In light of the fact that the main betaxanthin (miraxanthin V) and the major betacyanin (2-descarboxy-betanidin) in hairy root cultures of yellow beet (Beta vulgaris L.) are both dopamine-derived, the occurrence of similar structures for the minor betacyanins was also suggested. By HPLC comparison with the betacyanins obtained by dopamine administration to beet seedlings, enzymatic hydrolysis, LCMS and 1H NMR analyses, the minor betacyanins from hairy roots were identified as 2-descarboxy-betanin and its 6′-O-malonyl derivative. A short-term dopamine administration experiment with fodder beet seedlings revealed that the condensation step between 2-descarboxy-cyclo-Dopa and betalamic acid is the decisive reaction, followed by glucosylation and acylation. From these data a pathway for the biosynthesis of dopamine-derived betalains is proposed. Furthermore, the occurrence of these compounds in various cell and hairy root cultures as well as beet plants (Fodder and Garden Beet Group) is shown.

Combinatorial chemistry is common place today in chemical synthesis. Virtually thousands of derivatives of a molecule can be achieved by automated systems. The use of biological systems to exploit combinatorial chemistry (combinatorial biochemistry) now has multiple examples in the polyketide field. The modular functional domain structure of polyketide synthases have been recombined through genetic engineering into unnatural constellations in heterologous hosts in order to produce polyketide structures not yet discovered in nature. We present herein an example for a potential type of combinatorial biochemistry in alkaloidal systems using various combinations of Thalictrum tuberosum (meadow rue) O-methyltransferase subunits that result in heterodimeric enzymes with substrate specificities that differ from those of the homodimeric native enzymes.

A series of linear and angular prenylated furanocoumarins and a benzofuran derivative were isolated from leaves and twigs of Dorstenia gigas (Moraceae), a plant occurring endemically on Socotra Island (Yemen). The structures were elucidated by spectroscopic methods (NMR, MS, UV) and chemical derivatization.

Exogenous jasmonate treatment of Nicotiana attenuata Torr. ex Wats. plants elicits durable resistance against herbivores and attack from its specialist herbivore, Manduca sexta, results in an amplification of the transient wound-induced increase in endogenous jasmonic acid levels (JA). To understand whether this “JA burst” is under transcriptional control, we cloned allene oxide synthase (AOS; EC 4.2.1.92), the enzyme that catalyzes the dehydration of 13(S)-hydroperoxy octadecatrienoic acid to an allene oxide, the first specific reaction in JA biosynthesis. An AOS cDNA coding for a 520 aa protein (58.6 kDa) with an isoelectric point of 8.74 was overexpressed in bacteria and determined to be a functional AOS. Southern blot analysis indicated the presence of more than one gene and AOS transcripts were detected in all organs, with the highest levels in stems, stem leaves and flowers. Attack by M. sexta larvae resulted in a sustained JA burst producing an endogenous JA amount 9-fold above control levels and 3-fold above maximum wound-induced levels, a response which could be mimicked by the addition of Manduca oral secretion and regurgitant to puncture wounds. M. sexta attack, wounding and regurgitant treatment transiently increased AOS transcript in the wounded leaf, but increases were not proportional to the JA response. Moreover, transcript accumulation lagged behind JA accumulation. Systemic wound-induced increases in AOS transcript, AOS activity or JA accumulation could not be detected. We conclude that increase in AOS transcript does not contribute to the initial increase in endogenous JA, but may contribute to sustaining the JA burst.The accumulation of allene oxide synthase transcripts after mechanical wounding, treatment with larval regurgitant, and herbivore attack are compared and correlated with the respective jasmonic acid accumulation.

The betalains of yellow, orange and red inflorescences of common cockscomb (Celosia argentea var. cristata) were compared and proved to be qualitatively identical to those of feathered amaranth (Celosia argentea var. plumosa). In addition to the known compounds amaranthin and betalamic acid, the structures of three yellow pigments were elucidated to be immonium conjugates of betalamic acid with dopamine, 3-methoxytyramine and (S)-tryptophan by various spectroscopic techniques and comparison to synthesized reference compounds; the latter two are new to plants. Among the betacyanins occurring in yellow inflorescences in trace amounts, the presence of 2-descarboxy-betanidin, a dopamine-derived betacyanin, has been ascertained. The detection of high dopamine concentration may be of toxicological relevance in use of yellow inflorescences as a vegetable and in traditional Chinese medicine, common uses for the red inflorescences of common cockscomb.The betaxanthins of two Celosia argentea varieties were identified as betalamic acid conjugates of dopamine (1), 3-methoxytyramine (2) and (S)-tryptophan.

The patterns of secondary metabolites in leaves of yeast invertase-transgenic tobacco plants (Nicotiana tabacum L. cv. Samsun NN) were analyzed. Plants expressing cytosolic yeast-derived invertase (cytInv) or apoplastic (cell wall associated) yeast invertase (cwInv) showed a characteristic phytochemical phenotype compared to untransformed controls (wild-type plants). The level of phenylpropanoids decreased in the cytInv plants but increased in the cwInv plants, which showed an induced de novo synthesis of a caffeic acid amide, i.e. N-caffeoylputrescine. In addition, the level of the coumarin glucoside scopolin was markedly enhanced. Increased accumulation of scopolin in the cwInv plants is possibly correlated with the induction of defense reactions and the appearance of necrotic lesions similar to the hypersensitive response caused by avirulent pathogens. This is consistent with results from potato virus Y-infected plants. Whereas there was no additional increase in the coumarins in leaves following infection in cwInv plants, wild-type plants showed a slight increase and cytInc a marked increase.