Separation of different ion structures in atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS)

This study demonstrates how positive ion atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS) can be used to produce different ionic forms of an analy te and how these can be separated. When hexane:toluene (9:1) is used as a solvent, 2,6-di-tert-butylpyridine (2,6-DtBPyr) and 2,6-di-tert-4-methylpyridine (2,6-DtB-4-MPyr) efficiently produce radical cations [M]⁺ and protonated [M + H]⁺ molecules, whereas, when the sample solvent is hexane, protonated molecules are mainly formed. Interestingly, radical cations drift slower in the drift tube than the protonated molecules. It was observed that an oxygen adduct ion, [M + O₂]⁺, which was clearly seen in the mass spectra for hexane:toluene (9:1) solutions, shares the same mobility with radical cations, [M]⁺. Therefore, the observed mobility order is most likely explained by oxygen adduct formation, i.e., the radical cation forrning a heavier adduct. For pyridine and 2-tert-butylpyridine, only protonated molecules could be efficiently formed in the conditions used. For 1- and 2-naphthol it was observed that in hexane the protonated molecule typically had a higher intensity than the radical cation, whereas in hexane:toluene (9:1) the radical cation [M]⁺ typically had a higher intensity than the protonated molecule [M + H]⁺. Interestingly, the latter drifts slower than the radical cation [M]⁺, which is the opposite of the drift pattern seen for 2,6-DtBPyr and 2,6-DtB-4-MPyr.     

Letter: A simple ion source set-up for desorption/ionization on silicon with ion mobility spectrometry and ion mobility spectrometry-mass spectrometry

Using a simple ion source set-up, laser desorption/ionization on silicon (DIOS) was demonstrated with the use of a custom-made drift tube ion mobility spectrometer (IMS), mounted on a commercial triple quadrupole mass spectrometer, and with an IMS equipped with a Faraday plate detector. DIOS was tested by mobility measurement of tetrapropylammonium iodide, tetrabutylammonium iodide and tetrapentylammonium iodide, whilst 2,6-di-tert- butylpyridine was used as a standard. The reduced mobilities measured for the test halides are in concordance with previously obtained ion mobility spectrometry-mass spectrometry data.     

Residual solvent content in heatset offset print

A method was developed for measuring the residual solvent content in a dried offset print. The method is based on hexane extraction. The presence of additives and resins in the printing inks necessitated purification of the extract on an aluminum oxide column. In the study concerning the effect of the heatset web offset drying process on print quality, a distinct correlation was found between the residual solvent content of the print and the drying parameters.     

Lipase-catalyzed acylation in a continuous down-flow fixed-bed reactor

The kinetic resolution of racemic 1-phenylethanol with ethyl acetate was investigated in a down-flow fixed-bed reactor operated in a continuous mode mainly at the molar ratio of 1: 3 in 400 mL toluene at 70°C. The catalytic activity of the immobilized lipase was studied by: (i) changing the flow rates, (ii) utilizing different substrate concentrations, (iii) applying step changes using ethyl acetate, ethyl benzene, acetic acid, acetophenone etc., (iv) investigating the inhibitory effect of either the desired or the stoichiometric products (R)-1-phenylethyl acetate and ethanol, respectively), (v) elucidating the effect of water on the activity and stability of the immobilized lipase. The residence time distribution and the reactor hydrodynamics were also discussed along with kinetic modelling. The results were linked to the one-pot reactions.     

The Chebotarev theorem for ergodic toral automorphisms with respect to (<Emphasis Type="Italic">G</Emphasis>, ρ)–extensions

We consider distribution results for closed orbits of the partially hyperbolic system: an ergodic toral automorphism à with respect to a (G, )–extension A. In particular we obtain an analogue of the Chebotarev theorem in this situation which is an asymptotic formula for the number of closed orbits of the base transformation according to how they lift onto the extension space. To arrive at this result we introduce a cyclic extension  of A and deduce that  and A is essentially a group extension and homogeneous extension of à respectively. This observation of a group extension is similar to the setting previously studied by Parry & Pollicott and using the prime orbit theorem of Waddington we then derive at an auxiliary result for the group extension analogoues to Parry & Pollicott. Finally we relate this auxiliary result to the homogeneous extension by resorting to the work of Noorani & Parry.     

Analysis of catecholamines by capillary electrophoresis and capillary electrophoresis-nanospray mass spectrometry. Use of aqueous and non-aqueous solutions compared with physical parameters

Catecholamines were analysed in aqueous and alcoholic non-aqueous solutions by capillary electrophoresis and capillary electrophoresis-mass spectrometry using sheathless nanospray coupling. Decreases in the electrophoretic mobilities of the catecholamines and in the electroosmotic mobilities were observed from water to 1-propanol. Separations were more efficient in all non-aqueous media than in water. The diffusion coefficients of the catecholamines in the different media were determined. The solvent had little effect on the sensitivity of the UV or MS detection. Both methods were successfully applied to the analysis of urine samples.     

Electronic and structural properties of Si10 cluster

Possible structures for Si₁₀ cluster are considered using a tight-binding model and drawing on significant work done in the past. It is shown that the tight-binding parametrization, fitted to the bulk, is also valid for smaller systems. This model is found to essentially reproduce other published results, but requires much less effort thanab initio techniques—thus, allowing the study of a wide variety of structures and their ions. However, unlike classical force-field calculations, it yields information about the electronic structure of clusters. A new geometric structure for Si₁₀ is found, which is not only of lowest energy, but which also matches the experimental photoelectron band gap and explains the experimental reactivity data. Because of the Jahn-Teller effect, the photoelectron spectrum is very sensitive to geometry. Also, ionization of the cluster alters the geometry slightly.     

Synthesis of 9-Alkyl- and 9-Arylthiophenanthrenes

A simple method for the preparation of 9-alkyl- and 9-arylthio-phenanthrenes from 9-bromophenanthrene and a thiol is described.     

Maximal spanning trees,asset graphs and random matrix denoising in the analysis of dynamics of financial networks

We study the time dependence of maximal spanning trees and asset graphs based on correlation matrices of stock returns. In these networks the nodes represent companies and links are related to the correlation coefficients between them. Special emphasis is given to the comparison between ordinary and denoised correlation matrices. The analysis of single- and multi-step survival ratios of the corresponding networks reveals that the ordinary correlation matrices are more stable in time than the denoised ones. Our study also shows that some information about the cluster structure of the companies is lost in the denoising procedure. Cluster structure that makes sense from an economic point of view exists, and can easily be observed in networks based on denoised correlation matrices. However, this structure is somewhat clearer in the networks based on ordinary correlation matrices. Some technical aspects, such as the random matrix denoising procedure, are also presented.