Why is copper locally etched by scanning electrochemical microscopy?

The etching of thin copper films by scanning electrochemical microscopy (SECM) was investigated. It is not trivial that locally injected charge by an oxidized mediator will lead to dissolution of copper as the charge can easily be dissipated by lateral charge propagation. We studied the effect of different parameters, such as thickness of the Cu film and concentration of the mediator, on the efficiency of etching. The feedback current is the sum of three charge transfer contributions: diffusion of mediator species, chemical reaction on the surface and lateral charge propagation across the copper film. We have introduced an approach for isolating the lateral contribution and studied the parameters affecting the fate of the locally injected charge. We found that etching becomes effective once the lateral contribution cannot dissipate the locally injected charge. This occurs as the concentration of the etchant increases or the film thickness decreases. Measuring the steady-state current above Cu films with different thickness, allowed estimating the potential difference across the Cu area underneath the tip. We conclude that driving local processes, such as etching, depends on creating a mechanism which maintains the injected charge focused.     

Synthesis of epi-oxetin via a serine-derived 2-methyleneoxetane

The unique reactivity of 2-methyleneoxetanes and 1,5-dioxaspiro[3.2]hexanes has been exploited for the synthesis of epi-oxetin (26), an oxetane-containing beta-amino acid. While the preparation of the natural product oxetin (1) was the original goal, the unexpected diastereoselectivity of an precedented reduction provided the epi-oxetin framework. The methodology described herein should be amenable for the preparation of oxetin with a change in nitrogen protection.     

Water-soluble, electroactive, and photoluminescent quaterthiophene-dinucleotide conjugates

Quaterthiophene-dinucleotide conjugates 5'TA3'-t4-3'AT5', 5'AA3'-t4-3'AA5', and 5'TT3'-t4-3'TT5' (TA: thymidine-adenosine, AA: adenosine-adenosine, TT: thymidine-thymidine) were synthesized and analyzed by a combination of spectroscopy and microscopy, electrical characterization, and theoretical calculations. Circular dichroism (CD) experiments demonstrated a transfer of chirality from the dinucleotides to quaterthiophene at high ionic strength and in cast films. The films were photoluminescent and electroactive. CD and photoluminescence spectra and current density/voltage plots (measured under dynamic vacuum) displayed significant variation on changing the dinucleotide scaffold. Molecular mechanics and molecular dynamics calculations indicated that the conformation and packing modes of the conjugates are the result of a balance between intra- and intermolecular nucleobase-thiophene stacking interactions and intramolecular hydrogen bonding between the nucleobases.     

Mechanistic study of asymmetric oxidative biaryl coupling: evidence for self-processing of the copper catalyst to achieve control of oxidase vs oxygenase activity

Copper(I) and copper(II) 1,5-diaza-cis-decalin complexes [(N2)Cu] are effective precatalysts for aerobic oxidative coupling of naphthol substrates. Mechanistic studies, however, reveal that these complexes are not the reactive form of the catalyst under steady-state conditions. Rather, the active catalyst forms in a presteady-state self-processing step that involves oxygenation of the naphthol substrate. The oxygenated substrate, NapHOX, serves as a cofactor that combines with the (N2)Cu complexes to achieve highly selective, steady-state oxidase reactivity (aerobic oxidative biaryl coupling).     

Catalytic enantioselective Meerwein-Eschenmoser Claisen rearrangement: asymmetric synthesis of allyl oxindoles

The first catalytic, enantioselective Meerwein-Eschenmoser Claisen rearrangement has been achieved. Palladium(II) BINAP or phosphinooxazoline catalysts were employed to generate oxindole products with 100% conversion and up to 92% ee.     

Laplacian Flow of Closed G$$_$$-Structures Inducing Nilsolitons

We study the existence of left invariant closed \(G_2\)-structures defining a Ricci soliton metric on simply connected nonabelian nilpotent Lie groups. For each one of these \(G_2\)-structures, we show long time existence and uniqueness of solution for the Laplacian flow on the noncompact manifold. Moreover, considering the Laplacian flow on the associated Lie algebra as a bracket flow on \({\mathbb {R}}^7\) in a similar way as in Lauret (Commun Anal Geom 19(5):831–854, 2011) we prove that the underlying metrics \(g(t)\) of the solution converge smoothly, up to pull-back by time-dependent diffeomorphisms, to a flat metric, uniformly on compact sets in the nilpotent Lie group, as \(t\) goes to infinity.     

On Models of Directed Path Graphs Non Rooted Directed Path Graphs

A directed path graph is the intersection graph of a family of directed subpaths of a directed tree. A rooted directed path graph is the intersection graph of a family of directed subpaths of a rooted tree. Clearly, rooted directed path graphs are directed path graphs. Several characterizations are known for directed path graphs: one by forbidden induced subgraphs and one by forbidden asteroids. It is an open problem to find such characterizations for rooted directed path graphs. With the purpose of proving knowledge in this direction, we show in this paper properties of directed path models that can not be rooted for chordal graphs with any leafage and with leafage four. Therefore, we prove that for leafage four directed path graphs minimally non rooted directed path graphs have a unique asteroidal quadruple, and can be characterized by the presence of certain type of asteroidal quadruples.     

Polyphenolic Flavonoid Compound Quercetin Effects in the Treatment of Acute Myeloid Leukemia and Myelodysplastic Syndromes

Flavonoids are ubiquitous groups of polyphenolic compounds present in most natural products and plants. These substances have been shown to have promising chemopreventive and chemotherapeutic properties with multiple target interactions and multiple pathway regulations against various human cancers. Polyphenolic flavonoid compounds can block the initiation or reverse the promotion stage of multistep carcinogenesis. Quercetin is one of the most abundant flavonoids found in fruits and vegetables and has been shown to have multiple properties capable of reducing cell growth in cancer cells. Acute myeloid leukemia (AML) and myelodysplastic syndromes (MDS) therapy remains a challenge for hematologists worldwide, and the outcomes for patients with both disorders continue to be poor. This scenario indicates the increasing demand for innovative drugs and rational combinative therapies. Herein, we discuss the multitarget effects of the flavonoid quercetin, a naturally occurring flavonol, on AML and MDS.     

Rational approximations of the Arrhenius integral using Jacobi fractions and gaussian quadrature

The aim of this work is to find approaches for the Arrhenius integral by using the n-th convergent of the Jacobi fractions. The n-th convergent is a rational function whose numerator and denominator are polynomials which can be easily computed from three-term recurrence relations. It is noticed that such approaches are equivalent to the one established by the Gauss quadrature formula and it can be seen that the coefficients in the quadrature formula can be given as a function of the coefficients in the recurrence relations. An analysis of the relative error percentages in the approximations is also presented.     

Calorimetric and SEM studies of PHB–PET polymeric blends

PHB [poly (3-hydroxybutyrate)], post-consumer soft-drink bottles poly (ethylene terephthalate) PET (herein named PET-R) and PHBPET-R (blends of PHB and PET-R in several compositions) samples were evaluated by differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM) in order to verify their thermal properties and porosity according to amounts of PET-R added the blends. The DSC curve showed that the solvents used to solve the polymer mixture cause changes in the thermal behavior of PET-R films and in PHBPET-R blends. SEM studies of the PHBPET-R blends show that with a gradual mass increase of PET-R, there are gradual increases in the porosity of the films.