Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell

This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.     

Sorption of methanol,dimethyl carbonate,methyl acetate,and acetone vapors in CTA and PTMSP: General findings from the GAB Analysis

Sorption of vapors of four organic compounds in two glassy polymers, cellulose triacetate (CTA) and poly[(trimethylsilyl)propyne] (PTMSP), has been reported and analyzed in terms of Guggenheim‐Anderson‐De Boer (GAB) model. These two structurally and physicochemically different glassy polymers both independently showed that one sorption site was formed by about three monomeric units. This finding held true for vapors of all characterized compounds; that is, for methanol, for its derivatives dimethyl carbonate and methyl acetate, and for acetone. The “rule of three” might thus also be applicable to other sorbates and glassy polymers. Further, an original modification of the GAB model for the sorption of alcohols in PTMSP was derived and successfully tested. Overall, the analyses of the sorption isotherms, heats of sorption and diffusion coefficients supported the view that the sorption of vapors in glassy polymers has adsorptive nature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 561–569     

Preparative separation of immunoglobulins from bovine colostrum by continuous divergent-flow electrophoresis

Immunoglobulins in bovine colostrum were separated and fractionated from other proteins using the method and instrumentation developed in our laboratory. The proposed separation was based on bidirectional isotachophoresis/moving boundary electrophoresis with electrofocusing of the analytes in a pH gradient from 3.9 to 10.1. The preparative instrumentation included the trapezoidal non-woven fabric that served as separation space with divergent continuous flow. The defatted and casein precipitate-free colostrum supernatant was loaded directly into the instrument without any additional colostrum pre-preparation. Immunoglobulin G was fractionated from other immune proteins such as bovine serum albumin, β-lactoglobulin, and α-lactalbumin, and was continuously collected in separated fractions over 3 h. The fractions were further processed, and isolated immunoglobulin G in the liquid fractions was confirmed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and by re-focusing in gel isoelectric focusing. Separated immunoglobulin G was detected in seven fractions by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with a gradually decreased concentration in the fractions. Re-focusing of the proteins in the fractions by gel isoelectric focusing revealed multiple separated zones of immunoglobulin G with the isoelectric point values covering the range from 5.4 to 7.2. Each fraction contained distinct zones with gradually increased isoelectric point values and decreased concentrations from fraction to fraction.     

Arrival time distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility–mass spectrometry of hyaluronan‐derived oligosaccharides

Hyaluronic acid is a naturally occurring linear polysaccharide with substantial medical potential. In this work, discrimination of tyramine‐based hyaluronan derivatives was accessed by ion mobility–mass spectrometry of deprotonated molecules and nuclear magnetic resonance spectroscopy. As the product ion mass spectra did not allow for direct isomer discrimination in mixture, the reductive labeling of oligosaccharides as well as stable isotope labeling was performed. The ion mobility separation of parent ions together with the characteristic fragmentation for reduced isomers providing unique product ions allowed us to identify isomers present in a mixture and determine their mutual isomeric ratio. The determination used simple recalculation of arrival time distribution areas of unique ions to areas of deprotonated molecules. Mass spectrometry data were confirmed by nuclear magnetic resonance spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

High‐throughput workflow for identification of phosphorylated peptides by LC‐MALDI‐TOF/TOF‐MS coupled to in situ enrichment on MALDI plates functionalized by ion landing

We report an MS‐based workflow for identification of phosphorylated peptides from trypsinized protein mixtures and cell lysates that is suitable for high‐throughput sample analysis. The workflow is based on an in situ enrichment on matrix‐assisted laser desorption/ionization (MALDI) plates that were functionalized by TiO₂ using automated ion landing apparatus that can operate unsupervised. The MALDI plate can be functionalized by TiO₂ into any array of predefined geometry (here, 96 positions for samples and 24 for mass calibration standards) made compatible with a standard MALDI spotter and coupled with high‐performance liquid chromatography. The in situ MALDI plate enrichment was compared with a standard precolumn‐based separation and achieved comparable or better results than the standard method. The performance of this new workflow was demonstrated on a model mixture of proteins as well as on Jurkat cells lysates. The method showed improved signal‐to‐noise ratio in a single MS spectrum, which resulted in better identification by MS/MS and a subsequent database search. Using the workflow, we also found specific phosphorylations in Jurkat cells that were nonspecifically activated by phorbol 12‐myristate 13‐acetate. These phosphorylations concerned the mitogen‐activated protein kinase/extracellular signal‐regulated kinase signaling pathway and its targets and were in agreement with the current knowledge of this signaling cascade. Control sample of non‐activated cells was devoid of these phosphorylations. Overall, the presented analytical workflow is able to detect dynamic phosphorylation events in minimally processed mammalian cells while using only a short high‐performance liquid chromatography gradient. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and Catalytic Use of Gold(I) Complexes Containing a Hemilabile Phosphanylferrocene Nitrile Donor

