The Uranyl Cation as a Visible‐Light Photocatalyst for C(sp3)−H Fluorination

The fluorination of unactivated C(sp³)?H bonds remains a desirable and challenging transformation for pharmaceutical, agricultural, and materials scientists. Previous methods for this transformation have used bench‐stable fluorine atom sources; however, many still rely on the use of UV‐active photocatalysts for the requisite high‐energy hydrogen atom abstraction event. Uranyl nitrate hexahydrate is described as a convenient, hydrogen atom abstraction catalyst that can mediate fluorinations of certain alkanes upon activation with visible light.     

Plasmon single- and multi-quantum excitation in free metal clusters as seen by photoelectron spectroscopy

Plasmons are investigated in free nanoscale Na, Mg, and K metal clusters using synchrotron radiation-based x-ray photoelectron spectroscopy. The core levels for which the response from bulk and surface atoms can be resolved are probed over an extended binding energy range to include the plasmon loss features. In all species the features due to fundamental plasmons are identified, and in Na and K also those due to either the first order plasmon overtones or sequential plasmon excitation are observed. These features are discussed in view of earlier results for planar macroscopic samples and free clusters of the same materials.     

CONCERNING THE ORIGIN OF CHARGE AT THE POLYSTYRENE PARTICLE/WATER INTERFACE

The electrophoretic mobility behavior of well-characterized polystyrene latex particles, carrying one type of surface functional endgroups, has been studied as a function of pH. At low pH, the interaction of protons with the functional endgroups increased in the order: Hydroxyl > carboxyl > sulfate; at high pH the order of interaction was reversed; and at intermediate pH no interactions were observed. The particles of the polystyrene latexes in their different forms at the intermediate pH range, dispersed in deionized water, all exhibited the same mobility irrespective of the functional endgroup. The origin of charge in these systems is explained as being the result of either the preferential adsorption of hydroxyl ions or an electron - injection mechanism due to the overlap of local intrinsic molecular - ion states in polystyrene and water. At low concentrations of functional endgroups, the surface properties of the polystyrene latexes are largely dependent upon the hydrophobic nature of the surface.     

Tetrathienoacene copolymers as high mobility, soluble organic semiconductors

Increasing the rigidity of the thiophene monomer through the use of an alkyl-substituted core that consists of four fused thiophene rings is shown to be a promising route toward high-performance organic semiconductors. We report on a dialkylated tetrathienoacene copolymer that can be deposited from solution to yield ordered films with a short pi-pi distance of 3.76 A and with a field-effect hole mobility that exceeds 0.3 cm2/V.s. This polymer enables simple transistor fabrication at relatively low temperatures, which is particularly important for the realization of large-area, mechanically flexible electronics.     

The effect of shear on colloidal aggregation and gelation studied using small-angle light scattering

In situ light scattering measurements were performed to investigate the effect of low shear rates (0.13-3.56 s(-1)) on an aggregating colloidal system made of 20 nm polystyrene particles. The aggregating system was subjected to a shear for a short period (ca. 33 s) and only once at various times after the onset of aggregation. The effect of shear (aggregation kinetics and morphology) was studied both in a cluster dilute and in a cluster dense regime (see introduction). Our results have shown that shear can enhance the aggregation and gelation. Shear induced growth can yield hybrid superaggregates when the system is dense.     

Locally algebraic vectors in the Breuil–Herzig ordinary part

For a fairly general reductive group \({G_{/\mathbb{Q}_p}}\), we explicitly compute the space of locally algebraic vectors in the Breuil–Herzig construction \({\Pi(\rho)^{ord}}\), for a potentially semistable Borel-valued representation \({\rho}\) of \({Gal(\bar{\mathbb{Q}}_p/\mathbb{Q}_p)}\). The point being we deal with the whole representation, not just its socle—and we go beyond \({GL_n(\mathbb{Q}_p)}\). In the case of \({GL_2(\mathbb{Q}_p)}\), this relation is one of the key properties of the \({p}\)-adic local Langlands correspondence. We give an application to \({p}\)-adic local-global compatibility for \({\Pi(\rho)^{ord}}\) for modular representations, but with no indecomposability assumptions.     

