HORMESIS AND A CHEMICAL RAISON D’ÊTRE FOR SECONDARY PLANT METABOLITES

In plants, accumulation in specific compartments and huge structural diversity of secondary metabolites is one trait that is not understood yet. By exploring the diverse abiotic and biotic interactions of plants above- and belowground, we provide examples that are characterized by nonlinear effects of the secondary metabolites. We propose that redox chemistry, specifically the reduction of reactive oxygen species (ROS) and, in their absence, reduction of molecular oxygen by the identical secondary metabolite, is an important component of the hormetic effects caused by these compounds. This is illustrated for selected phenols, terpenoids, and alkaloids. The redox reactions are modulated by the variable availability of transition metals that serve as donors of electrons in a Fenton reaction mode. Low levels of ROS stimulate growth, cell differentiation, and stress resistance; high levels induce programmed cell death. We propose that provision of molecules that can participate in this redox chemistry is the raison d’être for secondary metabolites. In this context, the presence or absence of functional groups in the molecule is more essential than the whole structure. Accordingly, there exist no constraints that limit structural diversity. Redox chemistry is ubiquitous, from the atmosphere to the soil

(±)-Catechin: Chemical Weapon, Antioxidant, or Stress Regulator?

(±)-Catechin is a flavan-3-ol that occurs in the organs of many plant species, especially fruits. Health-beneficial effects have been studied extensively, and notable toxic effects have not been found. In contrast, (±)-catechin has been implicated as a ‘chemical weapon’ that is exuded by the roots of Centaurea stoebe, an invasive knapweed of northern America. Recently, this hypothesis has been rejected based on (±)-catechin’s low phytotoxicity, instability at pH levels higher than 5, and poor recovery from soil. In the current study, (±)-catechin did not inhibit the development of white and black mustard to an extent that was comparable to the highly phytotoxic juglone, a naphthoquinone that is allegedly responsible for the allelopathy of the walnut tree. At high stress levels, caused by sub-lethal methanol concentrations in the medium, and a 12 h photoperiod, (±)-catechin even attenuated growth retardation. A similar effect was observed when (±)-catechin was assayed for brine shrimp mortality. Higher concentrations reduced the mortality caused by toxic concentrations of methanol. Further, when (±)-catechin was tested in variants of the deoxyribose degradation assay, it was an efficient scavenger of reactive oxygen species (ROS) when they were present in higher concentrations. This antioxidant effect was enhanced when iron was chelated directly by (±)-catechin. Conversely, if iron was chelated to EDTA, pro-oxidative effects were demonstrated at higher concentrations; in this case (±)-catechin reduced molecular oxygen and iron to reagents required by the Fenton reaction to produce hydroxyl radicals. A comparison of cyclic voltammograms of (±)-catechin with the phytotoxic naphthoquinone juglone indicated similar redox-cycling properties for both compounds although juglone required lower electrochemical potentials to enter redox reactions. In buffer solutions, (±)-catechin remained stable at pH 3.6 (vacuole) and decomposed at pH 7.4 (cytoplasm) after 24 h. The results support the recent rejection of the hypothesis that (±)-catechin may serve as a ‘chemical weapon’ for invasive plants. Instead, accumulation and exudation of (±)-catechin may help plants survive periods of stress

Pseudogap in a thin film of a conventional superconductor

A superconducting state is characterized by the gap in the electronic density of states which vanishes at the superconducting transition temperature Tc. It was discovered that in high temperature superconductors a noticeable depression in the density of states still remains even at temperatures above Tc; this feature being called pseudogap. Here we show that a pseudogap exists in a conventional superconductor: ultrathin titanium nitride films over a wide range of temperatures above Tc. Our study reveals that this pseudogap state is induced by superconducting fluctuations and favored by two-dimensionality and by the proximity to the transition to the insulating state. A general character of the observed phenomenon provides a powerful tool to discriminate between fluctuations as the origin of the pseudogap state, and other contributions in the layered high temperature superconductor compounds.Comment: 26 pages, 4 figure

