Mass spectrum of nitromethane

The mass spectrum of nitromethane points to rupture of the CH₃? NO₂ bond as the dominant primary reaction, as also observed in pyrolysis, photolysis and radiolysis. Isomerization of the molecular ion to the nitrite configuration seems to contribute little in the mass spectrum of nitromethane, in contrast to those of nitrobenzene and other nitroarenes. The nitrite ion is probably the immediate precursor of [NO]⁺ at its appearance potential, but most of the [NO]+ yield seems to stem from secondary decomposition of excited [NO₂]⁺.     

The long-lived molecular ion of propionitrile: An ion cyclotron resonance study

Evidence has been reported that primary loss of H and of HCN from the molecular ions of propionitrile, isobutyronitrile and butyronitrile in the mass spectrometer is preferentially preceded by hydrogen migration from C-2 to C-1. Ion cyclotron double resonance spectra of proton (or deuteron-) transfer products derived from propionitrile-2-d2 and -3-d3 and a series of bases provide evidence that such migration occurs also in long-lived propionitrile molecular ions.     

Some aspects of the mass spectra of triptycene and tri- and diphenylmethanes

Mass spectra of isotope-labeled triptycenes, triphenylmethanes and diphenylmethanes rule out the bulk of postulated decomposition mechanisms and fragment-ion structures. The formation of [M ? H]⁺ and [M ? 2H]²⁺ from triptycene, of [M ? H]⁺, [M ? CH₃]⁺ and [M ? CH₄]⁺ from triphenylmethane, and of [M ? H]²⁺ and [M ? 2H]²⁺-as well as the previously reported [M ? H]⁺ and [M ? CH₃]⁺-from diphenylmethane all seem to be preceded or accompanied by complete loss of position identity of the α and ring hydrogens in the original molecules. A statistical preference for loss of α hydrogens is found in the process leading to [M ? 2H]⁺ and [M ? H]²⁺ from triptycene, as in the formation of [M ? H]²⁺ from toluene.     

Ultraviolet spectra of metal ions in 6M hydrochloric acid

Ultraviolet absorption spectra of 66 metal ions in aqueous 6M hydrochloric acid were recorded and the spectra of 36 metal ions that absorb appreciably are reported. The absorption of these metal ions is sufficient to permit their detection in liquid chromatography.     

Collocation methods for parabolic partial differential equations in one space dimension

Summary Collocation at Gaussian points for a scalarm-th order ordinary differential equation has been studied by C. de Boor and B. Swartz. J. Douglas, Jr. and T. Dupont, using collocation at Gaussian points, and a combination of energy estimates and approximation theory have given a comprehensive theory for parabolic problems in a single space variable. While the results of this report parallel those of Douglas and Dupont, the approach is basically different. The Laplace transform is used to lift the results of de Boor and Swartz to linear parabolic problems. This indicates a general procedure that may be used to lift schemes for elliptic problems to schemes for parabolic problems. Additionally there is a section on longtime integration and A-stability.Supported by the Office of Naval Research under contract N-00014-67-A-0128-0004     

On the Multiplicity of Solutions Of a Differential Equation Arising in Chemical Reactor Theory

Consider the boundary value problem where β ? 0, τ ? 0. We are concerned with a mathematically rigorous numerical study of the number of solutions in any bounded portion of the positive quadrant (τ ? 0, β ? 0) of the τ, β plane. These correct computational results may then be matched with asymptotic (β→∞, τ ? 0) results developed earlier. These numerical results are based on the development of a posteriori error estimates for the numerical solution of an associated initial-value problem and a priori bounds on .     

The smallestn-uniform hypergraph with positive discrepancy

A two-coloring of the verticesX of the hypergraphH=(X, ε) by red and blue hasdiscrepancy d ifd is the largest difference between the number of red and blue points in any edge. A two-coloring is an equipartition ofH if it has discrepancy 0, i.e., every edge is exactly half red and half blue. Letf(n) be the fewest number of edges in ann-uniform hypergraph (all edges have sizen) having positive discrepancy. Erd?s and Sós asked: isf(n) unbounded? We answer this question in the affirmative and show that there exist constantsc ₁ andc ₂ such that $$\frac{{c_1 \log (snd(n/2))}}{{\log \log (snd(n/2))}} \leqq f(n) \leqq c_2 \frac{{\log ^3 (snd(n/2))}}{{\log \log (snd(n/2))}}$$ where snd(x) is the least positive integer that does not dividex.     

Copper-mediated intra-ligand oxygen transfer in gas-phase complexes with 3-nitrotyrosine

Gas-phase ternary complexes with Cu(II) and 2,2'-bipyridine (bpy) of tyrosine, 3-aminotyrosine, 3-nitrotyrosine and 3-nitrotyrosine methyl ether are formed readily upon electrospraying aqueous methanol solutions containing the components. In contrast to Cu(bpy) complexes of tyrosine, 3-aminotyrosine and other aromatic amino acids, the complexes of 3-nitrotyrosine and its methyl ether undergo unusual collisionally activated dissociations (CADs) that involve Cu-mediated transfer of an oxygen atom from the nitro group. With 3-nitrotyrosine this results in an expulsion of carbonic acid, H(2)CO(3), whereas with 3-nitrotyrosine methyl ether an OH migration forms Cu(OH)bpy(+) as the predominant product. To the best of our knowledge, this is the first case of an intra-ligand redox reaction in a gas-phase organometallic complex. The reaction mechanism of this unusual dissociation was elucidated by a combination of isotope labeling, accurate mass measurements, energy-resolved CAD mass spectra and density functional theory calculations of ion structures and relative energies.     

Recognizing Berge Graphs

A graph is Berge if no induced subgraph of G is an odd cycle of length at least five or the complement of one. In this paper we give an algorithm to test if a graph G is Berge, with running time O(|V (G)|⁹). This is independent of the recent proof of the strong perfect graph conjecture.* Currently this author is a Clay Mathematics Institute Research Fellow.** Supported by NSF grant DMI-0352885 and ONR grant N00014-97-1-0196. Supported by ONR grant N00014-01-1-0608, and NSF grant DMS-0070912. Supported by EPSRC grant GR/R35629/01.     

Synthesis of zirconocene-based silica phases and evaluation in lindane and heptachlor epoxide adsorption/desorption

Silica (350 m(2) g(-1)) was chemically modified with Cp2ZrCl2 and (nBuCp)2ZrCl2 by grafting. Hybrid silica bearing surface indene groups was synthesized by the sol-gel method, followed by metallation with ZrCl(4)2THF. The resulting phases were characterized by Rutherford backscattering spectrometry (RBS), 13C and 29Si magic angle spin nuclear magnetic resonance, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. According to RBS measurements, metal content was 0.2- to 0.3-wt% Zr/SiO2 for the grafted systems and 4.5-wt% Zr/SiO2 for the phase prepared by the sol-gel method. The solid phases were evaluated for the adsorption/preconcentration of lindane and heptachlor epoxide from aqueous solution. For comparative reasons, the commercial LC-18 phase was also evaluated. Analyte concentration was monitored by gas chromatography electron capture detection. For the grafted phases, the coordination sphere around the metal center seems not to influence the adsorption/desorption properties of these phases vis-a-vis the studied analytes. In the case of the phases prepared by the sol-gel method, recovery results were comparable to those observed for LC-18. Experiments using ZrO2 and ZrO2/SiO2 phases led to lower recovery results.