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Sorghum (Sorghum bicolor (L.) Moench) produces a range of defense phytochemicals containing a quinone core structure sorgoleone allelochemical, flavonoid phytoalexins, and a broad spectrum of polyphenols. Those phytochemicals react with the components of cellular and agroecosystems to form stable semiquinone radicals engaging in different proton-coupled electron transfer reactions. This unique redox reactivity of plant phenolics could be used to develop bioactive food ingredients and green pesticides. To achieve those application goals, chemical phenotyping methods sensitive to quinone-semiquinone-dihydroxybenzene redox cycles (e.g., electrochemical conversion with fluorescence detection) are in demand. https://www.selleckchem.com/products/Cyclopamine.html Chemometrics-based fingerprinting tools could facilitate on-farm screening of target traits for breeding innovations.Low-energy (3-25 eV) electron interactions with multilayers of 2'-deoxyadenosine 5'-monophosphate (dAMP) were probed using X-ray photoelectron spectroscopy (XPS). Understanding how electrons damage the nucleotide dAMP, which is a building block of DNA, can give insight into how the DNA undergoes radiation damage. Chemical modifications to the constituent units of the nucleotide were revealed in situ through monitoring of the O 1s, C 1s, and N 1s elemental transitions. It is shown that direct electron irradiation causes decomposition of both the base and sugar subunits, as well as cleavage of glycosidic and phosphoester bonds. Incident electrons undergo inelastic energy losses, including creation of core-excited resonances above 3-4 eV. In the condensed phase, these resonances decay via autoionization, producing electronically excited targets and less then 3 eV electrons. The excited states dissociate and the slow ( less then 3 eV) electrons are captured by neighboring molecules, forming molecular shape resonances that can lead to bond rupture. Since the observed chemical changes were similar at all incident electron energies studied, they can be primarily attributed to formation and decay of transient negative ions. Damage enhancements in the energy ranges typical of all scattering resonances are expected, with the damage probability dominated by the low-energy shape resonances.We present an accurate approach to compute X-ray photoelectron spectra based on the GW Green's function method that overcomes the shortcomings of common density functional theory approaches. GW has become a popular tool to compute valence excitations for a wide range of materials. However, core-level spectroscopy is thus far almost uncharted in GW. We show that single-shot perturbation calculations in the G0W0 approximation, which are routinely used for valence states, cannot be applied for core levels and suffer from an extreme, erroneous transfer of spectral weight to the satellite spectrum. The correct behavior can be restored by partial self-consistent GW schemes or by using hybrid functionals with almost 50% of exact exchange as a starting point for G0W0. We also include relativistic corrections and present a benchmark study for 65 molecular 1s excitations. Our absolute and relative GW core-level binding energies agree within 0.3 and 0.2 eV with experiment, respectively.An unprecedented copper-catalyzed reaction of sulfoxonium ylides and anthranils is reported that enables an easy access to 2,3-diaroylquinolines through a [4+1+1] annulation. Copper-catalyzed homocoupling of sulfoxonium ylides provided α,α,β-tricarbonyl sulfoxonium ylides, which provides a strategy to extend the carbon chain through C-C bond formation. The utility of the products as well as the mechanistic details of the process are presented.N-Phthalimido-d-cysteine allyl ester was S-alkylated with 2-iodoethanol. The derived β-thioaldehyde was condensed with Nα-tetrachlorophthalimidovalinamide to afford a Z-thioenamide. Removal of the tetrachlorophthalimido protecting group and homologation with N-Boc-l-leucine afforded the linear tripeptide. Removal of the Boc and allyl protecting groups, followed by carbodiimide-mediated cyclization, led to the 13-membered ring with the aminovinylcysteine moiety embedded. This constitutes the C-terminal macrocycle of all known members of the linardin family of peptides, including the antileukemia agent, cypemycin.A low-temperature, protecting-group-free oxidation of 2-substituted anilines has been developed to generate an electrophilic N-aryl nitrenoid intermediate that can engage in C-NAr bond formation to construct functionalized N-heterocycles. The exposure of 2-substituted anilines to PIFA and trifluoroacetic acid or 10 mol % Sc(OTf)3 triggers nitrenoid formation, followed by productive and selective C-NAr and C-C bond formation to yield spirocyclic- or bicyclic 3H-indoles or benzazepinones. Our experiments demonstrate the breadth of these oxidative processes, uncover underlying fundamental elements that control selectivity, and demonstrate how the distinct reactivity patterns embedded in N-aryl nitrenoid reactive intermediates can enable access to functionalized 3H-indoles or benzazepinones.The regioselective and regiodivergent addition of H-D to a variety of 1,1-diarylalkenes was realized utilizing selectively deuterated dihydroaromatic compounds, which were generated by cobalt catalysis. The reaction was initiated by catalytic amounts of BF3·Et2O by abstracting hydride or deuteride ions from the respective dihydroaromatic reducing agents and led to a highly regioselective incorporation of deuterium and hydrogen at the desired positions of the starting material.The first example of metal-free cyanomethylenation from alkyl nitriles of sp3 C-H bonds to afford quaternary carbon centers is described. This oxidative protocol is operationally simple and features good functional group compatibility. This method provides a novel approach to highly functionalized fluorene and oxindole derivatives, which are commonly used in material and pharmaceutical areas. Control experiments provide evidence of a radical reaction process.Thermal decomposition performance of the insensitive energetic compound 1,1-diamino-2,2-dintroethene (FOX-7) is essential for its application in the field of solid propellants. This study seeks to reveal the catalytic effects of reduced graphene oxide-bimetallic oxide nanocomposites (rGO-MFe2O4, M = Ni, Co, and Zn) on the thermal decomposition, kinetic parameters, and pyrolysis mechanism of energetic FOX-7. The results showed that the catalytic activities of the bimetallic iron oxide (NiFe2O4, CoFe2O4, and ZnFe2O4) increased obviously after anchoring on the surface of graphene. Particularly, the rGO-NiFe2O4 nanocomposite possessed the best catalytic activity for FOX-7 thermal decomposition. The high thermal decomposition peak temperature (THDP) and the apparent activation energy (Ea) of FOX-7 were decreased by 57.4 °C and 54.27 kJ mol-1 after mixing with the rGO-NiFe2O4 nanocomposite. The excellent catalytic activity of rGO-NiFe2O4 can be attributed to the synergistic interaction between rGO and NiFe2O4, which is beneficial for the reduction of activation energy and a high thermal decomposition peak temperature of FOX-7.
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