Summary: The plant hormone auxin is believed to influence almost every aspect of plant growth and development. Auxin transport, biosynthesis and degradation combine to form gradients of the hormone that influence a range of key developmental and environmental response processes. There is abundant genetic evidence for the existence of multiple pathways for auxin biosynthesis and degradation. The complexity of these pathways makes it difficult to obtain a clear picture of the relative importance of specific metabolic pathways during development. We have developed a sensitive mass spectrometry‐based method to simultaneously profile the majority of known auxin precursors and conjugates/catabolites in small amounts of Arabidopsis tissue. The method includes a new derivatization technique for quantification of the most labile of the auxin precursors. We validated the method by profiling the auxin metabolome in root and shoot tissues from various Arabidopsis thaliana ecotypes and auxin over‐producing mutant lines. Substantial differences were shown in metabolite patterns between the lines and tissues. We also found differences of several orders of magnitude in the abundance of auxin metabolites, potentially indicating the relative importance of these compounds in the maintenance of auxin levels and activity. The method that we have established will enable researchers to obtain a better understanding of the dynamics of auxin metabolism and activity during plant growth and development.
Strigolactones (SLs) constitute a new class of plant hormones which are active as germination stimulants for seeds of parasitic weeds of Striga, Orobanche, and Pelipanchi spp, in hyphal branching of arbuscular mycorrhizal (AM) fungi and as inhibitors of shoot branching. In this review, the focus is on molecular features of these SLs. The occurrence of SLs in root exudates of host plants is described. The naming protocol for SL according to the International Union of Pure and Applied Chemistry (IUPAC) rules and the 'at a glance' method is explained. The total synthesis of some natural SLs is described with details for all eight stereoisomers of strigol. The problems encountered with assigning the correct structure of natural SLs are analyzed for orobanchol, alectrol, and solanacol. The structure-activity relationship of SLs as germination stimulants leads to the identification of the bioactiphore of SLs. Together with a tentative mechanism for the mode of action, a model has been derived that can be used to design and prepare active SL analogs. This working model has been used for the preparation of a series of new SL analogs such as Nijmegen-1, and analogs derived from simple ketones, keto enols, and saccharine. The serendipitous finding of SL mimics which are derived from the D-ring in SLs (appropriately substituted butenolides) is reported. For SL mimics, a mode of action is proposed as well. Recent new results support this proposal. The stability of SLs and SL analogs towards hydrolysis is described and some details of the mechanism of hydrolysis are discussed as well. The attempted isolation of the protein receptor for germination and the current status concerning the biosynthesis of natural SLs are briefly discussed. Some non-SLs as germinating agents are mentioned. The structure-activity relationship for SLs in hyphal branching of AM fungi and in repression of shoot branching is also analyzed. For each of the principle functions, a working model for the design of new active SL analogs is described and its applicability and implications are discussed. It is shown that the three principal functions use a distinct perception system. The importance of stereochemistry for bioactivity has been described for the various functions.
Main conclusion The key step in the mode of action of strigolactones is the enzymatic detachment of the D-ring. The thus formed hydroxy butenolide induces conformational changes of the receptor pocket which trigger a cascade of reactions in the signal transduction. Abstract Strigolactones (SLs) constitute a new class of plant hormones which are of increasing importance in plant science. For the last 60 years, they have been known as germination stimulants for parasitic plants. Recently, several new bio-properties of SLs have been discovered such as the branching factor for arbuscular mycorrhizal fungi, regulation of plant architecture (inhibition of bud outgrowth and of shoot branching) and the response to abiotic factors, etc. To broaden horizons and encourage new ideas for identifying and synthesising new and structurally simple SLs, this review is focused on molecular aspects of this new class of plant hormones. Special attention has been given to structural features, the mode of action of these phytohormones in various biological actions, the design of SL analogs and their applications.
1 October 2020 in Plant Physiology and Biochemistry
Preparation of graphene derivatives using fluorographene (FG) as a precursor has become a key strategy for the large-scale synthesis of new 2-D materials (e.g. graphene acid, cyanographene, allyl-graphene) with tailored physicochemical properties. However, to gain full control over the derivatization process, it is essential to understand the reaction mechanisms and accompanying processes that affect the composition and structure of the final products. Despite the strength of C–F bonds and high chemical stability of perfluorinated hydrocarbons, FG is surprisingly susceptible to reactions under ambient conditions. There is clear evidence that nucleophilic substitution on FG is accompanied by spontaneous defluorination, and solvent-induced defluorination can occur even in the absence of any nucleophilic agent. Here, we show that distributed radical centers (fluorine vacancies) on the FG surface need to be taken into account in order to rationalize the defluorination mechanism. Depending on the environment, these radical centers can react as electron acceptors, electrophilic sites and/or cause homolytic bond cleavages. We also propose a new radical mechanism of FG defluorination in the presence of N,N′-dimethylformamide (DMF) solvent. Spin-trap experiments as well as 19F NMR measurements unambiguously confirmed formation of N,N′-dimethylformyl radicals and also showed that N,N′-dimethylcarbamoyl fluoride plays a key role in the proposed mechanism. These findings imply that point defects in 2D materials should be considered as key factor determining their chemical properties and reactivity.