We demonstrate that the plasmonic properties of realistic graphene and graphene-based materials can effectively and accurately be modeled by a novel, fully atomistic, yet classical, approach, named ωFQ. Such a model is able to reproduce all plasmonic features of these materials and their dependence on shape, dimension, and fundamental physical parameters (Fermi energy, relaxation time, and two-dimensional electron density). Remarkably, ωFQ is able to accurately reproduce experimental data for realistic structures of hundreds of nanometers (∼370k atoms), which cannot be afforded by any ab initio method. Also, the atomistic nature of ωFQ permits the investigation of complex shapes, which can hardly be dealt with by exploiting widespread continuum approaches.Current methods for Suzuki-Miyaura couplings of nontriflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe3, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the presence of aryl chlorides. This selectivity was exploited in the first Ni-catalyzed C-O-selective Suzuki-Miyaura coupling of chlorinated phenol derivatives where the oxygen-containing leaving group is not a fluorinated sulfonate such as triflate. Computational studies suggest that the origin of divergent selectivity between PMe3 and other phosphines differs from prior examples of ligand-controlled chemodivergent cross-couplings. PMe3 effects selective reaction at tosylate due to both electronic and steric factors. A close interaction between nickel and a sulfonyl oxygen of tosylate during oxidative addition is critical to the observed selectivity.Alcoholic beverages with low ethanol contents were produced by fermenting black currant juice with Saccharomyces and non-Saccharomyces yeasts without added sugar. The effects of different yeasts on the phenolic compounds (anthocyanins, hydroxycinnamic acids, flavonols, and flavan-3-ols) and other selected constituents (the ethanol content, residual sugars, organic acids, and color) of the black currants were assessed. Single yeast-fermented beverages had higher ethanol contents (3.84-4.47%, v/v) than those produced by sequential fermentation. In general, the fermentation of black currant juice increased the contents of organic acids and flavonols, whereas anthocyanin contents decreased. All of the fermentations decreased the contents of glycosylated nitrile-containing hydroxycinnamic acids, resulting in higher contents of the corresponding aglycons. Fermentation with Saccharomyces bayanus resulted in lower anthocyanin and organic acid contents compared to the other yeasts. Sequential fermentations with Saccharomyces cerevisiae and Metschnikowia pulcherrima led to the highest total hydroxycinnamic acids and anthocyanins among all of the fermentations.Lithium (Li) metal is the most promising negative electrode to be implemented in batteries for stationary and electric vehicle applications. For years, its use and subsequent industrialization were hampered because of the inhomogeneous Li+ ion reduction upon recharge onto Li metal leading to dendrite growth. The use of solid polymer electrolyte is a solution to mitigate dendrite growth. Li reduction leads typically to dense Li deposits, but the Li stripping and plating process remain nonuniform with local current heterogeneities. A precise characterization of the behavior of these heterogeneities during cycling is then essential to move toward an optimized negative electrode. In this work, we have developed a characterization method based on X-ray tomography applied to model Li symmetric cells to quantify and spatially probe the Li stripping/plating processes. Ante- and post-mortem cells are recut in smaller cells to allow a 1 μm voxel size resolution in a conventional laboratory scanner. The reconstructed cell volume is postprocessed to numerically reflatten the Li electrodes, allowing us a subsequent precise measurement of the electrode and electrolyte thicknesses and revealing local interface modifications. This in-depth analysis brings information about the location of heterogeneities and their impact on the electrode microstructure at both the electrode grains and grain boundaries. We show that the plating process (reduction) induces more pronounced heterogeneities compared to the stripping (oxidation) one. The existence of crosstalking between the electrodes is also highlighted. In addition, this simple methodology permits to finely retrieve and then surface map the local current density at both electrodes based on the local thickness change during the redox process.Biology relies almost exclusively on homochiral building blocks to drive the processes of life. Yet cross-chiral interactions can occur between macromolecules of the opposite handedness, including a previously described polymerase ribozyme that catalyzes the template-directed synthesis of enantio-RNA. The present study sought to optimize and generalize this activity, employing in vitro evolution to select cross-chiral polymerases that use either mono- or trinucleotide substrates that are activated as the 5'-triphosphate. There was only modest improvement of the former activity, but dramatic improvement of the latter, which enables the trinucleotide polymerase to react 102-103-fold faster than its ancestor and to accept substrates with all possible sequence combinations. The evolved ribozyme can assemble long RNAs from a mixture of trinucleotide building blocks, including a two-fragment form of the ancestral polymerase ribozyme. Further improvement of this activity could enable the generalized cross-chiral replication of RNA, which would establish a new paradigm for the chemical basis of Darwinian evolution.The therapeutic index of cytokines in cancer therapy can be increased by targeting strategies based on protein engineering with peptides containing the CNGRC (NGR) motif, a ligand that recognizes CD13-positive tumor vessels.  https://www.selleckchem.com/products/mdivi-1.html  We show here that the targeting domain of recombinant CNGRC-cytokine fusion proteins, such as NGR-TNF (a CNGRC-tumor necrosis factor-α (TNF) conjugate used in clinical studies) and NGR-EMAP-II, undergoes various post-translational modification and degradation reactions that lead to the formation of markedly heterogeneous products. These modifications include N-terminal cysteine acetylation or the formation of various asparagine degradation products, the latter owing to intramolecular interactions of the cysteine α-amino group with asparagine and/or its succinimide derivative. Blocking the cysteine α-amino group with a serine (SCNGRC) reduced both post-translational and degradation reactions. Furthermore, the serine residue reduced the asparagine deamidation rate to isoaspartate (another degradation product) and improved the affinity of NGR for CD13.