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Aliphatic compounds on plant surfaces, called epicuticular waxes, are the first line of defense against pathogens and pests, contribute to reducing water loss and determine other important phenotypes. Aliphatics can form crystals affecting light refraction, resulting in a color change and allowing identification of mutants in their synthesis or transport. The present study discloses three such Eceriferum (cer) genes in barley – Cer-c, Cer-q and Cer-u – known to be tightly linked and functioning in a biochemical pathway forming dominating amounts of β-diketone and hydroxy-β-diketones plus some esterified alkan-2-ols. These aliphatics are present in many Triticeae as well as dicotyledons such as Eucalyptus and Dianthus. Recently developed genomic resources and mapping populations in barley defined these genes to a small region on chromosome arm 2HS. Exploiting Cer-c and -u potential functions pinpointed five candidates, of which three were missing in apparent cer-cqu triple mutants. Sequencing more than 50 independent mutants for each gene confirmed their identification. Cer-c is a chalcone synthase-like polyketide synthase, designated diketone synthase (DKS), Cer-q is a lipase/carboxyl transferase and Cer-u is a P450 enzyme. All were highly expressed in pertinent leaf sheath tissue of wild type. A physical map revealed the order Cer-c, Cer-u, Cer-q with the flanking genes 101 kb apart, confirming they are a gene cluster, Cer-cqu. Homology-based modeling suggests that many of the mutant alleles affect overall protein structure or specific active site residues. The rich diversity of identified mutations will facilitate future studies of three key enzymes involved in synthesis of plant apoplast waxes.

A couple of novel crystalline aluminum(III) derivatives containing tridentate Schiff base ligand (HL) and β‐diketones (acetylacetone = acac, benzoylacetone = bnzac, and dibenzoylmethane = dbnz), namely, [Al(L)bnzac] [Al1], [Al(L)dnbz] [Al2], and [Al(L)acac] [Al3], are synthesized and characterized using different spectroscopic techniques and elemental analysis. Single crystal X‐ray diffraction analysis of Al2 and Al3 exhibits hexacoordinated geometry around aluminum center atom which is also confirmed using density functional theory (DFT). The ring‐opening polymerization (ROP) of caprolactone is evaluated to determine the catalytic potential of the complexes Al1–Al3 in the absence and presence of benzyl alcohol (BnOH). The effect of time and temperature is also examined and found that lesser steric effects of the ancillary ligand causes a higher polymerization rate. Gel permeation chromatography (GPC) is used to determine the molecular weight (Mn & Mw) and dispersity (Đ) values of polycaprolactone. Within first 2 h, Al3 exhibits excellent catalytic activity with 99% conversion at 110 °C (MnGPC = 1948 gmol−1, MwGPC = 2865 gmol−1, and Đ = 1.47). An end‐group study is performed using matrix‐assisted laser desorption ionization‐time of flight (MALDI‐TOF) spectrometry, and 1H NMR spectral analysis. Also, PCL is characterized using elemental, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analyses. First‐order kinetics are found in the monomer aligned with the activated monomer mechanism for the catalysts. Ring‐opening polymerization of ε‐caprolactone using Al(III) heteroleptic complexes containing tridentate Schiff base ligand and β‐diketones is evaluated to determine the catalytic potential of Al(III) complexes in absence as well as in presence of benzyl alcohol.

Societal Impact Statement In blueberry, fruit color is one of the most important quality traits affecting consumers' choices. Both pigments and waxes impact fruit color; however, their roles have not been clearly elucidated. Here, the contributions of waxes and anthocyanins to fruit color are characterized. A higher content of β‐diketones—the second largest wax group in blueberries—determines a lighter fruit color; hence revealing that, at harvest, waxes contribute more than anthocyanins in determining variations in fruit color among blueberry varieties. Summary Fruit color is one of the major quality traits determining the marketability of fruits by affecting consumers' choices. In blueberries, although fruit surface color is mainly determined by pigments (e.g., anthocyanins), cuticular waxes also play a role in modulating the surface color, and a lighter color given by a dense wax bloom is normally preferred by consumers. This study investigated the content and composition of cuticular waxes and their roles in modulating fruit surface color in 12 (seven northern highbush, three southern highbush, and two hybrids) blueberry genotypes at harvest (H1, representing the first commercial pick, and H2, representing the second commercial pick). The ultrastructural morphology of cuticular waxes was analyzed in four selected genotypes by scanning electron microscopy. The level and profile of anthocyanins and their contributions to the color were also assessed. Total cuticular wax content ranged from 27.7 to 95.8 μg cm−2 among genotypes at H1 and decreased by an average of 23.9% from H1 to H2. Triterpenoids (62.5% of the total cuticular waxes on average) and β‐diketones (22.9% on average) were the first and second largest wax groups in all genotypes, respectively. β‐Diketones were previously proven to affect leaf surface color in wheat; in this study, their content strongly correlated with the lightness of the blueberry surface. Scanning electron microscopy revealed distinct wax morphologies among genotypes. No significant relationships were found between total or individual anthocyanin concentrations and fruit surface color. Our results suggest that, at harvest, variation in the fruit surface color among blueberry genotypes is more closely related to the content and composition of cuticular waxes than the level and profile of anthocyanins, with β‐diketones being particularly important. This study provides new insights for blueberry breeding programs aiming to improve the surface color in order to meet the market demand. In blueberry, fruit color is one of the most important quality traits affecting consumers' choices. Both pigments and waxes impact fruit color; however, their roles have not been clearly elucidated. Here, the contributions of waxes and anthocyanins to fruit color are characterized. A higher content of β‐diketones—the second largest wax group in blueberries—determines a lighter fruit color; hence revealing that, at harvest, waxes contribute more than anthocyanins in determining variations in fruit color among blueberry varieties.

