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排序方式: 共有196条查询结果,搜索用时 31 毫秒
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Ottosson N Børve KJ Spångberg D Bergersen H Sæthre LJ Faubel M Pokapanich W Öhrwall G Björneholm O Winter B 《Journal of the American Chemical Society》2011,133(9):3120-3130
The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon 1s binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine. 相似文献
23.
Pokapanich W Kryzhevoi NV Ottosson N Svensson S Cederbaum LS Öhrwall G Björneholm O 《Journal of the American Chemical Society》2011,133(34):13430-13436
Auger electron spectroscopy combined with theoretical calculations has been applied to investigate the decay of the Ca 2p core hole of aqueous Ca(2+). Beyond the localized two-hole final states on the calcium ion, originating from a normal Auger process, we have further identified the final states delocalized between the calcium ion and its water surroundings and produced by core level intermolecular Coulombic decay (ICD) processes. By applying the core-hole clock method, the time scale of the core level ICD was determined to be 33 ± 1 fs for the 2p core hole of the aqueous Ca(2+). The comparison of this time constant to those associated with the aqueous K(+), Na(+), Mg(2+), and Al(3+) ions reveals differences of 1 and up to 2 orders of magnitude. Such large variations in the characteristic time scales of the core level ICD processes is qualitatively explained by different internal decay mechanisms in different ions as well as by different ion-solvent distances and interactions. 相似文献
24.
Wang E Ma Z Zhang Z Henriksson P Inganäs O Zhang F Andersson MR 《Chemical communications (Cambridge, England)》2011,47(17):4908-4910
A new low band gap polymer (E(g) = 1.6 eV) with alternating thiophene and isoindigo units was synthesized and characterized. A PCE of 3.0% and high open-circuit voltage of 0.89 V were realized in polymer solar cells, which demonstrated the promise of isoindigo as an electron deficient unit in the design of donor-acceptor conjugated polymers for polymer solar cells. 相似文献
25.
A branching process counted by a random characteristic has been defined as a process which at time t is the superposition of individual stochastic processes evaluated at the actual ages of the individuals of a branching population. Now characteristics which may depend not only on age but also on absolute time are considered. For supercritical processes a distributional limit theorem is proved, which implies that classical limit theorems for sums of characteristics evaluated at a fixed age point transfer into limit theorems for branching processes counted by these characteristics. A point is that, though characteristics of different individuals should be independent, the characteristics of an individual may well interplay with the reproduction of the latter. The result requires a sort of Lp-continuity for some 1 ? p ? 2. Its proof turns out to be valid for a wider class of processes than branching ones.For the case p = 1 a number of Poisson type limits follow and for p = 2 some normality approximations are concluded. For example results are obtained for processes for rare events, the age of the oldest individual, and the error of population predictions.This work has been supported by a grant from the Swedish Natural Science Research Council. 相似文献
26.
Asberg P Björk P Höök F Inganäs O 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7292-7298
The water-soluble zwitterionic polythiophene, poly(3-((S)-5-amino-5-carboxyl-3-oxapentyl)-2,5-thiophene) hydrochloride (POWT), is a conjugated polyelectrolyte (CPE) with properties well suited for biochip applications. CPEs readily form hydrogels when exposed to water-based buffer solutions or biomolecule solutions. In this work, we used in situ quartz crystal microbalance with dissipation (QCM-D) monitoring to collect information on the interaction between POWT films exposed to buffers with different pH and POWT/DNA chains. Our data show that POWT swells significantly when exposed to low-pH buffers, such as pH 4 acetate, this is seen as an increase in thickness and decrease in viscosity obtained via a Voight-based modeling of combined f and D QCM-D measurements. The magnitude of thickness and viscosity change upon changing from a pH 10 carbonate buffer to pH 4 acetate is 100% increase in thickness and 50% decrease in viscosity. The response of the hydrogel under pH change is well correlated with fluorescence data from POWT films on glass. The state of the hydrogel is important during interaction with biomolecules; illustrated by the observation that a swollen CPE hydrogel adsorbs a higher amount of DNA than a compacted one. In agreement with previous results, the QCM-D data confirmed that the POWT/DNA hydrogel sense complementary DNA specifically and with negligible binding of noncomplementary DNA. These results are important for efficient constructions of biochips in water environments using this class of materials. 相似文献
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Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations
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Dr. Naresh K. Jena Ida Josefsson Dr. Susanna K. Eriksson Prof. Anders Hagfeldt Prof. Hans Siegbahn Prof. Olle Björneholm Prof. Håkan Rensmo Dr. Michael Odelius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):4049-4055
Ab initio molecular dynamics (MD) simulations of the solvation of LiI3 in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I3? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I3? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I3? ion, and the geometric structure has been correlated with the electronic structure. 相似文献
29.
Phytochromes constitute a superfamily of photoreceptor proteins existing in two forms that absorb red (Pr) and far‐red (Pfr) light. Although it is well‐known that the conversion of Pr into Pfr (the biologically active form) is triggered by a Z→E photoisomerization of the linear tetrapyrrole chromophore, direct evidence is scarce as to why this reaction always occurs at the methine bridge between pyrrole rings C and D. Here, we present hybrid quantum mechanics/molecular mechanics calculations based on a high‐resolution Pr crystal structure of Deinococcus radiodurans bacteriophytochrome to investigate the competition between all possible photoisomerizations at the three different (AB, BC and CD) methine bridges. The results demonstrate that steric interactions with the protein are a key discriminator between the different reaction channels. In particular, it is found that such interactions render photoisomerizations at the AB and BC bridges much less probable than photoisomerization at the CD bridge. 相似文献
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