Initiation and inhibition of dealloying of single crystalline Cu3Au (111) surfaces

Dealloying is widely utilized but is a dangerous corrosion process as well. Here we report an atomistic picture of the initial stages of electrochemical dealloying of the model system Cu(3)Au (111). We illuminate the structural and chemical changes during the early stages of dissolution up to the critical potential, using a unique combination of advanced surface-analytical tools. Scanning tunneling microscopy images indicate an interlayer exchange of topmost surface atoms during initial dealloying, while scanning Auger-electron microscopy data clearly reveal that the surface is fully covered by a continuous Au-rich layer at an early stage. Initiating below this first layer a transformation from stacking-reversed toward substrate-oriented Au surface structures is observed close to the critical potential. We further use the observed structural transitions as a reference process to evaluate the mechanistic changes induced by a thiol-based model-inhibition layer applied to suppress surface diffusion. The initial ultrathin Au layer is stabilized with the intermediate island morphology completely suppressed, along an anodic shift of the breakdown potential. Thiol-modification induces a peculiar surface microstructure in the form of microcracks exhibiting a nanoporous core. On the basis of the presented atomic-scale observations, an interlayer exchange mechanism next to pure surface diffusion becomes obvious which may be controlling the layer thickness and its later change in orientation.     

Dual lithium insertion and conversion mechanisms in a titanium-based mixed-anion nanocomposite

The electrochemical reaction of lithium with a vacancy-containing titanium hydroxyfluoride was studied. On the basis of pair distribution function analysis, NMR, and X-ray photoelectron spectroscopy, we propose that the material undergoes partitioning upon initial discharge to form a nanostructured composite containing crystalline Li(x)TiO(2), surrounded by a Ti(0) and LiF layer. The Ti(0) is reoxidized upon reversible charging to an amorphous TiF(3) phase via a conversion reaction. The crystalline Li(x)TiO(2) is involved in an insertion reaction. The resulting composite electrode, Ti(0)-LiF/Li(x)TiO(2) ? TiF(3)/ Li(y)TiO(2), allows reaction of more than one Li per Ti, providing a route to higher capacities while improving the energy efficiency compared to pure conversion chemistries.     

P-C bond activation chemistry: evidence for 1,1-carboboration reactions proceeding with phosphorus-carbon bond cleavage

A series of diarylphosphinyl-substituted acetylenes of the type (aryl)(2)P-C≡C-R (aryl = phenyl or mesityl, R = Ph or n-propyl) react with the strongly Lewis acid reagent B(C(6)F(5))(3) in toluene at elevated temperatures (70-105 °C) to give the 1,1-carboboration products 4. Treatment of bis(diphenylphosphinyl)acetylene with B(C(6)F(5))(3) under analogous conditions proceeded with phosphinyl migration to yield the 1,1-carboboration product 4d, bearing a geminal pair of Ph(2)P substituents at one former acetylene carbon atom and a C(6)F(5) substituent and the remaining -B(C(6)F(5))(2) group at the other. Prolonged thermolysis of 4d resulted in an intramolecular aromatic substitution reaction by means of Ph(2)P attack on the adjacent C(6)F(5) ring to yield the zwitterionic phospha-indene derivative 7. The compounds 4a, 4c, 4d, and 7 were characterized by X-ray diffraction.     

Injury‐Triggered Blueing Reactions of Psilocybe “Magic” Mushrooms

Upon injury, psychotropic psilocybin‐producing mushrooms instantly develop an intense blue color, the chemical basis and mode of formation of which has remained elusive. We report two enzymes from Psilocybe cubensis that carry out a two‐step cascade to prepare psilocybin for oxidative oligomerization that leads to blue products. The phosphatase PsiP removes the 4‐O‐phosphate group to yield psilocin, while PsiL oxidizes its 4‐hydroxy group. The PsiL reaction was monitored by in situ ¹³C NMR spectroscopy, which indicated that oxidative coupling of psilocyl residues occurs primarily via C‐5. MS and IR spectroscopy indicated the formation of a heterogeneous mixture of preferentially psilocyl 3‐ to 13‐mers and suggest multiple oligomerization routes, depending on oxidative power and substrate concentration. The results also imply that phosphate ester of psilocybin serves a reversible protective function.     