A number of hitherto unknown trifluorinated beta-diketone oxymes were obtained by direct nitrosation with sodium nitrite in an acidic medium. 4,4,4-Trifluoro-2-(hydroxyimino)-1-(thiophene-2-yl)butane-1,3-dione and 4,4,4-trifluoro-2-(hydroxyimino)-1-phenylbutane-1,3-dione have been characterized by various physicochemical methods. The structure of the formed compounds was confirmed using FTIR, UV-visible spectroscopy, NMR and GC-MS. The spectral characteristics of the obtained compounds were modeled using DFT and TD-DFT calculations.

Cuticular waxes coating leaf surfaces can help plants tolerate drought events by reducing non-stomatal water loss. Despite their role in drought tolerance, little is known about how cuticular wax composition has changed during breeding in Canadian bread wheat ( Triticum aestivum L.) varieties. To fill in this gap, flag leaves of the Canadian Heritage Bread Wheat Panel, which include 30 varieties released between 1842 and 2018, were surveyed to determine if and how cuticular wax composition in wheat has changed at two breeding ecozones over this period. Following this, a subset of varieties was subjected to drought conditions to compare their responses. As expected, modern varieties outperformed old varieties with a significantly larger head length and reaching maturity earlier. Yet, when challenged with drought, old varieties were able to significantly increase the accumulation of β-diketones to a higher extent than modern varieties. Furthermore, RNAseq was performed on the flag leaf of four modern varieties to identify potential markers that could be used for selection of higher accumulation of cuticular waxes. This analysis revealed that the W1 locus is a good candidate for selecting higher accumulation of β-diketones. These findings indicate that the variation in cuticular waxes upon drought could be further incorporated in breeding of future bread wheat varieties.

Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing carbon dioxide as double synthons via bimolecular reduction remains challenging. Here, by leveraging the bimolecular reduction of carbon dioxide to carbonyl and methyl respectively, we describe a Pd-catalyzed trifunctionalization of alkynes with aryl iodide for the first time and showcase its advantages on the formation of various β-diketones and their application in the constructing of heterocyclic compounds with important biological activity, including pyrimidine, oxazole, pyrazole

Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N -heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations. Axially chiral compounds are commonly found in nature. Here, the authors show the highly enantioselective construction of axially chiral biaryls via an N -heterocyclic carbenes-catalyzed [3+3] atroposelective annulation of ynals with cyclic 1,3-diones.

In this issue of Journal of Experimental Botany (pages 2715–2730) Schneider et al. report the identity of three genes from barley described in the 1970s as important for the synthesis of β-diketone cuticular waxes, thereby revealing a novel polyketide synthase pathway responsible for their production. It is a perfect example of how modern sequencing technologies can resolve age-old questions on important food crops.

In this study, β-diketone derivative new carboxamide Eu(III) and Tb(III) lanthanide complexes were synthesized and characterized by FT-IR, elemental analysis, UV–Vis, and molar conductivity techniques. There is no electrolytic conductivity in the compounds. Moreover, the photoluminescence properties and thermal behavior of the synthesized lanthanide complexes were investigated. Photoluminescence data revealed that the Tb(III) complex showed metal-based f-f transitions. The β-diketone derivative carboxamide ligand exhibited as antenna that transmitted the excited energy to the emission energy levels of the Tb(III) ion. These metal complexes were screened in two different common cancer cell lines and a human normal embryonic kidney cell line for 48 h. The results showed that these complexes have more antiproliferative activities in the colon cancer cell line compared to the lung cancer cell line.

As the simplest alkyne and an abundant chemical feedstock, acetylene is an ideal two-carbon building block. However, in contrast to substituted alkynes, catalytic methods to incorporate acetylene into fine chemicals are quite limited. Herein, we developed a photoredox-catalyzed synthetic protocol for diverse C2-linked molecules via a molecular glue strategy using gaseous acetylene under mild conditions. Initiated by addition of an acyl radical to acetylene, two cascade transformations follow. One involves a double addition for the formation of 1,4-diketones and the other where the intermediate vinyl ketone is intercepted by a radical formed from a heterocycle. In addition to making two new C-C bonds, two C-H bonds are also created in two mechanistically distinct ways: one via a C-H abstraction and the other via protonation. This system offers a reliable and safe way to incorporate gaseous acetylene into fine chemicals and expands the utility of acetylene in organic synthesis. Although acetylene is an ideal two-carbon building block, very few catalytic methods can be applied to incorporate acetylene into fine chemicals. Here, the authors show photoredox-catalyzed syntheses of C2- linked molecules with gaseous acetylene under mild conditions.