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1.
2.
R. Euler B. Fricke T. Morović W. -D. Sepp A. Rosén 《Zeitschrift für Physik A Hadrons and Nuclei》1980,297(2):101-104
Total energy SCF calculations were performed for noble gas difluorides in a relativistic procedure and compared with analogous non-relativistic calculations. The discrete variational method with numerical basis functions was used. Rather smooth potential energy curves could be obtained. The theoretical Kr-F and Xe-F bond distances were calculated to be 3.5 a.u. and 3.6 a.u. which should be compared with the experimental values of 3.54 a.u. and 3.7 a.u. Although the dissociation energies are off by a factor of about five it was found that ArF2 may be a stable molecule. Theoretical ionization energies for the outer levels reproduce the experimental values for KrF2 and XeF2 to within 2 eV. 相似文献
3.
Márton Balázs Firas Rassoul-Agha Timo Seppäläinen 《Communications in Mathematical Physics》2006,266(2):499-545
We study space-time fluctuations around a characteristic line for a one-dimensional interacting system known as the random average process. The state of this system is a real-valued function on the integers. New values of the function are created by averaging previous values with random weights. The fluctuations analyzed occur on the scale n 1/4, where n is the ratio of macroscopic and microscopic scales in the system. The limits of the fluctuations are described by a family of Gaussian processes. In cases of known product-form invariant distributions, this limit is a two-parameter process whose time marginals are fractional Brownian motions with Hurst parameter 1/4. Along the way we study the limits of quenched mean processes for a random walk in a space-time random environment. These limits also happen at scale n 1/4 and are described by certain Gaussian processes that we identify. In particular, when we look at a backward quenched mean process, the limit process is the solution of a stochastic heat equation. 相似文献
4.
Gerhard Buchbauer Johanna Gabmeier Ernst Haslinger Wolfgang Robien Harald Steindl 《Helvetica chimica acta》1985,68(1):231-235
Synthesis and Reactions of the Bicyclo[6.4.0]dodecane-3-carboxylic Acid Derivatives The synthesis and some consecutive reactions of the compounds 5-8 , derivatives of bicyclo[6.4.0]dodecane-3-carboxylic acid ( 1 ), are described. The esters 7 and 8 can be obtained by Baeyer-Villiger oxidation of 2-hydroxy-8-methyltricyclo[7.3.1.02,7]tridecan-13-one ( 4 ) and subsequent hydrolysis of the lactone 5 . The structure and configuration of these compounds has been evaluated by spectroscopic techniques (mainly 2D-NMR methods). The formation of 7 via 1,2-H shift and subsequent isomerization to 8 has been studied. The esters 11 and 13 are formed stereospecifically from 7 and 8 . 相似文献
5.
Graveland-Bikker JF Ipsen R Otte J de Kruif CG 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6841-6846
Self-assembly of alpha-lactalbumin after partial hydrolysis by a protease from Bacillus licheniformis can result in nanotubular structures, which show many similarities to microtubules. Calcium plays a crucial role in this process. The objective of this investigation was to study the role of calcium in more detail. The kinetics of the hydrolysis step and the self-assembly step were monitored by respectively liquid chromatography-mass spectrometry and dynamic light scattering. The microstructure of the gels finally formed was investigated by transmission electron microscopy. This investigation demonstrates that calcium accelerated the kinetics of the self-assembly, but it had no effect on the hydrolysis kinetics. As a result of the accelerated self-assembly kinetics at a high calcium concentration, the time of gelation decreased as well. A minimum concentration of calcium needed to obtain the tubular alpha-lactalbumin structures was determined. Below R = 1.5 (mole calcium/mole alpha-lactalbumin), turbid gels with randomlike structure were obtained. Between R = 1.5 and R = 6, translucent gels with a fine stranded network of tubules were formed, while higher calcium concentrations had a negative effect on the tubule formation, resulting in amorphous structures. The optimum calcium concentration for alpha-lactalbumin nanotube formation seemed to be around R = 3. 相似文献
6.
Gajewski JJ Bocian W Brichford NL Henderson JL 《The Journal of organic chemistry》2002,67(12):4236-4240
The competitive kinetics of additions of allyl to benzaldehyde-h and -d from allyltributyl tin, from diisopropyltartrylallyl boronate, and from allyl bromide and zinc dust in aqueous tetrahydrofuran have inverse secondary deuterium kinetic isotope effects, SDKIEs. These inverse SDKIEs are in contrast to the normal SDKIEs that were obtained with allyl lithium and allyl Grignard, suggesting rate-determining single-electron transfer in these cases. By various MO calculations the transition state for addition of allyl boronate occurs with substantial B-O bond formation and little C-C bond formation. The magnitudes of the SDKIEs with the other two allylating reagents, when compared with reasonable equilibrium isotope effects for the addition, suggest transition states with substantial C-C bond formation. 相似文献
7.
