Silver stain removal using H2O2 for enhanced peptide mass mapping by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Hydrogen peroxide solutions are reported for the removal of silver stain from proteins isolated in polyacrylamide gels. Removal of silver stain prior to in-gel digestion is shown to enhance sensitivity and sequence coverage of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) peptide mass maps. The rate of silver removal using H2O2 is influenced by H2O2 concentration and increases with increasing pH. The presence of complexation reagents such as ammonia from mass spectrometry compatible ammonium bicarbonate solutions enhances the efficiency and speed of H2O2-mediated silver removal. H2O2-mediated silver removal using the described procedure does not appear to have any detrimental effects on proteins but is observed to produce a slightly elevated level of methionine oxidization over that usually observed in in-gel tryptic digestion.     

The diameter of domination k-critical graphs

A graph is k-domination-critical if γ(G) = k, and for any edge e not in G, γ(G + e) = k ? 1. In this paper we show that the diameter of a domination k-critical graph with k ≧ 2 is at most 2k ? 2. We also show that for every k ≧ 2, there is a k-domination-critical graph having diameter [(3/2)k ? 1]. We also show that the diameter of a 4-domination-critical graph is at most 5.     

Membrane selectivity for an aqueous system by dynamic osmometry

Commercial and fractionated samples of poly(ethylene glycol) and a sample of Dextran were used as standards to show the limitation of a cellulose acetate membrane for osmotic pressure determination of molecular weight in an aqueous system. The leakage of this membrane was much greater in the aqueous system than in organic solvents.     

A conserved asparagine in a ubiquitin-conjugating enzyme positions the substrate for nucleophilic attack

The mechanism used by the ubiquitin-conjugating enzyme, Ubc13, to catalyze ubiquitination is probed with three computational techniques: Born–Oppenheimer molecular dynamics, single point quantum mechanics/molecular mechanics energies, and classical molecular dynamics. These simulations support a long-held hypothesis and show that Ubc13-catalyzed ubiquitination uses a stepwise, nucleophilic attack mechanism. Furthermore, they show that the first step—the formation of a tetrahedral, zwitterionic intermediate—is rate limiting. However, these simulations contradict another popular hypothesis that supposes that the negative charge on the intermediate is stabilized by a highly conserved asparagine (Asn79 in Ubc13). Instead, calculated reaction profiles of the N79A mutant illustrate how charge stabilization actually increases the barrier to product formation. Finally, an alternate role for Asn79 is suggested by simulations of wild-type, N79A, N79D, and H77A Ubc13: it stabilizes the motion of the electrophile prior to the reaction, positioning it for nucleophilic attack. © 2019 Wiley Periodicals, Inc.     

Detection of a single electron in xenon-based electroluminescent detectors

It is experimentally shown that a single ionization electron can be detected by various xenon-based electroluminescent detectors with optical readout, such as a high-pressure cylindrical gas counter, a two-phase detector with gas amplification, and a two-phase detector with a plane-parallel and uniform electric field. The sensitivity of the detectors was 7, 18, and 15 photoelectrons respectively. The coordinate resolution of the two-phase detector for electrons resulting from field emission at the cathode was σ _X,Y = 5.2 mm.     

From solid state to solution: advancing chemistry of Bi-Bi and Bi-Rh paddlewheel carboxylates

The first successful high-yield solution synthesis of homobimetallic Bi(2)(O(2)CCF(3))(4) (1), as well as heterobimetallic BiRh(O(2)CCF(3))(4) (2) and BiRh(O(2)CCF(2)CF(3))(4) (3), complexes is reported. It is based on one-pot reduction reactions starting from Bi(III) and Rh(II) carboxylates and using Bi metal as a reducing agent. The presence of small amounts of diphenyl ether was found to facilitate this reaction, most probably because of its good solubilizing and π-stabilizing abilities. The latter is illustrated by the isolation and structural characterization of a π-adduct of 1 with diphenyl ether, [Bi(2)(O(2)CCF(3))(4)·1/2Ph(2)O]. Importantly, the new approach expands to solution the chemistry of Bi(II) that was previously limited to the solid state only. The solution procedure developed for the preparation of heterometallic BiRh(O(2)CCF(3))(4) is now one step shorter and gives the product in excellent yield compared with the previously reported method based on sublimation-deposition technique. It is also performed on a greater scale (~10-20 times) and makes further scale-up feasible, if needed. Moreover, it eliminates the isolation of the hard-to-handle unsolvated Bi(II) trifluoroacetate used earlier as a starting material. A new polymorph of BiRh(O(2)CCF(3))(4) (2) was crystallized from solution in this work. The solution approach was also applied to the synthesis of a new heterobimetallic carboxylate with perfluorinated propionate ligands, BiRh(O(2)CCF(2)CF(3))(4) (3). All products are fully characterized by spectroscopic and single crystal X-ray diffraction methods. Complexes 2 and 3 exhibit similar solid state structures based on heterobimetallic paddlewheel units forming infinite 1D chains through intermolecular Rh···O interactions.     

Hamiltonian results in K1,3-free graphs

There have been a number of results dealing with Hamiltonian properties in powers of graphs. In this paper we show that the square and the total graph of a K_1,3-free graph are vertex pancyclic. We then discuss some of the relationships between connectivity and Hamiltonian properties in K_1,3-free graphs.     

Chemical and Physical Analysis of Acetate-Oxide Sol-Gel Processing Routes for the Y-Ba-Cu-O System

The formation of three sols by fluorine-free aqueous and non-aqueous processes were analyzed and modified to vary the chemical properties of the sols (inks) to suit a variety of deposition processes such as dip-coating and ink-jet coating/printing. Ink-jet printing requires high wetting angles; choosing the right complexing agents to modify the ink allows the formation of droplets with high wetting angles on the surface. Dip-coating and ink-jet coating require low wetting angles; additives added to the sols reduce wetting angles to 10^∘ and allow complete coverage of the substrate surface. The deposition theories and requirements are briefly discussed, as are some initial tests with the printing and converting of the developed superconducting inks.