Terpene synthases and pathways in animals: enzymology and structural evolution in the biosynthesis of volatile infochemicals

Tholl, Dorothea; Rebholz, Zarley; Morozov, Alexandre V.; O’Maille, Paul E.

doi:10.1039/d2np00076h

Cited by 12 publications

(7 citation statements)

References 174 publications

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“…TSs have now been discovered and characterized from various kingdoms of life, ,− but scaling terpenoid production to levels suitable for industry using heterologous expression of precursor pathways and TSs in microbes (e.g., E. coli) presents major roadblocks.…”

Section: Introductionmentioning

confidence: 99%

Decoding Catalysis by Terpene Synthases

Whitehead,

Leferink,

Johannissen

et al. 2023

ACS Catal.

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The review by Christianson, published in 2017 on the twentieth anniversary of the emergence of the field, summarizes the foundational discoveries and key advances in terpene synthase/cyclase (TS) biocatalysis (Christianson, D. W. Chem Rev 2017, 117 (17), 11570–11648. DOI: 10.1021/acs.chemrev.7b00287). Here, we review the TS literature published since then, bringing the field up to date and looking forward to what could be the near future of TS rational design. Many revealing discoveries have been made in recent years, building on the knowledge and fundamental principles uncovered during those initial two decades of study. We use these to explore TS reaction chemistry and see how a combined experimental and computational approach helps to decipher the complexities of TS catalysis. Revealed are a suite of catalytic motifs which control product outcome in TSs, some obvious, some more subtle. We examine each in detail, using the most recent papers and insights to illustrate how exactly this fascinating class of enzymes takes a single acyclic substrate and turns it into the many thousands of complex terpenoids found in Nature. We then explore some of the recent strategies for TS engineering, including machine learning and other data-driven approaches. From this, rational and predictive engineering of TSs, “designer terpene synthases”, will begin to emerge as a realistic goal.

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Section: Introductionmentioning

confidence: 99%

Decoding Catalysis by Terpene Synthases

Whitehead,

Leferink,

Johannissen

et al. 2023

ACS Catal.

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“…Terpenoids are known for their extensive evolutionary divergence, with many instances of lineage-specific pathways and, therefore, metabolites. Despite the occurrence of many common and unique terpenoids in animals, terpenoid diversification is better understood in plants and microbes (Beran et al, 2019; Tholl et al, 2023). In plants, terpenoid diversity is mainly determined by the activity of TPSs, which have high evolutionary divergence and functional plasticity (Karunanithi and Zerbe, 2019).…”

Section: Discussionmentioning

confidence: 99%

Identification and characterisation ofPlanococcus citri cis- andtrans-isoprenyl diphosphate synthase genes, supported by short- and long-read transcriptome data

Juteršek

Gerasymenko

Petek

et al. 2023

Preprint

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Many insect species rely on diverse terpenoids for their development and interorganismal interactions. However, little is known about terpenoid biosynthesis in insects. The monoterpenoid sex pheromones of mealybugs and scale insects (Coccoidea) are particularly enigmatic, with several species producing unique structures presumed to result from the irregular coupling activity of unidentified isopentenyl diphosphate synthases (IDSs). Enzymes capable of similar transformations have previously only been described from a few plant, bacterial and archaeal species. To investigate if insect irregular monoterpenes can be biosynthesised by similar enzymes, we performed a comprehensive search for IDS coding sequences in the genome ofPlanococcus citri, a widespread agricultural pest. We complemented the availableP. citrigenome data with newly generated short- and long-read transcriptome data. The identified candidate genes had homology to both short- and long-chain IDSs and some appeared to be paralogous, indicating gene duplications and consequent IDS gene family expansion inP. citri. We tested the activity of eleven candidate gene products, confirming in vitro regular activity for five enzymes, one of which (transIDS5) also produced the irregular prenyl diphosphates, maconelliyl and lavandulyl diphosphate. Targeted mutagenesis of selected aspartates and a lysine in the active site oftransIDS5 uncovered their importance for chain length preference and irregular coupling. This work provides an important foundation for deciphering terpenoid biosynthesis in mealybugs, as well as a potential source of enzymes for the biotechnological production of sustainable insect pest management products.

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“…298 They are mainly produced by various plants, fungi and some animals, and rarely by bacteria, which are responsible for characteristic scents and avours, in many cases as a defense strategy of the producer. [299][300][301][302][303][304] The condensation of isoprene results in the creation of a linear polyene structure with methyl group branches in a single step facilitated by terpene synthases. 305 Following this initial formation, the terpenoid building blocks can undergo various post-modications, including oxidation, reduction, cyclization, rearrangement, and the addition of sugar, amino acids, or fatty acids, contributing to the diverse array of terpenoid structures and functionalities found in nature.…”

Section: Reviewmentioning

confidence: 99%