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321.
D. Kaczmarek S. Shaqiri B. Atakan T. Kasper 《Proceedings of the Combustion Institute》2021,38(1):233-241
Methane based polygeneration processes in piston engines offer the possibility of a controllable and flexible conversion of energy, to up-convert low value chemicals and to store energy. These processes preferably take place under fuel-rich conditions and at high pressures. Under fuel-rich conditions, there was one experimental report that a distinctive negative temperature coefficient (NTC) behavior occurs in methane oxidation (Petersen et al., 1999). To design a polygeneration process, reliable kinetic models are required to capture the impact of pressure and equivalence ratio variations on reactivity of the gas mixtures. Here, the experimental basis for methane oxidation is expanded to high pressures and very fuel-rich conditions and compared to literature models, both with special emphasis on the NTC behavior. The oxidation of methane/oxygen mixtures at 2 ≤ Φ≤ 20 and pressures ranging from 1 to 20 bar is investigated. The literature reaction mechanisms are assessed with respect to their ability to predict this phenomenon and used to identify reaction pathways. It is found that NTC behavior occurs in a temperature range between 700 and 1000 K and at pressures higher than 5 bar. The lower temperature limit is slightly shifted towards higher temperatures with decreasing equivalence ratio. In addition, the higher the equivalence ratio, the broader the pressure range, in which the NTC behavior is observed. In general, predictions of some models are in good agreement with the experimental data. Reaction path analyses reveal that the competition between oxidation and recombination pathways are responsible for the NTC region in methane oxidation. 相似文献
322.
Dr. Christian Kofoed Dr. Shunliang Wu Dr. Kasper K. Sørensen Tuule Treiberg Dr. Johnny Arnsdorf Dr. Sara P. Bjørn Dr. Tanja L. Jensen Bjørn G. Voldborg Dr. Mikkel B. Thygesen Prof. Knud J. Jensen Dr. Sanne Schoffelen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(15):e202200147
Chemical modification of proteins has numerous applications, but it has been challenging to achieve the required high degree of selectivity on lysine amino groups. Recently, we described the highly selective acylation of proteins with an N-terminal Gly-His6 segment. This tag promoted acylation of the N-terminal Nα-amine resulting in stable conjugates. Herein, we report the peptide sequences Hisn-Lys-Hism, which we term Lys-His tags. In combination with simple acylating agents, they facilitate the acylation of the designated Lys Nϵ-amine under mild conditions and with high selectivity over native Lys residues. We show that the Lys-His tags, which are 7 to 10 amino acids in length and still act as conventional His tags, can be inserted in proteins at the C-terminus or in loops, thus providing high flexibility regarding the site of modification. Finally, the selective and efficient acylation of the therapeutic antibody Rituximab, pure or mixed with other proteins, demonstrates the scope of the Lys-His tag acylation method. 相似文献
323.
324.
Michael R. Harpham Son C. Nguyen Zongrui Hou Jeffrey C. Grossman Charles B. Harris Michael W. Mara Andrew B. Stickrath Yosuke Kanai Alexie M. Kolpak Donghwa Lee Di‐Jia Liu Justin P. Lomont Kasper Moth‐Poulsen Nikolai Vinokurov Lin X. Chen K. Peter C. Vollhardt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2012,124(31):7812-7816
325.
326.
Controlling the reciprocity between chemical reactivity and supramolecular structure is a topic of great interest in the emergence of molecular complexity. In this work, we investigate the effect of a covalent reaction as a trigger to depolymerize a supramolecular assembly. We focus on the impact of an in situ thiol–ene reaction on the (co)polymerization of three derivatives of benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with cysteine, hexylcysteine, and alkyl side chains: Cys-BTA, HexCys-BTA, and a-BTA. Long supramolecular polymers of Cys-BTA can be depolymerized into short dimeric aggregates of HexCys-BTAvia the in situ thiol–ene reaction. Analysis of the system by time-resolved spectroscopy and light scattering unravels the fast dynamicity of the structures and the mechanism of depolymerization. Moreover, by intercalating the reactive Cys-BTA monomer into an unreactive inert polymer, the in situ thiol–ene reaction transforms the intercalator into a sequestrator and induces the depolymerization of the unreactive polymer. This work shows that the implementation of reactivity into supramolecular assemblies enables temporal control of depolymerization processes, which can bring us one step closer to understanding the interplay between non-covalent and covalent chemistry.We report on the controlled depolymerization of supramolecular 1D polymers into well-defined dimers triggered by a covalent reaction on the side chains of the monomer. 相似文献
327.