Rapid Construction of a Benzo‐Fused Indoxamycin Core Enabled by Site‐Selective C−H Functionalizations

Methods for functionalizing carbon–hydrogen bonds are featured in a new synthesis of the tricyclic core architecture that characterizes the indoxamycin family of secondary metabolites. A unique collaboration between three laboratories has engendered a design for synthesis featuring two sequential C?H functionalization reactions, namely a diastereoselective dirhodium carbene insertion followed by an ester‐directed oxidative Heck cyclization, to rapidly assemble the congested tricyclic core of the indoxamycins. This project exemplifies how multi‐laboratory collaborations can foster conceptually novel approaches to challenging problems in chemical synthesis.     

Quantification of Lysine Acetylation and Succinylation Stoichiometry in Proteins Using Mass Spectrometric Data-Independent Acquisitions (SWATH)

Post-translational modification of lysine residues by N_?-acylation is an important regulator of protein function. Many large-scale protein acylation studies have assessed relative changes of lysine acylation sites after antibody enrichment using mass spectrometry-based proteomics. Although relative acylation fold-changes are important, this does not reveal site occupancy, or stoichiometry, of individual modification sites, which is critical to understand functional consequences. Recently, methods for determining lysine acetylation stoichiometry have been proposed based on ratiometric analysis of endogenous levels to those introduced after quantitative per-acetylation of proteins using stable isotope-labeled acetic anhydride. However, in our hands, we find that these methods can overestimate acetylation stoichiometries because of signal interferences when endogenous levels of acylation are very low, which is especially problematic when using MS1 scans for quantification. In this study, we sought to improve the accuracy of determining acylation stoichiometry using data-independent acquisition (DIA). Specifically, we use SWATH acquisition to comprehensively collect both precursor and fragment ion intensity data. The use of fragment ions for stoichiometry quantification not only reduces interferences but also allows for determination of site-level stoichiometry from peptides with multiple lysine residues. We also demonstrate the novel extension of this method to measurements of succinylation stoichiometry using deuterium-labeled succinic anhydride. Proof of principle SWATH acquisition studies were first performed using bovine serum albumin for both acetylation and succinylation occupancy measurements, followed by the analysis of more complex samples of E. coli cell lysates. Although overall site occupancy was low (<1%), some proteins contained lysines with relatively high acetylation occupancy.

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Localized versus delocalized excitations just above the 3d threshold in krypton clusters studied by Auger electron spectroscopy

We present Auger spectroscopy studies of large krypton clusters excited by soft x-ray photons with energies on and just above the 3d(52) ionization threshold. The deexcitation spectra contain new features as compared to the spectra measured both below and far above threshold. Possible origins of these extra features, which stay at constant kinetic energies, are discussed: (1) normal Auger process with a postcollision interaction induced energy shift, (2) recapture of photoelectrons into high Rydberg orbitals after Auger decay, and (3) excitation into the conduction band (or "internal" ionization) followed by Auger decay. The first two schemes are ruled out, hence internal ionization remains the most probable explanation.     

H2S ultrafast dissociation probed by energy-selected resonant Auger electron-ion coincidence measurements

We have studied the ultrafast dissociation of the H2S molecule upon S 2p3/2-->6a1 inner-shell excitation by combining high-resolution resonant Auger spectroscopy and energy-selected Auger electron-ion coincidence measurements. Auger final states have been correlated to the different fragmentation pathways (S+, HS+, and H2S+ ions). As an original result, we evidence a three-step mechanism to describe the resonant production of S+: the Auger recombination in the HS* fragment is followed for the A 3Pi and c 1Pi states by the S++H fragmentation mechanism.