Odd‐even effect during layer‐by‐layer assembly of polyelectrolytes inspired by marine mussel

Biomimetic polyelectrolyte of Dopa modified poly(acrylic acid) (PAADopa) was synthesized taking advantage of Dopa, the major unit of marine adhesive proteins. Zinc crosslinked PAADopa (PAADopa‐Zn) were formed at acidic pH for more compact structure and assembled with the positively charged polyethylenimine (PEI) to build robust polyelectrolyte multilayers at high salt concentration. Effects of pH, crosslinking degree, and salt concentration on polymer structure, film building process, and morphology were investigated, respectively. An “odd‐even” effect was observed by quartz crystal microbalance with dissipation and AFM in the presence of zinc ion, which becomes more obvious with an optimum crosslinking degree (Zn/Dopa = 2.0) under high salt concentration (0.6 M NaCl). It indicates the different swollen properties of PEI chain and PAADopa‐Zn complexes during the layer‐by‐layer building process under optimum crosslinking degree of PAADopa‐Zn at high salt concentration. Such odd‐even phenomenon of the biocompatible system is of critical importance for understanding the mechanism of layer formation and film structures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 245–255     

Investigation of magnetic properties in 57Fe/Al multilayers

Fe/Al multilayer thin films prepared by ion beam sputtering, with an overall atomic concentration ratio of Fe/Al = 1:2 have been studied by x-ray diffraction spectroscopy (XRD), X-ray reflectivity (XRR) and D.C. Magnetization. These studies show the formation of Fe–Al intermetallic layers. Two magnetic regions and transition temperatures of 473 and 533 K are evident from magnetization studies. Conversion Electron Mössbauer Spectroscopy (CEMS) shows formation of off-stoichiometric Fe₃Al like phase and phases consisting of pure Fe and Fe-rich extended Fe–Al solutions.     

UNIFORM SUPERCONVERGENCE OF A FINITE ELEMENT METHOD WITH EDGE STABILIZATION FOR CONVECTION-DIFFUSION PROBLEMS

In the present paper the edge stabilization technique is applied to a convection-diffusion problem with exponential boundary layers on the unit square, using a Shishkin mesh with bilinear finite elements in the layer regions and linear elements on the coarse part of the mesh. An error bound is proved for ‖πu-u^h‖Е, where πu is some interpolant of the solution u and uh the discrete solution. This supercloseness result implies an optimal error estimate with respect to the L2 norm and opens the door to the application of postprocessing for improving the discrete solution.     

Xanthene-modified and hangman iron corroles

Iron corroles modified with a xanthene scaffold are delivered from easily available starting materials in abbreviated reaction times. These new iron corroles have been spectroscopically examined with particular emphasis on defining the oxidation state of the metal center. Investigation of their electronic structure using (57)Fe Mo?ssbauer spectroscopy in conjunction with density functional theory (DFT) calculations reveals the non-innocence of the corrole ligand. Although these iron corroles contain a formal Fe(IV) center, the deprotonated corrole macrocycle ligand is one electron oxidized. The electronic ground state of these complexes is best described as an intermediate spin S = 3/2 Fe(III) site strongly antiferromagnetically coupled to the S = 1/2 of the monoradical dianion corrole [Fe(III)Cl-corrole(+?)]. We show here that iron corroles as well as xanthene-modified and hangman xanthene iron corroles are redox active and catalyze the disproportionation of hydrogen peroxide via the catalase reaction, and that this activity scales with the oxidation potential. The meso position of corrole macrocycle is susceptible toward nucleophilic attack during catalase turnover. The reactivity of peroxide within the hangman cleft reported here adds to the emerging theme that corroles are good at catalyzing two-electron activation of the oxygen-oxygen bond in a variety of substrates.     

Polyhedral approximation of ellipsoidal uncertainty sets via extended formulations: a computational case study

Robust optimization is an important technique to immunize optimization problems against data uncertainty. In the case of a linear program and an ellipsoidal uncertainty set, the robust counterpart turns into a second-order cone program. In this work, we investigate the efficiency of linearizing the second-order cone constraints of the latter. This is done using the optimal linear outer-approximation approach by Ben-Tal and Nemirovski (Math Oper Res 26:193–205, 2001) from which we derive an optimal inner approximation of the second-order cone. We examine the performance of this approach on various benchmark sets including portfolio optimization instances as well as (robustified versions of) the MIPLIB and the SNDlib.     

Purity of potassium hydrogen phthalate, determination with precision coulometric and volumetric titration--a comparison

The mass fraction of potassium hydrogen phthalate (KHP) from a specific batch was certified as an acidimetric standard. Two different analytical methods on a metrological level were used to carry out certification analysis: precision constant current coulometric and volumetric titration with NaOH. It could be shown that with a commercial automatic titration system in combination with a reliable software for the end-point detection it is possible to produce equivalent results with the same accuracy in comparison to a definite method handled by a fundamental apparatus for traceable precision coulometry. Prerequisite for titrations are that a high number of single measurement are applied which are calibrated with a high precision certified reference material.     

Water uptake analysis of acceptor-doped lanthanum orthoniobates

In this work, lanthanum orthoniobates doped with either antimony, calcium, or both have been synthesized and studied. The water uptake of the investigated materials has been analyzed by means of thermogravimetric studies. The results show the difference between the thermodynamics of hydration between the lanthanum orthoniobate system and other proton conducting ceramics. The relation between the water uptake and effective acceptor doping for the investigated system has been found, and the energetics of the water uptake relation are discussed.

     

A Very Strong Methylation Agent: [Me2Cl][Al(OTeF5)4]

A new chloronium‐containing salt, [Me₂Cl][Al(OTeF₅)₄], was synthesized on multigram scale by means of a simple one‐pot procedure. The isolated product can be handled at room temperature and used as a strong electrophilic methylation agent. This is demonstrated by the methylation of the very weak bases P(CF₃)₃, PF₃, MeI, and MeBr.