Item type:Thesis, Open Access

Investigations on the formation of rosmarinic acid in Anthoceros agrestis and Melissa officinalis.

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Philipps-Universität Marburg

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Abstract

Rosmarinic acid (RA) is a natural product found in Anthoceros agrestis with amounts of up to 4 % of dry weight investigated in this work. The biosynthetic pathway for RA has been fully elucidated for Plectranthus scutellarioides with L-tyrosine and L-phenylalanine serving as precursors. An essential step in this biosynthesis is the ester linkage of 4-coumaroyl-CoA and 4-hydroxyphenyllactate by rosmarinic acid synthase (RAS) to form 4-coumaroyl-4’-hydroxyphenyllactate which is then further hydroxylated to form RA. However, for A. agrestis no ortholog to RAS has been found. With RAS being an acyltransferase of the BAHD family a search for sequences containing conserved motifs characteristic for BAHD acyltransferases resulted in several sequences, with AaHCT6 being the most similar to RAS from P. scutellarioides. However, investigations on heterologously expressed AaHCT6 showed, that it does not catalyze the reaction of 4-coumaroyl-CoA and 4-hydroxyphenyllactate or 3,4-dihydroxyphenyllactate, as it was initially proposed (Petersen et al. 1993; Petersen 1997; Petersen and Simmonds 2002). A catalogue of 55 potential acceptor substrates was tested for acceptance by AaHCT6 and resulted in acceptance for shikimate, 3-hydroxyanthranilate and 2,3-dihydroxybenzoate with caffeoyl-CoA and 4-coumaroyl-CoA as donor substrates. Enzyme kinetic measurements revealed the highest affinity for 4-coumaroyl-CoA as donor substrate and shikimate as acceptor substrate, followed by 3-hydroxyanthranilate and 2,3- dihydroxybenzoate. For 3-hydroxyanthranilate the product formation occurs via amide linkage, 173 whereas with shikimate and 2,3-dihydroxybenzoate product formation occurs via ester linkage. AaHCT1 was successfully amplified from total RNA, ligated into several expression vectors and introduced into prokaryotic and eukaryotic organisms for heterologous expression. However, an expression of the protein of interest was not successful. AaHCT2 was successfully expressed in E. coli and investigations on substrate acceptance revealed an acceptance for two small alkanols as acceptor substrates, methanol and ethanol, with caffeoyl-CoA as donor substrates. AaHCT5 was successfully expressed in E. coli as verified by Western blot. However, no substrate accepted by this enzyme was found out of the catalogue of 55 potential substrates. The sequence coding for AaHCT7, although discovered in a late stage of this work, was successfully amplified from total RNA. An incorporation into the vector pDrive was successful as verified by sequencing. However, an incorporation into the expression vector pET-15b was not successful as it was implemented in a reverse orientation as verified by sequencing. To date, the ester- forming step of the rosmarinic acid pathway for Anthoceros agrestis is still unclear. Chances are that this step is being catalyzed by an enzyme of the BAHD acyltransferase family, as it is demonstrated for plants of the Lamiaceae family. However, it cannot be ruled out that this step might be catalyzed by an enzyme of a completely different class. Furthermore, it is possible that this step might be catalyzed by an enzyme exhibiting acyltransferase activity but lacking (or deviating from) the conserved sequences typical for BAHD acyltransferases. In addition to elucidating the function and role of HCTs found in A. agrestis, this work also delves into the exploration of electricity as a potential elicitor for the production of the specialized metabolite rosmarinic acid in suspension cultures of Melissa officinalis. Initial experiments involving electric fields demonstrated varying effects on metabolite accumulation, indicating the need for further optimization and investigation into the application of electric current as an elicitor. However, the results showed that the application of a chemical elicitor, methyl jasmonate, consistently outperforms electric stimulation in enhancing RA production, highlighting the economic practicality of methyl jasmonate as a preferred elicitor for specialized metabolite enhancement rather than complex setups with electric wiring.

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Ernst, Lucien: Investigations on the formation of rosmarinic acid in Anthoceros agrestis and Melissa officinalis.. : Philipps-Universität Marburg 2024-12-09. DOI: https://doi.org/10.17192/z2024.0493.