Removal of the chloride ligand from [AuCl( 1 ‐κP)] ( 2 ) containing a P‐monodentate 1′‐(diphenylphosphanyl)‐1‐cyanoferrocene ligand ( 1 ), by using silver(I) salts affords cationic complexes of the type [Au( 1 )]X, which exist either as cyclic dimers [Au( 1 )]₂X₂ ( 3 a , X=SbF₆; 3 c , X=NTf₂) or linear coordination polymers [Au( 1 )]_nX_n ( 3 a′ , X=SbF₆; 3 b′ , X=ClO₄), depending on anion X and the isolation procedure. As demonstrated for 3 a′ , the polymers can be readily cleaved by the addition of donors, such as Cl^?, tetrahydrothiophene (tht) or 1 , giving rise to the parent compound 2 , [Au(tht)( 1 ‐κP)][SbF₆] ( 5 a ) or [Au( 1 ‐κP)₂][SbF₆] ( 4 a ), respectively, of which the last two compounds can also be prepared by stepwise replacement of tht in [Au( 1 ‐κP)₂][SbF₆]. The particular combination of a firmly coordinated (phosphane) and a dissociable (nitrile) donor moieties renders complexes 3/3′ attractive for catalysis because they can serve as shelf‐stable precursors of coordinatively unsaturated Au^I fragments, analogous to those that result from the widely used [Au(PR₃)(RCN)]X catalysts. The catalytic properties of the Au‐ 1 complexes were evaluated in model annulation reactions, such as the synthesis of 2,3‐dimethylfuran from (Z)‐3‐methylpent‐2‐en‐4‐yn‐1‐ol and oxidative cyclisation of alkynes with nitriles to produce 2,5‐disubstituted 1,3‐oxazoles. Of the compounds tested ( 2 , 3 a′ , 3 b′ , 3 a , 4 a and 5 a ), the best results were consistently achieved with dimer 3 c , which has good solubility in organic solvents and only one firmly bound donor at the gold atom. This compound was advantageously used in the key steps of annuloline and rosefuran syntheses.     

High Performance Liquid Chromatography/Electrochemistry/High Resolution Electrospray Ionization‐Mass Spectrometry (HPLC/EC/HR ESI‐MS) Characterization of Selected Cytokinins Oxidation Products

Electrochemistry combined with mass spectrometry represents an emerging analytical technique used to study the oxidation pathway of various drugs and in vivo occurring compounds, continuously showing a capability to generate many known metabolites or new oxidation products. An on‐line HPLC/EC/HR ESI‐MS method had been used to investigate the oxidation of selected cytokinin compounds. This setup allowed rapid identification and general structure elucidation of the obtained products. An electrochemical oxidation of isopentenyladenine resulted in five products, including hydroxylated and dehydrogenated products, which correlates very well with its in vivo metabolism. Electrochemical conversion of trans‐zeatin revealed six products, with two dehydrogenation products corresponding to its in vivo occurring metabolites. cis‐Zeatin oxidation in the electrochemical cell gave rise to eight products, resembling similarity to trans‐zeatin oxidation. All three compounds underwent a complete turnover mainly through two oxidation reactions occurring in the electrochemical cell? dehydrogenation and a less typical aliphatic hydroxylation. The resulting products are in correlation with their known in vivo metabolism.     

Creating Space for Large Acceptors: Rational Biocatalyst Design for Resveratrol Glycosylation in an Aqueous System

Polyphenols display a number of interesting properties but their low solubility limits practical applications. In that respect, glycosylation offers a solution for which sucrose phosphorylase has been proposed as a cost‐effective biocatalyst. However, its activity on alternative acceptor substrates is too low for synthetic purposes and typically requires the addition of organic (co‐)solvents. Here, we describe the engineering of the enzyme from Thermoanaerobacterium thermosaccharolyticum to enable glycosylation of resveratrol as test case. Based on docking and modeling studies, an active‐site loop was predicted to hinder binding. Indeed, the unbolted loop variant R134A showed useful affinity for resveratrol (K_m=185 mM ) and could be used for the quantitative production of resveratrol 3‐α‐glucoside in an aqueous system. Improved activity was also shown for other acceptors, introducing variant R134A as promising new biocatalyst for glycosylation reactions on bulky phenolic acceptors.