Reactive layer-by-layer films from solutions containing silicic acid and a Ti(IV) complex: preferential incorporation of silica and interactions of the obtained films with hexacyanoferrate anions

The concept of reactive layer-by-layer (LBL) deposition allows the build-up of films containing polycations and oxide particles, namely, silica and poorly crystalline anatase. Because polyelectrolyte multilayer films have been produced from blended polyanions or polycations solutions and since preferential incorporation of one of the partners of the blend has been found in most cases, one should wonder if a preferential polycondensation of either silica or titania should occur when the reactive deposition is performed from a solution containing a precursor of both inorganic species. X-ray photoelectron (XPS) and UV-visible spectroscopies show that the reactive LBL films made from the blend and poly(diallyldimethylammonium chloride) (PDADMAC) incorporate predominantly silica over TiO(2) over the whole molar fraction range of the silicic acic/hydrosoluble Ti(IV) complex. The transparency of the films below 365 nm, corresponding to the band edge of TiO(2), can easily be modulated. The silica/TiO(2) films are all able to bind hexacyanoferrate owing to the presence of the polycation allowing the binding of the oxide particles to the substrate. However, the binding capacity of the film does not scale proportionally to its thickness. The films made from eight dipping cycles showed a sudden decrease in their binding capacity for hexacyanoferrate when the molar fraction of the titanium complex was higher than ～0.6 in the blend. For the same films, electrochemical impedance spectra (EIS) showed marked differences with a change in film composition: the more TiO(2) in the film, the higher the resistance to electron and to mass transfer. Therefore, EIS helps to explain the reduced surface concentration measured by means of cyclic voltammetry for films rich in TiO(2).     

Mass Spectrometry Analysis of 2-Nitrophenylhydrazine Carboxy Derivatized Peptides

Peptides with two or more basic residues, including those with post-translational modifications (PTMs), such as methylation and phosphorylation, can be highly hydrophilic and, therefore, are often difficult to be retained on a reversed-phase (RP) column. In addition, these highly hydrophilic peptides may carry two or more positive charges, which often fragment poorly upon collisionally activated dissociation (CAD), resulting in few sequence-specific ions. C-terminal rearrangement may also occur during CAD. Furthermore, some PTMs are labile and tend to be lost when subjected to CAD as is the case with phosphorylation on serine or threonine. To overcome the difficulties of separation, detection, and fragmentation of highly hydrophilic peptides, we report here the effect of carboxy group derivatization with 2-nitrophenylhydrazine (this strategy will be called NPHylation for simplicity). NPHylation significantly increases the hydrophobicity of the peptides, eliminates C-terminal rearrangement in all cases, and offers enhanced sensitivity in some cases. In addition, the CAD spectra of the resulting NPHylated peptides carry more sequence-specific ions due to significant reduction of sequence scrambling as observed for peptide EHAGVISVL. Furthermore, the different carboxy derivatives of this peptide undergo sequence scrambling to varying degrees, which clearly demonstrates that the C-terminus has a profound effect on peptide fragmentation. Finally, sequence scrambling is a charge dependent phenomenon, which affects CAD of doubly charged peptides far more than their singly charged counterparts.     

Small x resummation with quarks: Deep-inelastic scattering

We extend our previous results on small-x resummation in the pure Yang–Mills theory to full QCD with n_f quark flavours, with a resummed two-by-two matrix of resummed quark and gluon splitting functions. We also construct the corresponding deep-inelastic coefficient functions, and show how these can be combined with parton densities to give fully resummed deep-inelastic structure functions F₂ and F_L at the next-to-leading logarithmic level. We discuss how this resummation can be performed in different factorization schemes, including the commonly used scheme. We study the importance of the resummation effects by comparison with fixed-order perturbative results, and we discuss the corresponding renormalization and factorization scale variation uncertainties. We find that for x below 10⁻² the resummation effects are comparable in size to the fixed order NNLO corrections, but differ in shape. We finally discuss the phenomenological impact of the small-x resummation, specifically in the extraction of parton distribution from present day experiments and their extrapolation to the kinematics relevant for future colliders such as the LHC.     

