Role of nitrogen in the mobility drop of electrons in modulation-doped GaAsN/AlGaAs heterostructures

We report transport properties of a 2 dimension electron gas (2DEG) in molecular beam epitaxy-grown GaAs_1−xN_x/AlGaAs modulation-doped heterostructures. Quantum oscillations in far infrared cyclotron resonance prove the efficient electron transfer and formation of the 2DEG. The 2DEG mobility strongly depends on the N concentration in the channel layer. It shows a drastic decrease as compared to N-free samples, even for the smallest amount of N (0.02%). For this N composition, the electron effective mass was found to be 0.073m₀. Reduced growth temperature (450 °C) was found to improve the mobility of N-containing channels. Examination of transport properties from 4 to 300 K and cyclotron resonance experiments give evidence of the presence of ionised impurity-like scattering centres in GaAsN.     

Poly(N-vinylimidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids

In this study we report the novel polymeric resin poly(N-vinyl imidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids. The monomer to crosslinker ratio and the porogen composition were optimized for isolating phenolic acids diluted in acetonitrile at normal phase chromatography conditions, first. Acetonitrile serves as polar, aprotic solvent, dissolving phenolic acids but not interrupting interactions with the stationary phase due to the approved Hansen solubility parameters. The optimized resin demonstrated high loading capacities and adsorption abilities particularly for phenolic acids in both, acetonitrile and aqueous solutions. The adsorption behavior of aqueous standards can be attributed to ion exchange effects due to electrostatic interactions between protonated imidazole residues and deprotonated phenolic acids. Furthermore, adsorption experiments and subsequent curve fittings provide information of maximum loading capacities of single standards according to the Langmuir adsorption model. Recovery studies of the optimized polymer in the normal-phase and ion-exchange mode illustrate the powerful isolation properties for phenolic acids and are comparable or even better than typical, commercially available solid phase extraction materials. In order to prove the applicability, a highly complex extract of rosemary leaves was purified by poly(N-vinyl imidazole/ethylene glycol dimethacrylate) and the isolated compounds were identified using UHPLC–qTOF-MS.     

Positive block matrices and numerical ranges

Any positive matrix M partitioned in four n-by-n blocks satisfies the unitarily invariant norm inequality $6M6\le 6M_{1,1}+M_{2,2}+\omega I6$, where ω is the width of the numerical range of $M_{1,2}$. Some related inequalities and a reverse Lidskii majorization are given.     

Convergence of the Two‐Dimensional Dynamic Ising‐Kac Model to

The Ising‐Kac model is a variant of the ferromagnetic Ising model in which each spin variable interacts with all spins in a neighborhood of radius γ ^{? 1} for around its base point. We study the Glauber dynamics for this model on a discrete two‐dimensional torus for a system size and for an inverse temperature close to the critical value of the mean field model. We show that the suitably rescaled coarse‐grained spin field converges in distribution to the solution of a nonlinear stochastic partial differential equation. This equation is the dynamic version of the quantum field theory, which is formally given by a reaction‐diffusion equation driven by an additive space‐time white noise. It is well‐known that in two spatial dimensions such equations are distribution valued and a Wick renormalization has to be performed in order to define the nonlinear term. Formally, this renormalization corresponds to adding an infinite mass term to the equation. We show that this need for renormalization for the limiting equation is reflected in the discrete system by a shift of the critical temperature away from its mean field value.© 2016 by the authors. Communications on Pure and Applied Mathematics is published by Wiley Periodicals, Inc., on behalf of the Courant Institute of Mathematics.     

Design of robust binary film onto carbon surface using diazonium electrochemistry

The electroreduction of functionalized aryldiazonium salts combined with a protection-deprotection method was evaluated for the fabrication of organized mixed layers covalently bound onto carbon substrates. The first modification consists of the grafting of a protected 4-((triisopropylsilyl)ethynyl)benzene layer onto the carbon surface on which the introduction of a second functional group is possible without altering the first grafted functional group. After deprotection, we obtained an ultrathin robust layer presenting high densities of both active ethynylbenzene groups (available for "click" chemistry) and the second functional group. The strategy was successfully demonstrated using azidomethylferrocene to react with ethynyl moieties in the binary film by "click" chemistry, and NO(2)-phenyl as the second functional group. Two possible modification pathways with different orderings of the various steps were considered to show the influence and importance of the protection-deprotection process on the final surface obtained. Using mild conditions for the grafting of the second layer maintains a concentration of active ethynyl groups similar to that obtained for a one-component monolayer while achieving a high surface concentration of the second modifier. Considering the wide range of functional aryldiazonium salts that could be electrodeposited onto carbon surfaces and the versatility and specificity of the "click" chemistry, this approach appears very promising for the preparation of mixed layers in well-controlled conditions without altering the reactivity of either functional group.     

Rates of intra- and intermolecular electron transfers in hydrogenase deduced from steady-state activity measurements

Electrons are transferred over long distances along chains of FeS clusters in hydrogenases, mitochondrial complexes, and many other respiratory enzymes. It is usually presumed that electron transfer is fast in these systems, despite the fact that there has been no direct measurement of rates of FeS-to-FeS electron transfer in any respiratory enzyme. In this context, we propose and apply to NiFe hydrogenase an original strategy that consists of quantitatively interpreting the variations of steady-state activity that result from changing the nature of the FeS clusters which connect the active site to the redox partner, and/or the nature of the redox partner. Rates of intra- and intermolecular electron transfer are deduced from such large data sets. The mutation-induced variations of electron transfer rates cannot be explained by changes in intercenter distances and reduction potentials. This establishes that FeS-to-FeS rate constants are extremely sensitive to the nature and coordination of the centers.     

On the elucidation of the mechanism of Vinca alkaloid fluorination in superacidic medium

Detailed investigations on one of the key steps of the superacidic fluorination of Vinca alkaloids that is the origin of C20' activation are reported. While two different pathways can be envisioned for the emergence of the transient secondary carbocationic intermediate, isotopic labeling experiments unambiguously revealed the involvement of a 1,2-hydride shift mechanism.     

Highly efficient one-pot access to functionalized arylboronic acids via noncryogenic bromine/magnesium exchanges

A general and convenient protocol for the electrophilic borylation of aryl Grignard reagents prepared from arylbromides by direct insertion of magnesium in the presence of LiCl or by Mg/Br exchange with (i)PrMgCl·LiCl has been developed. Various aryl boronic acids were synthesized in a straightforward manner in excellent yields at 0 °C.     

Modulating the photophysical properties of azamacrocyclic europium complexes with charge-transfer antenna chromophores

Two europium complexes with bis(bipyridine) azamacrocyclic ligands featuring pendant arms with or without π-conjugated donor groups are synthesized and fully characterized by theoretical calculations and NMR spectroscopy. Their photophysical properties, including two-photon absorption, are investigated in water and in various organic solvents. The nonfunctionalized ligand gives highly water-stable europium complexes featuring bright luminescence properties but poor two-photon absorption cross sections. On the other hand, the europium complex with an extended conjugated antenna ligand presents a two-photon absorption cross section of 45 GM at 720 nm but is poorly luminescent in water. A detailed solvent-dependent photophysical study indicates that this luminescence quenching is not due to the direct coordination of O-H vibrators to the metal center but to the increase of nonradiative processes in a protic solvent induced by an internal isomerization equilibrium.