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41.
Anu Teearu Signe Vahur Uku Haljasorg Ivo Leito Tõiv Haljasorg Lauri Toom 《Journal of mass spectrometry : JMS》2014,49(10):970-979
2,5‐Dihydroxybenzoic acid (DHB) is one of the most widely used and studied matrix compounds in matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry. However, the influence of ageing of the DHB solution on the MALDI mass spectra has not been yet systematically studied. In this work, the possible changes occurring in the acidified acetonitrile/water solution of the MALDI matrix compound DHB during 1‐year usage period have been monitored with MALDI‐Fourier transform ion cyclotron resonance mass spectrometer (MALDI‐FT‐ICR‐MS) and attenuated total reflectance Fourier transform infrared (ATR‐FT‐IR) spectroscopy. No significant ageing products have been detected. The ability of the aged DHB solution to act as a MALDI matrix was tested with two materials widely used in art and conservation – bone glue (a proteinaceous material) and shellac resin (a resinous material) – and good results were obtained. A number of peaks in the mass spectra measured from the DHB solution were identified, which can be used for internal calibration of the mass axis. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
42.
Raili Pönni Lauri Rautkari Callum A. S. Hill Tapani Vuorinen 《Cellulose (London, England)》2014,21(3):1217-1226
Deuterium exchange in a deuterium oxide (D2O) atmosphere (95 % relative humidity), quantified by a dynamic vapor sorption (DVS) apparatus, was applied for assessing the accessibility of hydroxyl groups in birch kraft pulps. Achieving the maximum deuteration level exhibited slower kinetics than was earlier reported for experiments with ground wood and bacterial cellulose. The deuterium exchange process followed two parallel phenomena. Applying multiple drying and rewetting cycles gave kinetic information also on the hornification phenomenon occurring during these cycles. Dry birch pulps treated with sodium hydroxide solution of varying alkalinities at elevated temperatures were assessed for their accessible hydroxyl groups by DVS with deuterium exchange. This method was evaluated against deuteration combined with Fourier transform infra-red spectroscopy and water retention value (WRV). DVS measurements were in correlation with WRV and both the methods indicated that an alkaline treatment of dry birch pulp improves cellulose accessibility. The level of irreversible deuteration also decreased as the alkalinity was increased. DVS was shown to provide quantitative information on the accessibility but to be a time-consuming method for the pulp samples. A potential means to decrease the duration of the measurement is increased D2O exposure by excluding the drying phases. 相似文献
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Sandip A. Kadam Kerli Martin Kristjan Haav Dr. Lauri Toom Dr. Charly Mayeux Astrid Pung Prof. Philip A. Gale Dr. Jennifer R. Hiscock Dr. Simon J. Brooks Dr. Isabelle L. Kirby Dr. Nathalie Busschaert Prof. Ivo Leito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5145-5160
The binding constants (log Kass) of small synthetic receptor molecules based on indolocarbazole, carbazole, indole, urea and some others, as well as their combinations were measured for small carboxylate anions of different basicity, hydrophilicity and steric demands, that is, trimethylacetate, acetate, benzoate and lactate, in 0.5 % H2O/[D6]DMSO by using the relative NMR‐based measurement method. As a result, four separate binding affinity scales (ladders) including thirty‐eight receptors were obtained with the scales anchored to indolocarbazole. The results indicate that the binding strength is largely, but not fully, determined by the strength of the primary hydrogen‐bonding interaction. The latter in turn is largely determined by the basicity of the anion. The higher is the basicity of the anion the stronger in general is the binding, leading to the approximate order of increasing binding strength, lactate<benzoate<acetate≤trimethylacetate, which holds with all investigated receptors. Nevertheless, there are a number of occasions when the binding order changes with changing of the carboxylate anion, sometimes quite substantially. Principal component analysis (PCA) reveals that this is primarily connected to preferential binding of trimethylacetate, supposedly caused by an additional hydrophobic/solvophobic interaction. These findings enable making better predictions, which receptor framework or cavity is best suited for carboxylate anions in receptor design. 相似文献