Secondary or Specialized Metabolites, or Natural Products: A Case Study of Untargeted LC–QTOF Auto-MS/MS Analysis

The large structural diversity of specialized metabolites represents a substantial challenge in untargeted metabolomics. Modern LC–QTOF instruments can provide three- to four-digit numbers of auto-MS/MS spectra from sample sets. This case study utilizes twelve structurally closely related flavonol glycosides, characteristic specialized metabolites of plant tissues, some of them isomeric and isobaric, to illustrate the possibilities and limitations of their identification. This process requires specific software tools that perform peak picking and feature alignment after spectral deconvolution and facilitate molecular structure base searching with subsequent in silico fragmentation to obtain initial ideas about possible structures. The final assignment of a putative identification, so long as spectral databases are not complete enough, requires structure searches in a chemical reference database, such as SciFindern, in attempts to obtain additional information about specific product ions of a metabolite candidate or check its feasibility. The highlighted problems in this process not only apply to specialized metabolites in plants but to those occurring in other organisms as well. This case study is aimed at providing guidelines for all researchers who obtain data from such analyses but are interested in deeper information than just Venn diagrams of the feature distribution in their sample groups

Oxygen, life forms, and the evolution of sexes in multicellular eukaryotes

The evolutionary advantage of different sexual systems in multicellular eukaryotes is still not well understood, because the differentiation into male and female individuals halves offspring production compared with asexuality. Here we propose that various physiological adaptations to oxidative stress could have forged sessility versus motility, and consequently the evolution of sexual systems in multicellular animals, plants, and fungi. Photosynthesis causes substantial amounts of oxidative stress in photoautotrophic plants and, likewise, oxidative chemistry of polymer breakdown, cellulose and lignin, for saprotrophic fungi. In both cases, its extent precludes motility, an additional source of oxidative stress. Sessile life form and the lack of neuronal systems, however, limit options for mate recognition and adult sexual selection, resulting in inefficient mate-searching systems. Hence, sessility requires that all individuals can produce offspring, which is achieved by hermaphroditism in plants and/or by multiple mating types in fungi. In animals, motility requires neuronal systems, and muscle activity, both of which are highly sensitive to oxidative damage. As a consequence, motility has evolved in animals as heterotrophic organisms that (1) are not photosynthetically active, and (2) are not primary decomposers. Adaptations to motility provide prerequisites for an active mating behavior and efficient mate-searching systems. These benefits compensate for the 'cost of males', and may explain the early evolution of sex chromosomes in metazoans. We conclude that different sexual systems evolved under the indirect physiological constraints of lifestyles

Quinolinic Acid: Neurotoxin or Oxidative Stress Modulator?

Quinolinic acid (2,3-pyridinedicarboxylic acid, QUIN) is a well-known neurotoxin. Consequently, QUIN could produce reactive oxygen species (ROS). ROS are generated in reactions catalyzed by transition metals, especially iron (Fe). QUIN can form coordination complexes with iron. A combination of differential pulse voltammetry, deoxyribose degradation and Fe(II) autoxidation assays was used for explorating ROS formation in redox reactions that are catalyzed by iron in QUIN-Fe complexes. Differential pulse voltammetry showed an anodic shift of the iron redox potential if iron was liganded by QUIN. In the H2O2/FeCl3/ascorbic acid variant of the deoxyribose degradation assay, the dose-response curve was U-shaped. In the FeCl3/ascorbic acid variant, QUIN unambiguously showed antioxidant effects. In the Fe(II) autoxidation assay, QUIN decreased the rate of ROS production caused by Fe(II) oxidation. Our study confirms that QUIN toxicity may be caused by ROS generation via the Fenton reaction. This, however, applies only for unnaturally high concentrations that were used in attempts to provide support for the neurotoxic effect. In lower concentrations, we show that by liganding iron, QUIN affects the Fe(II)/Fe(III) ratios that are beneficial to homeostasis. Our results support the notion that redox chemistry can contribute to explaining the hormetic dose-response effects