Study of amyloid β-peptide (Aβ12-28-Cys) interactions with Congo red and β-sheet breaker peptides using electrochemical impedance spectroscopy

A surface-based approach is presented to study the interactions of Aβ12-28-Cys assembled on gold surfaces with Congo red (CR) and a β-sheet breaker (BSB) peptide. The various aspects of the peptide film have been examined using different electrochemical and surface analytical techniques. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) results using redox probes [Fe(CN)(6)](3-/4-) show that Aβ12-28-Cys on gold forms a stable and reproducible blocking film. EIS analysis shows that CR and BSB have different effects on the electrochemical properties of Aβ12-28-Cys films, presumably due to changes in the interactions between the film and CR and BSB. EIS results indicate that in the case of CR film resistance decreases significantly presumably due to better penetration of the solution-based redox probe into the film, whereas in the case of BSB, the film resistance increases. We interpret this difference to BSB being able to interact with the Aβ12-28-Cys on the surface and presumably forming a film that presents a higher resistance for electron transfer from the redox probe to the solution.     

N-Doped Hybrid Graphene and Boron Nitride Armchair Nanoribbons As Nonmagnetic Semiconductors with Widely Tunable Electronic Properties

Russian Journal of Physical Chemistry A - The electronic and chemical properties of N-doped hybrid graphene and boron nitride armchair nanoribbons (N-doped a-GBNNRs) in comparison with graphene...     

A Fujiwara-Moritani-Type Alkenylation Using a Traceless Directing Group Strategy: A Rare Example of C−C Bond Formation towards the C2-Carbon of Terminal Alkenes

Herein we report, a rhodium-catalyzed Fujiwara-Moritani-type reaction of unactivated terminal alkenes and benzoic acid derivatives bearing electron donating residues under mild conditions. The acid functionality acts as a traceless directing group delivering products alkenylated in meta-position to the electron donating substituent in contrast to the usually obtained ortho- and para-substitution in Friedel-Crafts-type reactions. Remarkably, the new C−C bond is formed to the C2 of the terminal olefin, in contrast to similar reported transformations. Initially formed mixtures of exo- and endo-double bond isomers can be efficiently isomerized to the more stable endo-products.     

Molecular electrocatalysis at soft interfaces

The fundamental aspects of electrochemistry at liquid-liquid interfaces are introduced to present the concept of molecular electrocatalysis. Here, a molecular catalyst is adsorbed at the interface to promote a proton coupled electron transfer reaction such as hydrogen evolution or oxygen reduction using lipophilic electron donors.     

Hydrogen Evolution at Liquid–Liquid Interfaces

Blowing bubbles : Hydrogen evolution by proton reduction with [(C₅Me₅)₂Fe] occurs at a soft interface between water and 1,2‐dichloroethane (DCE). The reaction proceeds by proton transfer assisted by [(C₅Me₅)₂Fe] across the water–DCE interface with subsequent proton reduction in DCE. The interface essentially acts as a proton pump, allowing hydrogen evolution by directly using the aqueous proton.

     

Detection of hydrogen peroxide produced at a liquid/liquid interface using scanning electrochemical microscopy

Scanning electrochemical microscopy (SECM) was used to monitor in situ hydrogen peroxide (H₂O₂) produced at a polarized water/1,2-dichloroethane (DCE) interface. The water/DCE interface was formed between a DCE droplet containing decamethylferrocene (DMFc) supported on a solid electrode and an acidic aqueous solution. H₂O₂ was generated by reducing oxygen with DMFc at the water/DCE interface, and was detected with a SECM tip positioned in the vicinity of the interface using a substrate generation/tip collection mode. This work shows unambiguously how the H₂O₂ generation depends on the polarization of the liquid/liquid interface, and how proton-coupled electron transfer reactions can be controlled at liquid/liquid interfaces.     

Type and conductor of simplicial affine semigroups

We provide a generalization of pseudo-Frobenius numbers of numerical semigroups to the context of the simplicial affine semigroups. In this way, we characterize the Cohen-Macaulay type of the simplicial affine semigroup ring $\mathbb{K}[S]$. We define the type of S, $\mathrm{type}(S)$, in terms of some Apéry sets of S and show that it coincides with the Cohen-Macaulay type of the semigroup ring, when $\mathbb{K}[S]$ is Cohen-Macaulay. If $\mathbb{K}[S]$ is a d-dimensional Cohen-Macaulay ring of embedding dimension at most $d+2$, then $\mathrm{type}(S)\le 2$. Otherwise, $\mathrm{type}(S)$ might be arbitrary large and it has no upper bound in terms of the embedding dimension. Finally, we present a generating set for the conductor of S as an ideal of its normalization.