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Anne-Marja Uusitalo Tuula T. Pakkanen Minna Krger-Laukkanen Lauri Niinist Kimmo Hakala Santeri Paavola Barbro Lfgren 《Journal of molecular catalysis. A, Chemical》2000,160(2):343-356
Heterogeneous metallocene catalysts were prepared by adsorbing rac-Et(Ind)2ZrCl2 on a modified silica surface in solution. The modification of silica was conducted in gas phase with atomic layer chemical vapor deposition (ALCVD) technique, where the silica, preheated at either 350 or 600°C, was allowed to react with vaporized trimethylaluminum (TMA) at 250°C. Modified carriers and heterogeneous catalysts were characterized with FTIR, 1H MAS (magic-angle spinning) NMR, 13C, and 29Si CP (cross-polarization) MAS NMR spectroscopies and elemental analyses. In the reaction of TMA with silica, a saturated surface was formed consisting of different (---O)4−nSi(CH3)n (n=1, 2 or 3) and ---AlCH3 groups. The ratio of ---SiMe to ---AlMe groups was approximately 1.5 in the TMA/SiO2 carriers. When the metallocene was adsorbed onto the carrier it seemed to react with the surface ---AlCH3 groups and possibly ---ZrCH3 groups were formed. Heterogeneous catalysts were tested in the polymerization of ethylene and propylene in the presence of methylalumoxane (MAO). And they produced similar polymer as the homogeneous rac-Et(Ind)2ZrCl2 catalyst, but with lower activity. A catalyst with the best activity was achieved from silica that was preheated at 600°C. Moreover, leaching of catalyst was examined whereupon a part of zirconium was observed to desorb from the carrier. 相似文献
47.
We present the first monolithically integrated silicon/glass liquid chromatography-electrospray ionization microchip for mass spectrometry. The microchip is fabricated by bonding a silicon wafer, which has deep reactive ion etched micropillar-filled channels, together with a glass lid. Both the silicon channel and the glass lid have a through-wafer etched sharp tip that produces a stable electrospray. The microchip is also compatible with laser induced fluorescence (LIF) detection, due to the glass lid. Separation of drugs in less than 5 minutes using either SiO(2) (normal phase) or C(18) coated (reversed-phase) pillars with good sensitivity was demonstrated with mass spectrometric detection as well as separation of fluorescent compounds with LIF detection. 相似文献
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49.
Lauri Oksanen 《偏微分方程通讯》2013,38(9):1492-1518
We consider boundary measurements for the wave equation on a bounded domain M ? ?2 or on a compact Riemannian surface, and introduce a method to locate a discontinuity in the wave speed. Assuming that the wave speed consist of an inclusion in a known smooth background, the method can determine the distance from any boundary point to the inclusion. In the case of a known constant background wave speed, the method reconstructs a set contained in the convex hull of the inclusion and containing the inclusion. Even if the background wave speed is unknown, the method can reconstruct the distance from each boundary point to the inclusion assuming that the Riemannian metric tensor determined by the wave speed gives simple geometry in M. The method is based on reconstruction of volumes of domains of influence by solving a sequence of linear equations. For τ ∈C(?M) the domain of influence M(τ) is the set of those points on the manifold from which the distance to some boundary point x is less than τ(x). 相似文献
50.
X-ray fluorescence spectrometry (XRF) was applied to determine aluminium in AlCl3- and Al2O3-modified silica catalyst supports that were prepared by gas-solid reactions in an atomic layer epitaxy (ALE) process using
aluminium chloride or aluminium chloride and water as adsorbates and silica as support. INAA and AAS were used as reference
methods to determine the aluminium content of the supports. The calibration of XRF results was done by plotting the Al/Si
intensity ratios against the aluminium content as determined by atomic absorption spectrometry (AAS) and verified by instrumental
neutron activation analysis (INAA). Correlation factors for the calibration graphs were 0.984 for AlCl3/SiO2 and 0.995 for Al2O3/ SiO2 samples in the aluminium content range 0–2.6 g Al per 100 g of sample.
Received: 19 October 1998 / Accepted: 14 December 1998 相似文献