Notes

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Despite the broad relevance of copper nanoparticles in industrial applications, the fundamental understanding of oxidation and reduction of copper at the nanoscale is still a matter of debate and remains within the realm of bulk or thin film-based systems. Moreover, the reported studies on nanoparticles vary widely in terms of experimental parameters and are predominantly carried out using either ex situ observation or environmental transmission electron microscopy in a gaseous atmosphere at low pressure. Hence, dedicated studies in regards to the morphological transformations and structural transitions of copper-based nanoparticles at a wider range of temperatures and under industrially relevant pressure would provide valuable insights to improve the application-specific material design. In this paper, copper nanoparticles are studied using in situ Scanning Transmission Electron Microscopy to discern the transformation of the nanoparticles induced by oxidative and reductive environments at high temperatures. reduction-induced fragmentation of the oxide phase. In a broader perspective, this study offers insights into the mobility of the copper phase during its oxidation-reduction process in terms of microstructural evolution as a function of nanoparticle size, reaction gas, and temperature.Copper nitride (Cu3N) was used as a heterogeneous catalyst for the hydroxylation of aryl halides under ligand-free conditions. The cubic Cu3N nanoparticles showed high catalytic activity, comparable to those of conventional Cu catalysts with nitrogen ligands, demonstrating that the nitrogen atoms in Cu3N act as functional ligands that promote hydroxylation.Myers-Saito cycloaromatization (MSC) is the working mechanism of many natural enediyne antibiotics with high antitumor potency. However, the presence of the equilibrium between diradical and zwitterionic intermediates in MSC severely hinders further improvement in cytotoxicity toward tumor cells. To this end, a series of maleimide-based enediynes with cyclopropane moieties were synthesized for enhanced cytotoxicity toward tumor cells. By taking advantage of radical clock reactions, the diradical intermediates generated from MSC would rearrange to new diradicals with much longer separation and weaker interactions between two radical centers. The computational study suggested a low energy barrier (4.4 kcal mol-1) for the radical rearrangement through the cyclopropane ring-opening process. Thermolysis experiments confirmed that this radical rearrangement results in the formation of a new diradical intermediate, followed by abstracting hydrogen atoms from 1,4-cyclohexadiene. Interestingly, the DNA cleavage ability and cytotoxicity of enediynes were significantly enhanced after the introduction of cyclopropane moieties. In addition, these maleimide-based enediynes exhibited a similar cytotoxicity under hypoxic conditions to that under normoxic conditions, which is beneficial for treating solid tumors where hypoxic environments frequently lead to deteriorated efficiency of many antitumor drugs. Docking studies indicated that the diradical intermediate was located between the minor groove of DNA with a binding energy of -7.40 kcal mol-1, which is in favor of intracellular DNA damage, and thereby inducing cell death via an apoptosis pathway as suggested by immunofluorescence analysis.In the discussion of chirality recognition, steric considerations and strongly directed interactions such as hydrogen bonds are primarily discussed. However, given the sheer size of biomolecules, it is expected that dispersion forces could also play a determining role for aggregate formation and associated chirality recognition. With the example of diol molecules, we explore different factors in the formation of homo- and hetero-dimers as well as their relative stability. By comparing density functional results with the analysis of local correlation methods, we infer the impact of dispersion not only on the energies but also on the structures of such chiral aggregates. A local orbital based scheme is used to calculate wave function dispersion-free gradients and compare to uncorrected density functional structures.Hepatocyte apoptosis is involved in the pathogenesis of alcohol-associated liver disease (ALD) and anti-apoptotic agents/extracts are thereby of great importance in the prevention/treatment of ALD. selleck inhibitor In this study, the protective effects of 10 edible flowers against ethanol-induced cell death were investigated in HepG2 cells, with rose (Rosa rugosa) showing the strongest activity. Therefore, rose was chosen for further separation and purification of bioactive fractions. A special fraction, SLs, was found to significantly increase the viability of EtOH-treated cells and attenuated EtOH-induced apoptosis partially via the activation of the AMPK/SIRT1 signaling pathway. Chromatographic analysis identified a series of hydroxycinnamic acid amides, kaempferol glycosides, and quercetin glycosides in this fraction, while the following intracellular uptake and cytotoxicity studies revealed that N1,N5,N10-(E)-tri-p-coumaroylspermidine (a hydroxycinnamic acid amide) in this fraction exhibited remarkable hepatoprotective activity with similar effective dosage to sulforaphane. Hence, our results highlighted the anti-alcohol and hepatoprotective benefits of consuming rose.Here we show a new and significant application area for mass spectrometry imaging. The potential for fingerprints to reveal drug use has been widely reported, with potential applications in forensics and workplace drug testing. However, one unsolved issue is the inability to distinguish between drug administration and contamination by contact. Previous work using bulk mass spectrometry analysis has shown that this distinction can only be definitively made if the hands are washed prior to sample collection. Here, we illustrate how three mass spectrometry imaging approaches, desorption electrospray ionisation (DESI), matrix assisted laser desorption ionisation (MALDI) and time of flight secondary ion mass spectrometry (ToF-SIMS) can be used to visualise fingerprints at different pixel sizes, ranging from the whole fingerprint down to the pore structure. We show how each of these magnification scales can be used to distinguish between cocaine use and contact. We also demonstrate the first application of water cluster SIMS to a fingerprint sample, which was the sole method tested here that was capable of detecting excreted drug metabolites in fingerprints, while providing spatial resolution sufficient to resolve individual pore structure.
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