PI by NMR: Probing CH–π Interactions in Protein–Ligand Complexes by NMR Spectroscopy

While CH–π interactions with target proteins are crucial determinants for the affinity of arguably every drug molecule, no method exists to directly measure the strength of individual CH–π interactions in drug–protein complexes. Herein, we present a fast and reliable methodology called PI (π interactions) by NMR, which can differentiate the strength of protein–ligand CH–π interactions in solution. By combining selective amino‐acid side‐chain labeling with ¹H‐¹³C NMR, we are able to identify specific protein protons of side‐chains engaged in CH–π interactions with aromatic ring systems of a ligand, based solely on ¹H chemical‐shift values of the interacting protein aromatic ring protons. The information encoded in the chemical shifts induced by such interactions serves as a proxy for the strength of each individual CH–π interaction. PI by NMR changes the paradigm by which chemists can optimize the potency of drug candidates: direct determination of individual π interactions rather than averaged measures of all interactions.     

Long-Term Colloidally Stable Aqueous Dispersions of ≤5 nm Spinel Ferrite Nanoparticles

Applications in biomedicine and ferrofluids, for instance, require long-term colloidally stable, concentrated aqueous dispersions of magnetic, biocompatible nanoparticles. Iron oxide and related spinel ferrite nanoparticles stabilized with organic molecules allow fine-tuning of magnetic properties via cation substitution and water-dispersibility. Here, we synthesize≤5 nm iron oxide and spinel ferrite nanoparticles, capped with citrate, betaine and phosphocholine, in a one-pot strategy. We present a robust approach combining elemental (CHN) and thermal gravimetric analysis (TGA) to quantify the ratio of residual solvent molecules and organic stabilizers on the particle surface, being of particular accuracy for ligands with heteroatoms compared to the solvent. SAXS experiments demonstrate the long-term colloidal stability of our aqueous iron oxide and spinel ferrite nanoparticle dispersions for at least 3 months. By the use of SAXS we approved directly the colloidal stability of the nanoparticle dispersions for high concentrations up to 100 g L⁻¹.     

A Highly Efficient and Broadly Applicable Cationic Gold Catalyst

Gold catalysts capable of promoting reactions at low‐level loadings under mild conditions are the exception rather than the norm. We examined reactions where the regeneration of cationic gold catalyst (e.g., protodeauration) was the turnover limiting stage. By manipulating electron density on the substituents around phosphorus and introducing steric handles we designed a phosphine ligand that contains two electron‐rich ortho‐biphenyl groups and a cyclohexyl substituent. This ligand formed a gold complex that catalyzed common types of gold‐catalyzed reactions including intra‐ and intermolecular X? H (X=C, N, O) additions to alkynes and cycloisomerizations, with high turnover numbers at room temperature or slightly elevated temperatures (≤50 °C). Our new ligand can be prepared in one step from commercially available starting materials.     

Dynamics of rigid and flexible polymer chains in confined geometries. part I: steady simple shear flow

This paper describes exact solutions to the response of both the elastic and rigid dumbbell models to a steady simple shear flow in a channel having a length scale comparable to the dumbbells themselves. Results are given for rheological properties over the entire range of the ratio of the channel width to the length of the dumbbell. It is found that both models lead to a decrease in viscosity as the channel is reduced in size with the elastic dumbbell predicting a stronger dependence on that parameter compared with the rigid dumbbell. The elastic dumbbell predicts shear independent rheological properties whereas the rigid dumbell predicts shear thinning as in the case of unbounded flows. The rate of shear thinning, however, decreases with decreasing channel width.