Why is silver catalytically active for NO reduction? A unique pathway via an inverted (NO)2 dimer

NO reduction on the noble metal Ag has been studied using density functional theory calculations. It was found that monomeric NO dissociation is subject to prohibitive barriers on Ag metal and is thus unlikely to account for the experimental observations for NO reduction over Ag-based catalysts. For the first time, a mechanism via an inverted (NO)(2) dimer is identified, which can explain both the high activity and the selectivity of this catalytic system. N(2)O is the major reduction product of the inverted (NO)(2) dimer, in accord with experiment. The physical origin of the Ag metallic state as a good catalyst is furthermore identified: Ag surfaces, including small clusters, have little or no covalent bonding ability but can bond ionically with adsorbates. We conclude that the variation of the ionic bonding strength of Ag toward different reactants determines its catalytic selectivity.     

Asymmetric transfer hydrogenation in water with a supported Noyori-Ikariya catalyst

[reaction: see text] The poly(ethylene glycol)-supported ruthenium precatalyst shown above is highly effective for asymmetric transfer hydrogenation of unfunctionalized aromatic ketones by HCOONa in neat water, affording fast rates, good to excellent enantioselectivities, and outstanding reusability.     

How to make a triangulation of polytopal

We introduce a numerical isomorphism invariant for any triangulation of . Although its definition is purely topological (inspired by the bridge number of knots), reflects the geometric properties of . Specifically, if is polytopal or shellable, then is ``small' in the sense that we obtain a linear upper bound for in the number of tetrahedra of . Conversely, if is ``small', then is ``almost' polytopal, since we show how to transform into a polytopal triangulation by local subdivisions. The minimal number of local subdivisions needed to transform into a polytopal triangulation is at least . Using our previous results [The size of triangulations supporting a given link, Geometry & Topology 5 (2001), 369-398], we obtain a general upper bound for exponential in . We prove here by explicit constructions that there is no general subexponential upper bound for in . Thus, we obtain triangulations that are ``very far' from being polytopal. Our results yield a recognition algorithm for that is conceptually simpler, although somewhat slower, than the famous Rubinstein-Thompson algorithm.

     

Changes in MRI signal intensity during hypercapnic challenge under conscious and anesthetized conditions

Most functional magnetic resonance imaging (fMRI) studies in animals are conducted under anesthesia to minimize motion artifacts. However, methods and techniques have been developed recently for imaging fully conscious rats. Functional MRI studies on conscious animals report enhanced BOLD signal changes as compared to the anesthetized condition. In this study, rats were exposed to different concentrations of carbon dioxide (CO(2)) while conscious and anesthetized to test whether cerebrovascular reactivity may be contributing to these enhanced BOLD signal changes. Hypercapnia produced significantly greater increases in MRI signal intensity in fully conscious animals (6.7-13.3% changes) as when anesthetized with 1% isoflurane (3.2-4.9% changes). In addition, the response to hypercapnia was more immediate in the conscious condition (< 30s) with signal risetimes twice as fast as in the anesthetized state (60s). Both cortical and subcortical brain regions showed a robust, dose- dependent increase in MRI signal intensity with hypercapnic challenge while the animals were conscious but little or no change when anesthetized. Baseline variations in MRI signal were higher while animals were conscious but this was off set by greater signal intensity changes leading to a greater contrast-to-noise ratio, 13.1 in conscious animals, as compared to 8.0 in the anesthetized condition. In summary, cerebral vasculature appears to be more sensitive to hypercapnic challenge in the conscious condition resulting in enhanced T2* MRI signal intensity and the potential for better BOLD signal changes during functional imaging.     

Measurements of F2 and xF(nu)(3) - xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe Data in a Physics Model-Independent Way

We report on the extraction of the structure functions F2 and DeltaxF(3) = xF(nu)(3)-xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe differential cross sections. The extraction is performed in a physics model-independent (PMI) way. This first measurement of DeltaxF(3), which is useful in testing models of heavy charm production, is higher than current theoretical predictions. The ratio of the F2 (PMI) values measured in nu(mu) and mu scattering is in agreement (within 5%) with the predictions of next-to-leading-order parton distribution functions using massive charm production schemes, thus resolving the long-standing discrepancy between the two sets of data.     

Observation and characterization of the fluorescence decay of the 2s2p(6)np 1P(o) excited states of Ne

Fluorescence decay of the 2s2p(6)np (1)P(o) excited states of neon has been observed directly for the first time. This process has also been observed indirectly by threshold photoelectron spectroscopy and in electron/photon coincidences. The measurements have allowed this weak decay channel to be characterized and branching ratios derived. The fluorescence excitation spectrum is well described by a simple Rydberg model that highlights the interplay and competition between the decay channels of autoionization and fluorescence.     

Semi‐automated tandem mass spectrometric (MS/MS) triple quadrupole operating parameter optimization for high‐throughput MS/MS detection workflows

This paper describes an automated workflow for the determination of selected reaction monitoring (SRM) transitions and optimum mass spectrometric (MS) instrument parameters. The approach uses a Nanomate from Advion Biosciences for automated infusion of small amounts of sample in combination with Automaton optimization software from Sciex. The results are stored in the Analyst software Compound Database for automated acquisition method building. Comparisons are presented between the more traditional optimization methods of manual flow injection optimization, Autotune infusion optimization, Automaton flow injection optimization and the Nanomate–Automaton optimization approach. Data is also presented to show that acquisition methods developed on the Sciex model API3000 instrument can be effectively transferred to the Sceix API4000 and API5000 model instruments. Copyright © 2009 John Wiley & Sons, Ltd.     

A [Cyclentetrakis(methylene)]tetrakis[2‐hydroxybenzamide] Ligand That Complexes and Sensitizes Lanthanide(III) Ions

The synthesis of the cyclen derivative H₄ L ¹ ?2 HBr containing four 2‐hydroxybenzamide groups is described. The spectroscopic properties of the Ln^III conplexes of L ¹ (Ln=Gd, Tb, Yb, and Eu) reveal changes of the UV/VIS‐absorption, circular‐dichroism‐absorption, luminescence, and circularly polarized luminescence spectra. It is shown that at least two metal‐complex species are present in solution, whose relative amounts are pH dependent. At pH>8.0, an intense long‐lived emission is observed (for [Tb L ¹ ] and [Yb L ¹ ]), while at pH<8.0, a weaker, shorter‐lived species predominates. Unconventional Ln^III emitters (Pr, Nd, Sm, Dy, and Tm) were sensitized in basic solution, both in the VIS and in the near‐IR, to measure the emission of these ions.     

The effects of sample preparation methods on the variability of the electrospray ionization response for model drug compounds

A post-column infusion system was developed in order to analyze suppression of electrospray ionization (ESI) tandem mass spectrometry response in the presence of endogenous plasma interferences. By enabling direct detection of these interfering components, this experimental system was used to analyze the ability of several common extraction procedures to remove endogenous plasma components that cause changes in the ESI response of model drug substances. Methyl-t-butyl ether (MTBE) liquid-liquid, Oasis and Empore solid-phase, and acetonitrile (ACN) protein precipitation sample preparation methods were tested using the post-column infusion system. In all cases, ACN protein precipitation samples showed the greatest amount of ESI response suppression while liquid-liquid extracts demonstrated the least. In addition, the three test compounds, phenacetin, caffeine, and a representative Merck compound, demonstrated that ESI response suppression is compound dependent. Suppression was greatest with caffeine, the most polar analyte, and the smallest for the Merck compound, the least polar analyte. Copyright 1999 John Wiley & Sons, Ltd.