The direct observation of a highly mobile positive ion in nanosecond pulse irradiated liquid cyclohexane

The electrical conductivity induced by pulse irradiation of liquid cyclohexane has been studied by means of microwave absorption. The conductivity in pure cyclohexane, due principally to the excess electron, is reduced to less than 10% of the initial value on addition of 5 × 10^?4 M of the electron scavenger SF₆. The conductivity remaining after addition of SF₆ is however more than an order of magnitude larger than expected for massive ions in cyclohexane and, since it is almost completely removed by the addition of 4 × 10^?3 M of the positive ion scavenger NH₃, is attributed mainly to the high mobility of the positive hole in this liquid. The ratio of the electron to hole mobility is determined to be 15. The mean lifetime of the hole under the present conditions is 86 ns. The rate constant for reaction of the hole with NH₃ is determined to be 1.8 × 10¹¹ M^?1 s^?1. From the conductivity remaining after removal of both the electron and the hole the sum of the mobilities of the resulting molecular ions is determined to be 8.4 × 10^?4 cm² V^?1 s^?1.     

The generating rank of the space of short vectors in the Leech lattice mod 2

Consider the partial linear space on the images in Λ/2Λ of the shortest nonzero vectors in the Leech lattice Λ, where the lines are the triples of vectors adding up to zero. We determine the universal embedding dimension and the generating rank of this space (both are 24) and classify its hyperplanes.     

Composition tunable cobalt-nickel and cobalt-iron alloy nanoparticles below 10?nm synthesized using acetonated cobalt carbonyl

A general organometallic route has been developed to synthesize Co(x)Ni(1-x) and Co(x)Fe(1-x) alloy nanoparticles with a fully tunable composition and a size of 4-10?nm with high yield. In contrast to previously reported synthesis methods using dicobalt octacarbonyl (Co(2)(CO)(8)), here the cobalt-cobalt bond in the carbonyl complex is first broken with anhydrous acetone. The acetonated compound, in the presence of iron carbonyl or nickel acetylacetonate, is necessary to obtain small composition tunable alloys. This new route and insights will provide guidelines for the wet-chemical synthesis of yet unmade bimetallic alloy nanoparticles. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s11051-012-0991-5) contains supplementary material, which is available to authorized users.     

Multivariate calibration leverages and spectral F‐ratios via the filter factor representation

Diagnostics are fundamental to multivariate calibration (MC). Two common diagnostics are leverages and spectral F‐ratios and these have been formulated for many MC methods such as partial least square (PLS), principal component regression (PCR) and classical least squares (CLS). While these are some of the most common methods of calibration in analytical chemistry, ridge regression is also common place and yet spectral F‐ratios have not been developed for it. Noting that ridge regression is a form of Tikhonov regularization (TR) and using the unifying filter factor representation for MC, this paper develops the filter factor form of leverages and spectral F‐ratios. The approach is applied to a spectral data set to demonstrate computational speed‐up advantages and ease of implementation for the filter factor representation. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterization of typical chemical background interferences in atmospheric pressure ionization liquid chromatography-mass spectrometry

The structures and origins of typical chemical background noise ions in positive atmospheric pressure ionization liquid chromatography/mass spectrometry (API LC/MS) are investigated and summarized in this study. This was done by classifying chemical background ions using precursor and product ion scans on most abundant background ions to draw a family tree of the commonly occurring chemical background ions. The possible structures and the origins of the major chemical background noise are clearly revealed in the family trees. In agreement with some suggestions in the literature, the chemical background ions studied so far can be classified mainly as either ions of contaminants (or their degradation fragments) or cluster-related ones. A significant contribution from the contaminants (airborne, from tubing and/or solvents) from plasticizer additives (phthalates, phenyl phosphates, sebacates and adipates, etc.) and silicones is concluded. These ions of contaminants can also serve as nuclei for the clustering of HPLC solvent or additives, such as water and acetic acid, thereby leading to a second family of background ions. This study explains the persistence of some chemical background noise even under fairly strong declustering conditions in API LC/MS. One of the other interesting conclusions is that there is a clear difference in structures between the chemical background ions and the protonated analytes generated under atmospheric pressure ionization. This conclusion will contribute to the on-going research efforts to exclusively remove or reduce the interference of chemical background noise in API LC/MS.     

On 3-chromatic distance-regular graphs

We give some necessary conditions for a graph to be 3-chromatic in terms of the spectrum of the adjacency matrix. For all known distance-regular graphs it is determined whether they are 3-chromatic. A start is made with the classification of 3-chromatic distance-regular graphs, and it is shown that such graphs, if not complete 3-partite, must have λ ≤ 1.     

Effect of the Solvent Flow Rate on the Ionization Efficiency in Atmospheric Pressure Photoionization-Mass Spectrometry

In the novel atmospheric pressure photoionization-mass spectrometry the ionization efficiency has been observed to decrease when the solvent flow rate is increased. The effect of the flow rate on the ionization efficiency was studied by comparing the behavior of two analytes, one of which is ionized through charge exchange, the other through proton transfer. Additional information about the ion loss mechanisms was obtained by comparing results obtained with two different APPI ion sources: a Sciex prototype and the Agilent/Syagen APPI source. In addition to the measurements done by using the mass analyzer, the total ion current in the ion source was obtained by measuring the currents of the ions arriving at curtain/end plate and orifice/capillary of the two mass spectrometers. The total ion current measurements showed a significant decrease at high solvent flow rates. Loss of dopant radical cations was thought to be the reason for the signal decrease of the analytes formed through charge exchange. Analytes formed through proton transfer were not as seriously ected by the high solvent flow rates, but some saturation of their signal was nevertheless observed. Loss of photons through absorption by solvent vapor is another mechanism that can be held responsible for a reduction of the total number of ions produced by the APPI source.     

Chain length effects in the competition between intramolecular hydrogen migrations in the molecular ions of hydrogen migration in the molecular ions of α-benzylamino-ω-benzyloxyalkanes as studied by deuterium labelling

The unimolecular decompositions upon electron impact of the bifunctional compounds ØCH₂-NH? (CH₂)_n-O? CH₂Ø(n=2 to 7)have been studied by deuterium labelling. The molecular ions lose a benzyl radical and/or a benzaldehyde molecule, depending on the length of the aliphatic chain. Both reactions appear to be the result of the transfer of a hydrogen atom to the charge localized amino function in a cyclic transition state. The ring size of this transition state turns out to play a far more important role than the difference in reactivity of the migrating hydrogen atoms.