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71.
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
72.
73.
Mark Paton Karri Muinonen Lauri J. Pesonen Tomas Kohout Martti Lehtinen 《Journal of Quantitative Spectroscopy & Radiative Transfer》2011,112(11):1803-1814
Meteorites have advanced our knowledge of processes in the Solar System with the application of high precision instruments here on Earth. The study of asteroids, the source of most meteorites, has in turn given us knowledge regarding the large scale evolution of the Solar System. Using the complementary information that asteroids and meteorites give us the story of our cosmic backyard can be more easily read. One efficient way to link meteorites to asteroids is by matching their respective reflectance spectra. There have been few convincing matches because of observational and scale differences as well as an incomplete knowledge of the light scattering physics involved. To better interpret the reflectance data we need to know the dependencies of the reflectance on physical properties and develop techniques for better comparisons of data sets. For these purposes we utilise our own measurements of 26 different meteorites together with spectra available on the NASA PDS.We find that normalisation of reflectance at a wavelength between 1.1 and 1.3 μm gives the closest match of spectra from meteorites common to both data sets. The depth of the spectra bands deepens by similar amounts for different types of surface texture alterations i.e. rock to sawn surface, rock to polished surface and rock to powdered surface. Principal Component Analysis (PCA) is able to easily place carbonaceous chondrites, ordinary chondrites and achondrites into distinct groups using their reflectance spectra. We track the variation of spectral features in principal component space by using a set of meteorite spectra synthesised from mineral and elemental spectra. A spectral agent that reduces the reflectance at all wavelengths is required, in addition to olivine, pyroxene and carbon, to generate a set of synthesised spectra to match the distribution of measured spectra, in principal component space. 相似文献
74.
Stable operation of a cw optical parametric oscillator near the signal-idler degeneracy 总被引:1,自引:0,他引:1
The frequency stability of a cw optical parametric oscillator (cw OPO) near the signal-idler degeneracy has been studied. The strong tendency of a near-degenerate OPO to mode hop has been suppressed by using a bulk Bragg grating as a spectral filter in the OPO cavity. An experimental demonstration of stable parametric oscillation in a single longitudinal mode of the OPO cavity is reported, together with the capability of tuning the signal-idler difference frequency from 1 to 4 THz. The OPO has potential use in cw terahertz generation. 相似文献
75.
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
76.
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
77.
The object of this paper is to show that 4-connected planar graphs are uniquely determined from their collection of edge-deleted subgraphs. 相似文献
78.
Josef Lauri 《Journal of Graph Theory》1979,3(3):269-286
The object of this paper is to show tht every planar graph of minimum valency 5 is reconstructible from its family of edge-deleted subgraphs. 相似文献
79.
The object of this paper is to show that every maximal planar graph is recognizable from its family of vertex-deleted subgraphs. 相似文献
80.
We have calculated the band profiles of the OH-stretching fundamental and overtone transitions in the proton donor unit of the water dimer complex. We have used a local mode Hamiltonian that includes both OH-stretching and OO-stretching motion but separates these adiabatically. The variation of OH-stretching frequency and anharmonicity with OO displacement from equilibrium contributes to the effective OO-stretching potentials for each OH-stretching state. The resulting OO-stretching energy levels and wave functions are used to simulate the vibrational profile of each OH-stretching transition. The coupled cluster with singles, doubles, and perturbative triples ab initio method with an augmented triple-zeta correlation consistent basis set has been used to obtain the necessary parameters, potentials, and dipole moment functions. We find that the OO-stretching transitions associated with a given hydrogen bonded OH-stretching transition are spread significantly and this spread increases with overtone. The spread is minor for the free OH-stretching transition. The inclusion of the OO-stretching mode has a limited effect on the overall OH-stretching band intensity. 相似文献