Maria Quant Andreas Erbs Hillers-Bendtsen Shima Ghasemi Mate Erdelyi Zhihang Wang Lidiya M. Muhammad Nina Kann Kurt V. Mikkelsen Kasper Moth-Poulsen 《Chemical science》2022,13(3):834
Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. In this context, bicyclooctadienes (BODs) undergo a photoinduced transformation to the corresponding higher energy tetracyclooctanes (TCOs), but the photoswitch system has not until now been evaluated for MOST application, due to the short half-life of the TCO form and limited available synthetic methods. The BOD system degrades at higher temperature via a retro-Diels–Alder reaction, which complicates the synthesis of the compounds. We here report a cross-coupling reaction strategy that enables an efficient synthesis of a series of 4 new BOD compounds. We show that the BODs were able to switch to the corresponding tetracyclooctanes (TCOs) in a reversible way and can be cycled 645 times with only 0.01% degradation. Half-lives of the TCOs were measured, and we illustrate how the half-life could be engineered from seconds to minutes by molecular structure design. A density functional theory (DFT) based modelling framework was developed to access absorption spectra, thermal half-lives, and storage energies which were calculated to be 143–153 kJ mol−1 (0.47–0.51 MJ kg−1), up to 76% higher than for the corresponding norbornadiene. The combined computational and experimental findings provide a reliable way of designing future BOD/TCO systems with tailored properties.Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. 相似文献
328.
M. Grasserbauer S. Paleczek J. Rendl A. Kasper H. Puxbaum 《Fresenius' Journal of Analytical Chemistry》1994,350(7-9):431-439
Background measurements at the high alpine station of the Sonnblick (altitude 3106 m) are reported. For a period of 13 months samples have been collected during 4 campaigns of 1–2 weeks duration each and analysed for their ionic and elemental composition, pH and conductivity. These samples were aerosols collected with filters, cloud water and precipitation. The samples were mainly analysed with ion chromatography (IC) and atomic absorption spectrometry (AAS). Analysis proved to be difficult due to the low amounts of aerosols collected and the low concentrations of components in cloud water and wet precipitation. Also major problems arose in sampling due to the extreme climatic conditions. The analytical techniques, particularly those for sampling the materials, are critically evaluated and results on pollutant levels, their variation with time and the distribution of the components between the gaseous and liquid phases are presented.Abbreviations ET-AAS
Electrothermal Atomic Absorption Spectrometry
- F-AAS
Flame Atomic Absorption Spectrometry
- FIA
Flow Injection Analysis
- IC
Ion Chromatography
Dedicated to Prof. Dr. Dieter Klockow on the occasion of his 60th birthday 相似文献
329.
U. Kasper 《Annalen der Physik》1979,491(2):135-147
Subject is considered on the level of classical field theory. We start from some aspects of the theory of ferromagnets. Their counterpart in classical field theory is pointed out using the over simplified model of a selfinteracting scalar field. The ground state (“vacuum expection value”) of the scalar field is interpreted as cosmic background field, which can be considered as constant for local physical phenomena. In practice, however, it is a function of the age of universe. Which kind of function it could be is suggested by a discussion of the cosmic variability of Eddington's number γ = 1040, which refers to Dirac's consideration of this problem. But contrary to Dirac's assumption that atomic quantities are constant, we suppose that the inertial mass of elementary particles is a function of the age of universe. The cosmic gravitational field is described by other equations than the gravitational field created by local matter distributions. The field equations for the local gravitational field we start from reduce to Einstein's equations, if we neglect the possible influence of the universe on local phenomena. In case that the cosmic matter is homogeneously and isotropically distributed, the field equations for the cosmic gravitational field permit only such a time dependent solution the three-spaces of which are linearly expanding and spherically closed. The different field equations for cosmic and local gravitational fields are considered approximations of more fundamental field equations which approximately split into two sets of equations, if it is possible to contrast local physical systems with the universe. The described cosmological model taken as a basis, the inertial mass of elementary particles becomes a function of the matter density creating the cosmic gravitational field. This could be considered as, at least, partly realisation of Mach's idea concerning the origin of inertia. Starting from the interpretation of the ground state (vacuum expection value) as a function of a certain cosmic background field, more realistic gage field models could give the following picture of cosmic development: In the far past there was a state of the universe characterized by enormous contraction of matter. In this stage of development, it was impossible to contrast particles with the universe. Matter expands and it becomes possible to contrast certain physical systems with the universe. But the ground state is such a symmetric one that only fields with vanishing rest mass can be contrasted with the universe (ferromagnet above Curie temperature). With further expansion of the universe the ground state will lose certain symmetry properties. By this it becomes possible that you get the impression there are particles with nonvanishing rest mass (ferromagnet below Curie temperature). Finally, the influence of the universe on local physical systems goes to zero with further expansion. Especially, this means the inertial mass of elementary particles goes to zero, too (Curie temperature of ferromagnetic material goes to zero with cosmic expansion). 相似文献
330.
Kasper K. S. Andersen Tilman Bauer Jesper Grodal Erik Kjaer Pedersen 《Inventiones Mathematicae》2004,157(1):1-10
We construct a connected finite loop space of rank 66 and dimension 1254 whose rational cohomology is not isomorphic as a graded vector space to the rational cohomology of any compact Lie group, hence providing a counterexample to a classical conjecture. Aided by machine calculation we verify that our counterexample is minimal, i.e., that any finite loop space of rank less than 66 is in fact rationally equivalent to a compact Lie group, extending the classical known bound of 5. Mathematics Subject Classification (2000) Primary: 55P35; Secondary: 55P15, 55R35 相似文献