We report a detailed investigation into the nature of products that are generated by the reactions of cyanamide and glyoxal, two small molecules of astrochemical and prebiotic significance, under different experimental conditions. The experimental data suggest that the formation of oligomeric structures is related in part to the formation of insoluble tholins in the presence of oxygen-containing molecules. Although oligomerization proceeds well in water, product isolation turned out to be impractical. Instead, solid precipitates were obtained easily in acetone. Crude mixtures have been thoroughly scrutinized by spectroscopic methods, in particular NMR and mass spectroscopy (ESI mode), which are all consistent with the generation of a few functional groups that are embedded into regular chains of five- and six-membered rings, thereby pointing to a supramolecular organization. Three different models of cross-condensation and chain growth are suggested. These synthetic explorations provide further insights into the formation of complex organic matter in interstellar scenarios and extraterrestrial bodies that might have played a pivotal role in chemical evolution.

In many viticulture regions, multiple summer stresses are occurring with increased frequency and severity because of warming trends. Kaolin-based particle film technology is a technique that can mitigate the negative effects of intense and/or prolonged drought on grapevine physiology. Although a primary mechanism of action of kaolin is the increase of radiation reflection, some indirect effects are the protection of canopy functionality and faster stress recovery by abscisic acid (ABA) regulation. The physiological mechanism underlying the kaolin regulation of canopy functionality under water deficit is still poorly understood. In a dry-down experiment carried out on grapevines, at the peak of stress and when control vines zeroed whole-canopy net CO2 exchange rates/leaf area (NCER/LA), kaolin-treated vines maintained positive NCER/LA (~2 µmol m−2 s−1) and canopy transpiration (E) (0.57 µmol m−2 s−1). Kaolin-coated leaves had a higher violaxanthin (Vx) + antheraxanthin (Ax) + zeaxanthin (Zx) pool and a significantly lower neoxanthin (Nx) content (VAZ) when water deficit became severe. At the peak of water shortage, leaf ABA suddenly increased by 4-fold in control vines, whereas in kaolin-coated leaves the variation of ABA content was limited. Overall, kaolin prevented the biosynthesis of ABA by avoiding the deviation of the VAZ epoxidation/de-epoxidation cycle into the ABA precursor (i.e., Nx) biosynthetic direction. The preservation of the active VAZ cycle and transpiration led to an improved dissipation of exceeding electrons, explaining the higher resilience of canopy functionality expressed by canopies sprayed by kaolin. These results point out the interaction of kaolin with the regulation of the VAZ cycle and the active mechanism of stomatal conductance regulation.

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A novel bud-forcing technique aimed at obtaining two crops (primary and forced) within the same season was tested on potted Pinot noir grapevines. Removing young, vegetative organs from primary shoots trimmed to six nodes in early summer allows dormant buds to break para-dormancy, leading to a delayed, second crop. Meanwhile, the primary crop is left untouched. In our study, bud-forcing was applied at three different timings (full flowering, fruit-set, groat-sized berries) and compared with an unforced control (UC). Vegetative growth, yield components, shoot and vine balance as leaf area-to-yield ratios, leaf gas exchange, and grape composition were determined. Regardless of the timing of application, forcing was effective at unlocking either apical or sub-apical dormant buds on the trimmed shoot, whereas the more basal nodes stayed dormant. The additional crop present on forced shoots was 40%–50% of primary crop, which equated to approximately 1 kg/vine for all treatments. Fruitfulness on newly formed forced shoots varied from 0.8 to 1.1 clusters/shoot. Primary clusters in vines subjected to forced treatments reached target maturity with a delay of 7–12 days compared to UC, whereas forced-crop, picked at the latest available date (October 7) showed higher total soluble solids, anthocyanins and phenolics than the primary crop while retaining higher acidity. This ripening behavior was reflected in the higher A rates measured in late season on the basal leaves of forced shoots versus those of primary shoots. Forcing did not compromise fruitfulness of the basal primary nodes, which set at about 1.2 inflorescence primordia/shoot. This is the first report supporting the feasibility of double cropping in Vitis vinifera L. in warm viticulture regions.

Complex matter involving urea and glyoxal mixtures mostly consist of non-aromatic heterocyclic growing units.

“Crop-forcing” is an effective technique to delay grape maturation to a period of lower temperatures, and in this way, improve grape quality. Because of the aggressiveness of this technique (removal of leaves and fruit to reinitiate a second vegetative cycle), it may affect the level of reserves and could provoke progressive vine exhaustion. The aim of the present work is to evaluate the short- and medium-term evolution of carbohydrate reserves in different plant organs and the effect of “crop-forcing” under different irrigation regimes on seasonal biomass production and its distribution. The study was carried out over a four years period (2017–2020), applying “crop-forcing” in three consecutive years (2017–2019) to the same vines on two different dates and using two irrigation strategies. The application of “crop-forcing” did not decrease root reserve levels in either the year of application or the following year, but did modify starch and soluble sugar levels in shoots and leaves in some moments of the vegetative cycle during the years of “crop-forcing” application. Total biomass production in terms of grams per vine was lower in the “crop-forcing” treatments and continued to be so when “crop-forcing” was no longer applied. The percentage of biomass in vegetative organs increased at the expense of productive organs.

We revisit herein the formation and structure of dihydroxy dioxanes, which can be obtained from prebiotically available precursors and can be regarded as primeval sugar surrogates. Previous studies dealing with the heterogeneous composition of interstellar bodies point to the existence of significant amounts of small polyalcohols along with oxygen-containing oligomers. Even though such derivatives did not give rise to nucleosides and oligonucleotides, nor they were incorporated into subsequent metabolic routes, molecular chimeras based on sugar-like species could be opportunistic scaffolds in pre-evolutionary scenarios. We could figure out that pseudosugars, assembled by hemiacetalic bonds from available precursors in both interstellar and terrestrial scenarios, were presumably more abundant than thought. Moreover, these species share some key features with naturally-occurring sugar rings, such as anomeric preferences, coordinating ability, and the prevalent occurrence of racemic compounds.

The condensation of cyanamide and glyoxal, two well-known prebiotic monomers, in an aqueous phase has been investigated in great detail, demonstrating the formation of oligomeric species of varied structure, though consistent with generalizable patterns. This chemistry involving structurally simple substances also illustrates the possibility of building molecular complexity under prebiotically plausible conditions, not only on Earth, but also in extraterrestrial scenarios. We show that cyanamide-glyoxal reactions in water lead to mixtures comprising both acyclic and cyclic fragments, largely based on fused five- and six-membered rings, which can be predicted by computation. Remarkably, such a mixture could be identified using high-resolution electrospray ionization (ESI) mass spectrometry and spectroscopic methods. A few mechanistic pathways can be postulated, most involving the intermediacy of glyoxal cyanoimine and further chain growth, thus increasing the diversity of the observed products. This rationale is supported by theoretical analyses with clear-cut identification of all of the stationary points and transition-state structures. The properties and structural differences of oligomers obtained under thermodynamic conditions in water as opposed to those isolated by precipitation from organic media are also discussed.