Measurement of deeply virtual compton scattering beam-spin asymmetries

The beam-spin asymmetries in the hard exclusive electroproduction of photons on the proton (e p-->epgamma) were measured over a wide kinematic range and with high statistical accuracy. These asymmetries result from the interference of the Bethe-Heitler process and of deeply virtual Compton scattering. Over the whole kinematic range (x(B) from 0.11 to 0.58, Q2 from 1 to 4.8 GeV2, -t from 0.09 to 1.8 GeV2), the azimuthal dependence of the asymmetries is compatible with expectations from leading-twist dominance, A approximately a sinphi/(1+c cosphi). This extensive set of data can thus be used to constrain significantly the generalized parton distributions of the nucleon in the valence quark sector.     

High-energy resummation of direct photon production at hadronic colliders

Direct photon production is an important process at hadron colliders, being relevant both for precision measurement of the gluon density, and as background to Higgs and other new physics searches. Here we explore the implications of recently derived results for high-energy resummation of direct photon production for the interpretation of measurements at the Tevatron and the LHC. The effects of resummation are compared to various sources of theoretical uncertainties like PDFs and scale variations. We show how the high-energy resummation procedure stabilizes the logarithmic enhancement of the cross section at high energy which is present at any fixed order in the perturbative expansion starting at NNLO. The effects of high-energy resummation are found to be negligible at Tevatron, while they enhance the cross section by a few percent for pT?10 GeV$p_T?10\text{GeV}$ at the LHC. Our results imply that the discrepancy at small pT$p_T$ between fixed order NLO and Tevatron data cannot be explained by unresummed high-energy contributions.     

Single-Molecule Two-Color Coincidence Detection of Unlabeled alpha-Synuclein Aggregates

Protein misfolding and aggregation into oligomeric and fibrillar structures is a common feature of many neurogenerative disorders. Single-molecule techniques have enabled characterization of these lowly abundant, highly heterogeneous protein aggregates, previously inaccessible using ensemble averaging techniques. However, they usually rely on the use of recombinantly-expressed labeled protein, or on the addition of amyloid stains that are not protein-specific. To circumvent these challenges, we have made use of a high affinity antibody labeled with orthogonal fluorophores combined with fast-flow microfluidics and single-molecule confocal microscopy to specifically detect α-synuclein, the protein associated with Parkinson's disease. We used this approach to determine the number and size of α-synuclein aggregates down to picomolar concentrations in biologically relevant samples.     

Photochemically Mediated Ring Expansion of Indoles and Pyrroles with Chlorodiazirines: Synthetic Methodology and Thermal Hazard Assessment

We demonstrate that arylchlorodiazirines serve as photo-activated halocarbene precursors for the selective one-carbon ring expansion of N-substituted pyrroles and indoles to the corresponding pyridinium and quinolinium salts. Preliminary investigations indicate that the same strategy also enables the conversion of N-substituted pyrazoles to pyrimidinium salts. The N-substituent of the substrate plays an essential role in: (1) increasing substrate scope by preventing product degradation, (2) enhancing yields by suppressing co-product inhibition, and (3) activating the azinium products towards subsequent synthetic manipulations. This latter point is illustrated by subjecting the quinolinium salts to four complementary partial reductions, which provide concise access to ring-expanded products with different degrees of increased C(sp³) character. Thermal analysis of the diazirines by differential scanning calorimetry (DSC) provides detailed insight into their energetic properties, and highlights the safety benefits of photolyzing—rather than thermolyzing—these reagents.     

Skeletal Editing: Interconversion of Arenes and Heteroarenes

Skeletal editing involves making specific point-changes to the core of a molecule through the selective insertion, deletion or exchange of atoms. It thus represents a potentially powerful strategy for the step-economic modification of complex substrates and is a perfect complement to methods such as C−H functionalization that target the molecular periphery. Given their ubiquity in biologically active compounds, the ability to perform skeletal editing on – and therefore interconvert between – aromatic heterocycles is especially valuable. This review summarizes both recent and key historical examples of skeletal editing as applied to interconversion of aromatic rings; we anticipate that it will serve to highlight not only the innovative and enabling nature of current skeletal editing methods, but also the tremendous opportunities that still exist in the field.