Development of proton-transfer ion trap-mass spectrometry: on-line detection and identification of volatile organic compounds in air

We present a newly developed instrument that uses proton-transfer ion trap-mass spectrometry (PIT-MS) for on-line trace gas analysis of volatile organic compounds (VOCs). The instrument is based on the principle of proton-transfer reaction-mass spectrometry (PTR-MS): VOCs are ionized using PTRs and detected with a mass spectrometer. As opposed to a quadrupole mass filter in a PTR-MS, the PIT-MS instrument uses an IT-MS, which has the following advantages: (1) the ability to acquire a full mass spectrum in the same time as one mass with a quadrupole and (2) extended analytical capabilities of identifying VOCs by performing collision-induced dissociation (CID) and ion molecule reactions in the IT. The instrument described has, at its current status, limits of detection between 0.05 and 0.5 pbbv for 1-min measurements for all tested VOCs. The PIT-MS was tested in an ambient air measurement in the urban area of Boulder, Colorado, and intercompared with PTR-MS. For all measured compounds the degree of correlation between the two measurements was high (r ² > 0.85), except for acetonitrile (CH₃CN), which was close to the limit of detection of the PIT-MS instrument. The two measurements agreed within less than 25%, which was within the combined measurement uncertainties. Automated CID measurements on m/z 59 during the intercomparison were used to determine the contributions of acetone and propanal to the measured signal; both are detected at m/z 59 and thus are indistinguishable in PTR-MS. It was determined that m/z 59 was mainly composed of acetone. An influence of propanal was detected only during a high pollution event. The advantages and future developments of PIT-MS are discussed.     

A Self‐Binding,Melt‐Castable,Crystalline Organic Electrolyte for Sodium Ion Conduction

The preparation and characterization of the cocrystalline solid–organic sodium ion electrolyte NaClO₄(DMF)₃ (DMF=dimethylformamide) is described. The crystal structure of NaClO₄(DMF)₃ reveals parallel channels of Na⁺ and ClO₄^? ions. Pressed pellets of microcrystalline NaClO₄(DMF)₃ exhibit a conductivity of 3×10^?4 S cm^?1 at room temperature with a low activation barrier to conduction of 25 kJ mol^?1. SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55–65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO₄(DMF)₃, permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles.     

Ceric-initiated polymerization onto polyacrylonitrile with carbohydrate end groups. Graft versus block copolymer formation

Starch-g-polyacrylonitrile (starch-g-PAN) copolymers were prepared by ceric ammonium nitrate initiation, and the major portion of the starch in these graft copolymers was then removed by acid hydrolysis to yield PAN with oligosaccharide end groups. Although these PAN-oligosaccharide samples reacted with methyl methacrylate in the presence of ceric ammonium nitrate, the resulting products were largely graft copolymers rather than the expected PAN-poly(methyl methacrylate) (PMMA) block copolymers. The following evidence is presented for a PAN-g-PMMA structure: (i) PAN without oligosaccharide end groups also produced a copolymer with methyl methacrylate under our reaction conditions. (ii) Starch-g-PAN (51 or 37% add-on) was a less reactive substrate toward ceric-initiated polymerization than PAN with oligosaccharide end groups. (iii) Low-add-on (18%) starch-g-PAN reacted with methyl methacrylate to give a final graft copolymer in which a large percentage of PMMA was grafted to the PAN component rather than to starch.     

Gradient Estimates in Fractional Dirichlet Problems

We obtain some fine gradient estimates near the boundary for solutions to fractional elliptic problems subject to exterior Dirichlet boundary conditions. Our results provide, in particular, the sign of the normal derivative of such solutions near the boundary of the underlying domain.

     

A supermartingale argument for characterizing the functional Hill process weak law for small parameters

The paper deals with the asymptotic laws of functionals of standard exponential random variables. These classes of statistics are closely related to estimators of the extreme value index when the underlying distribution function is in theWeibull domain of attraction.We use techniques based on martingales theory to describe the non-Gaussian asymptotic distribution of the aforementioned statistics.We provide results of a simulation study as well as statistical tests that may be of interest with the proposed results.     

Sharp local estimates for the Szegö–Weinberger profile in Riemannian manifolds

We study the local Szegö–Weinberger profile in a geodesic ball \(B_g(y_0,r_0)\) centered at a point \(y_0\) in a Riemannian manifold \(({\mathcal {M}},g)\) . This profile is obtained by maximizing the first nontrivial Neumann eigenvalue \(\mu _2\) of the Laplace–Beltrami Operator \(\Delta _g\) on \({\mathcal {M}}\) among subdomains of \(B_g(y_0,r_0)\) with fixed volume. We derive a sharp asymptotic bounds of this profile in terms of the scalar curvature of \({\mathcal {M}}\) at \(y_0\) . As a corollary, we deduce a local comparison principle depending only on the scalar curvature. Our study is related to previous results on the profile corresponding to the minimization of the first Dirichlet eigenvalue of \(\Delta _g\) , but additional difficulties arise due to the fact that \(\mu _2\) is degenerate in the unit ball in \(\mathbb {R}^N\) and geodesic balls do not yield the optimal lower bound in the asymptotics we obtain.     

Palladium‐catalysed Suzuki cross‐coupling of primary alkylboronic acids with alkenyl halides

The Suzuki reaction of primary alkylboronic acids with alkenyl halides proceeds nicely using the air‐stable catalyst PdCl(C₃H₅)(dppb), Cs₂CO₃ as base and toluene or xylene as solvent. A minor effect of the substituent position of the alkenyl bromide was observed. Quite similar yields were observed in the presence of α‐ or β‐substituted alkenyl bromides such as 2‐bromobut‐1‐ene or 1‐bromo‐2‐methylprop‐1‐ene with this catalyst. This reaction proceeded with a variety of alkylboronic acids such as 2‐phenylethylboronic acid or n‐octylboronic acid. Lower yields of coupling products were obtained in the presence of an alkenyl chloride. Copyright © 2008 John Wiley & Sons, Ltd.     

Work functions at facet edges

We perform ab initio pseudopotential calculations for metal crystals with finite facets of different crystallographic orientation to investigate the work function profile near crystal edges. We examine local edge effects, and address the problem of the coexistence of different face-dependent local work functions at crystal edges. By modeling the electronic dipoles at the metal surface, we show how nonvanishing surface charges spontaneously appear on metals with inequivalent facets. Our studies of Al crystal nanowires with (100) and (111) facets are extended to derive the dependence of the work function on the crystal morphology in the macroscopic limit.     

A note on Hardy’s inequalities with boundary singularities

Let Ω be a smooth bounded domain in R^N with N≥1. In this paper we study the Hardy-Poincaré inequalities with weight function singular at the boundary of Ω. In particular we give sufficient conditions so that the best constant is achieved.