 6,7-dihydrogeranyl diphosphate and (2R,3S)-methanogeranyl diphosphate, but 6,7-dihydrolinalool and homolinalool also comprised significant components of the respective product mixtures, indicating greater access of water to the active site of this enzyme compared to the olefin synthases; again, no direct evidence for the production of 6,7-dihydrolinalyl diphosphate or homolinalyl diphosphate was obtained. Resolution of the terpenol products of (+)-bornyl diphosphate synthase, by chiral phase separation, revealed the predominant formation of (3R)-dihydrolinalool from dihydrogeranyl diphosphate and of (4S)-homolinalool from (2R,3S)-methanogeranyl diphosphate. The opposite stereochemistries of these products indicates water trapping from opposite faces of the corresponding tertiary carbocationic intermediates of the respective reactions, a phenomenon that appears to result from the binding conformations of these substrate analogs. Although these experiments failed to provide direct evidence for the tertiary intermediate of the tightly coupled isomerization-cyclization sequence, they did reveal a mechanistic difference between the olefin synthases and bornyl diphosphate synthase involving access of water as a participant in the reaction." @default.
• W1991465229 created "2016-06-24" @default.
• W1991465229 creator A5038347649 @default.
• W1991465229 creator A5057022689 @default.
• W1991465229 creator A5060790939 @default.
• W1991465229 creator A5080338371 @default.
• W1991465229 date "2001-08-01" @default.
• W1991465229 modified "2023-09-27" @default.
• W1991465229 title "Mechanism of Monoterpene Cyclization: Stereochemical Aspects of the Transformation of Noncyclizable Substrate Analogs by Recombinant (−)-Limonene Synthase, (+)-Bornyl Diphosphate Synthase, and (−)-Pinene Synthase" @default.
• W1991465229 cites W1157062228 @default.
• W1991465229 cites W1504755473 @default.
• W1991465229 cites W1508698624 @default.
• W1991465229 cites W1509541226 @default.
• W1991465229 cites W1537812986 @default.
• W1991465229 cites W1544037236 @default.
• W1991465229 cites W1557346720 @default.
• W1991465229 cites W1559461130 @default.
• W1991465229 cites W1559601618 @default.
• W1991465229 cites W1603602355 @default.
• W1991465229 cites W1869944834 @default.
• W1991465229 cites W1896171101 @default.
• W1991465229 cites W1966592540 @default.
• W1991465229 cites W1971998602 @default.
• W1991465229 cites W1972008679 @default.
• W1991465229 cites W1979492674 @default.
• W1991465229 cites W1980122559 @default.
• W1991465229 cites W1992665072 @default.
• W1991465229 cites W1999059980 @default.
• W1991465229 cites W2000004567 @default.
• W1991465229 cites W2010013311 @default.
• W1991465229 cites W2011146657 @default.
• W1991465229 cites W2020499974 @default.
• W1991465229 cites W2023189428 @default.
• W1991465229 cites W2023408587 @default.
• W1991465229 cites W2028231353 @default.
• W1991465229 cites W2028965340 @default.
• W1991465229 cites W2029207696 @default.
• W1991465229 cites W2037976136 @default.
• W1991465229 cites W2038192562 @default.
• W1991465229 cites W2054314428 @default.
• W1991465229 cites W2064923892 @default.
• W1991465229 cites W2078117101 @default.
• W1991465229 cites W2080690387 @default.
• W1991465229 cites W2081184252 @default.
• W1991465229 cites W2081195862 @default.
• W1991465229 cites W2087219050 @default.
• W1991465229 cites W2090068673 @default.
• W1991465229 cites W2092926180 @default.
• W1991465229 cites W2094425862 @default.
• W1991465229 cites W2100837269 @default.
• W1991465229 cites W2102015267 @default.
• W1991465229 cites W2113410899 @default.
• W1991465229 cites W2116918100 @default.
• W1991465229 cites W2147767064 @default.
• W1991465229 cites W2399756941 @default.
• W1991465229 cites W2949435209 @default.
• W1991465229 cites W4234578412 @default.
• W1991465229 cites W4240971598 @default.
• W1991465229 cites W4293247451 @default.
• W1991465229 cites W4300629373 @default.
• W1991465229 doi "https://doi.org/10.1006/abbi.2001.2442" @default.
• W1991465229 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/11469803" @default.
• W1991465229 hasPublicationYear "2001" @default.
• W1991465229 type Work @default.
• W1991465229 sameAs 1991465229 @default.
• W1991465229 citedByCount "57" @default.
• W1991465229 countsByYear W19914652292012 @default.
• W1991465229 countsByYear W19914652292013 @default.
• W1991465229 countsByYear W19914652292014 @default.
• W1991465229 countsByYear W19914652292015 @default.
• W1991465229 countsByYear W19914652292016 @default.
• W1991465229 countsByYear W19914652292017 @default.
• W1991465229 countsByYear W19914652292018 @default.
• W1991465229 countsByYear W19914652292020 @default.
• W1991465229 countsByYear W19914652292021 @default.
• W1991465229 countsByYear W19914652292023 @default.
• W1991465229 crossrefType "journal-article" @default.
• W1991465229 hasAuthorship W1991465229A5038347649 @default.
• W1991465229 hasAuthorship W1991465229A5057022689 @default.
• W1991465229 hasAuthorship W1991465229A5060790939 @default.
• W1991465229 hasAuthorship W1991465229A5080338371 @default.
• W1991465229 hasConcept C112243037 @default.
• W1991465229 hasConcept C178790620 @default.
• W1991465229 hasConcept C181199279 @default.
• W1991465229 hasConcept C185592680 @default.
• W1991465229 hasConcept C2776134268 @default.
• W1991465229 hasConcept C2777278459 @default.
• W1991465229 hasConcept C2777671706 @default.
• W1991465229 hasConcept C43617362 @default.
• W1991465229 hasConcept C55493867 @default.
• W1991465229 hasConcept C71240020 @default.
• W1991465229 hasConceptScore W1991465229C112243037 @default.
• W1991465229 hasConceptScore W1991465229C178790620 @default.
• W1991465229 hasConceptScore W1991465229C181199279 @default.
• W1991465229 hasConceptScore W1991465229C185592680 @default.
• W1991465229 hasConceptScore W1991465229C2776134268 @default.
• W1991465229 hasConceptScore W1991465229C2777278459 @default.
• W1991465229 hasConceptScore W1991465229C2777671706 @default.

• next