A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance‐improved and cost‐reduced solid‐solution alloy nanoparticles of the Cu‐Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cu_xRu_1?x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.     

Power of isotopic fine structure for unambiguous determination of metabolite elemental compositions: In silico evaluation and metabolomic application

In mass spectrometry (MS)-based metabolomics studies, reference-free identification of metabolites is still a challenging issue. Previously, we demonstrated that the elemental composition (EC) of metabolites could be unambiguously determined using isotopic fine structure, observed by ultrahigh resolution MS, which provided the relative isotopic abundance (RIA) of ¹³C, ¹⁵N, ¹⁸O, and ³⁴S. Herein, we evaluated the efficacy of the RIA for determining ECs based on the MS peaks of 20,258 known metabolites. The metabolites were simulated with a ≤25% error in the isotopic peak area to investigate how the error size effect affected the rate of unambiguous determination of the ECs. The simulation indicated that, in combination with reported constraint rules, the RIA led to unambiguous determination of the ECs for more than 90% of the tested metabolites. It was noteworthy that, in positive ion mode, the process could distinguish alkali metal-adduct ions ([M + Na]⁺ and [M + K]⁺). However, a significant degradation of the EC determination performance was observed when the method was applied to real metabolomic data (mouse liver extracts analyzed by infusion ESI), because of the influence of noise and bias on the RIA. To achieve ideal performance, as indicated in the simulation, we developed an additional method to compensate for bias on the measured ion intensities. The method improved the performance of the calculation, permitting determination of ECs for 72% of the observed peaks. The proposed method is considered a useful starting point for high-throughput identification of metabolites in metabolomic research.     

Predicted radiolysis yield in a Fricke solution irradiated with various heavy ions

Experimental data on the spatial distribution of the energy deposited around an energetic heavy ion, from 1 MeV proton to 5.9 MeV/n uranium ion, which have been reported in the literature were documented to obtain a scaled radial dose distribution; (β/Z*)² D(Z*, β,t)=200 (for t=0–1), 200/t² (for t=1t_c), and 200 t_c/t³ (for t>t_c) where Z* and β are the effective charge and velocity relative to c, the velocity of light, of the incident ion, respectively, D the dose in unit of Gy, t the radial distance in unit of nm, t_c the critical distance empirically determined.

Then, if we know the yield of any chemical reaction as a function of dose from the results of experiments using γ-radiations or fast electrons or theoretical calculations, we can calculate the probability for the yield of the chemical reaction in the system bombarded with a heavy ion of the effective charge Z* and velocity β. The results of the present calculation of the LET-values and of G(Fe³⁺) in the ferrous sulfate acidic solution are presented and compared with reported experimental results.     

Stokesian dynamics simulation of the role of hydrodynamic interactions on the behavior of a single particle suspending in a Newtonian fluid. Part 1. 1D flexible and rigid fibers

As seen in textbooks of polymer physics, a linear polymer chain can be modeled as a filament of connected beads. This concept can also be adapted to fibers and, for example, flexible fibers can be modeled by considering a stretch force, bending and torsion torques with a non-slip condition between adjacent beads, following the particle simulation method. In predicting fiber motions and their relating rheological properties, the importance of hydrodynamic interactions should be analyzed, so in this work we study the effect of hydrodynamic interactions on the behavior of a single flexible fiber under shear using Stokesian dynamics simulation with a 11N × 11N mobility matrix, where N is the aspect ratio of the fiber. Our results indicate that hydrodynamic interaction becomes significant when the fiber is highly flexible.     

Analytical Hartree–Fock wave functions for the atoms Cs to Lr

 Analytical approximations to Hartree–Fock wave functions are constructed using Slater-type functions for the ground states of all 49 neutral atoms from Cs (Z=55) to Lr (Z=103). The current compilation is more extensive and more accurate than previous ones. The wave functions are available upon request from the authors or from the Web page http://www.unb.ca/chem/ajit/download.htm on the Internet. Received: 6 December 1999 / Accepted: 29 February 2000 / Published online: 12 May 2000     

Discussion of substantially identical gel points among multiallyl monomers based on characterization of resultant network polymer precursors consisting of oligomeric primary polymer chains

No difference in the actual gel points was substantially observed among three isomeric diallyl phthalates such as diallyl phthalate (DAP), diallyl isophthalate, and diallyl terephthalate (DAT); this interesting gelation behavior was discussed further in terms of the correlation between gelation and the difference in cyclization modes, and also, the difference in reactivity between the uncyclized and cyclized radicals for cross‐linking. In the present work, we tried to extend the preceding discussion to the polymerization of triallyl trimellitate (TAT) because the molecular structure of TAT is presumed to essentially involve the characteristics of three isomeric diallyl phthalates and, therefore, the enhanced gelation was expected in TAT polymerization. However, no enhancement of gelation was observed. For a full understanding of the gelation in multiallyl cross‐linking polymerization, we explored further the polymerizations of DAP, DAT, and TAT, especially focusing on the characterization of resultant network polymer precursors (NPPs) using SEC‐MALLS‐viscometry providing the correlation of [η] versus M_w of fractionated samples. Notably, the structure of NPP consisting of oligomeric primary polymer chains generated from specific allyl polymerization would become core‐shell type dendritic with the progress of polymerization. The correlation between delayed gelation and decreased reactivity of dendritic NPP for intermolecular cross‐linking is discussed. Conclusively, the reactivity for intermolecular cross‐linking between NPPs decreased with the progress of polymerization leading to a delayed gelation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2871–2881, 2009     

Preparation of calix[4]arene methylene crosslinked resins with 2-pyridyl pendant group and their adsorption behavior towards silver ion

Three different resins namely 1:5 MC-resin, 1:3 MC-resin and 1:1 MC-resin have been synthesized by methylene crosslinking of 2-pyridylcalix[4]arene. Adsorption behavior of these resins towards the metal ions existing in photographic waste was investigated. The resins show absolute efficiency for adsorption of silver ion with no affinity for other coexisting ions. First two resins form 1:1 complex whereas the third one forms 2:1 complex with silver ion. Maximum loading capacity of silver ion on the present resins was found to be 1.15, 1.29 and 0.69 mol kg^?1, respectively. Column chromatographic separation of silver ion in presence of excess of sodium ions was also carried out with 1:5 MC-resin. Selective adsorption of silver ions over excess of sodium ions was achieved.     

Allosteric coextraction of sodium and metal ions with calix[4]arene derivatives 1

Solvent extraction of three alkali metal ions with p-t-octylcalix[6]arene hexacarboxylic acid, p-t-octylcalix[4]arene tetracarboxylic acid, corresponding linear trimeric and monomeric analogs was investigated. Cyclic tetramer selectively extracts sodium ion among alkali ions at extremely low pH, while the corresponding cyclic hexamer, the trimer, and the monomer exhibited only poor extraction ability for all alkali metals examined. The detailed extractive investigation of sodium ions with the cyclic tetramer was carried out. It was found that two sodium ions are simultaneously extracted by a single molecule of calix[4]arene derivative and that the second sodium extraction is facilitated by the uptake of the first sodium. The self-coextraction mechanism of sodium ions proposed in the present paper also strongly supports allosteric coextraction of sodium and other metal ions. In the competitive extraction of four alkali metal ions, potassium ion was slightly extracted as the second ion at low pH region, whereas it was hardly extracted in the individual extraction system. The result also supports the coextraction mechanism and role of the first-extracted sodium ion as an allosteric trigger. The extraction equilibrium constants of the cyclic tetramer and two sodium ions, K _ex1 and K _ex2, were estimated.