Johanna Sabine Becker Jochen Westheide Anatolij I. Saprykin Horst Holzbrecher Uwe Breuer Hans -Joachim Dietze 《Mikrochimica acta》1997,125(1-4):153-160
For the determination of trace impurities in ceramic components of solid oxide fuel cells (SOFCs), some mass spectrometric methods have been applied such as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). Due to a lack of suitable standard reference materials for quantifying of analytical results on La
x
Sr
y
MnO3 cathode material a matrix-matched synthetic standard-high purity initial compounds doped with trace elements-was prepared in order to determine the relative sensitivity coefficients in SSMS and LA-ICP-MS. Radiofrequency glow discharge mass spectrometry (rf-GDMS) was developed for trace analysis and depth profiling of thick non-conducting layers. Surface analytical techniques, such as secondary ion mass spectrometry (SIMS) and sputtered neutral mass spectrometry (SNMS), were used to determine the element distribution on surfaces (homogeneity) and the surface contaminants of SOFC ceramic layers.Dedicated to Professor Dr. rer. nat. Hubertus Nickel on the occasion of his 65th birthday 相似文献
8.
Terephthalamide derivatives as mimetics of helical peptides: disruption of the Bcl-x(L)/Bak interaction 总被引:4,自引:0,他引:4
Yin H Lee GI Sedey KA Rodriguez JM Wang HG Sebti SM Hamilton AD 《Journal of the American Chemical Society》2005,127(15):5463-5468
A series of Bcl-x(L)/Bak antagonists, based on a terephthalamide scaffold, was designed to mimic the alpha-helical region of the Bak peptide. These molecules showed favorable in vitro activities in disrupting the Bcl-x(L)/Bak BH3 domain complex (terephthalamides 9 and 26, K(i) = 0.78 +/- 0.07 and 1.85 +/- 0.32 microM, respectively). Extensive structure-affinity studies demonstrated a correlation between the ability of terephthalamide derivatives to disrupt Bcl-x(L)/Bak complex formation and the size of variable side chains on these molecules. Treatment of human HEK293 cells with the terephthalamide derivative 26 resulted in disruption of the Bcl-x(L)/Bax interaction in whole cells with an IC(50) of 35.0 microM. Computational docking simulations and NMR experiments suggested that the binding cleft for the BH3 domain of the Bak peptide on the surface of Bcl-x(L) is the target area for these synthetic inhibitors. 相似文献
9.
The introduction of photoactive metal centres onto cyclodextrin receptors opens up new possibilities for the design of sensors, wires and energy conversion systems. This tutorial review focuses on strategies involving such metallocyclodextrins for the construction of supramolecular arrays with light-activated functions. The assembly procedures for building such arrays are presented, together with the features required for their functions both as sensors for ion or small molecule detection and as wires for photoinduced long-range energy or electron transport. Systems for metal ion sensing are described where the cyclodextrin plays a mediating role in influencing the luminescence properties of an organic probe, responsive to metal binding. Small molecule sensing by the cyclodextrin cavity is realised using luminescent lanthanide or transition metal functionalised cyclodextrins. The light signal of the photoactive metal is switched on or off upon binding an analyte in the cyclodextrin cavity. The metallocyclodextrin systems that function as wires are distinguished by the controlled assembly of transition metal polypyridine and metalloporphyrin units. These units have inherent photoactivity that defines the vectorial direction of energy or electron transfer processes through the wire. 相似文献
10.
Proteins are continuously synthesized during cell growth and proliferation. At the same time, excessive and misfolded proteins have to be degraded, otherwise they are a burden to cells. Protein degradation is essential to maintain proteostasis in cells, and dysfunction of protein degradation systems results in numerous diseases such as cancer and neurodegenerative diseases. Despite the importance of protein degradation, the degradation pathways of many proteins remain to be explored. Here, we comprehensively investigated the degradation of newly synthesized proteins in human cells by integrating metabolic labeling, click chemistry, and multiplexed proteomics, and systematic and quantitative analysis of newly synthesized proteins first revealed the degradation pathways of many proteins. Bioinformatic analysis demonstrates that proteins degraded through two major pathways have distinct properties and functions. Proteins degraded through the ubiquitin-proteasome pathway contain more disordered structures, whereas those through the autophagy-lysosome pathway have significantly higher hydrophobicity. Systematic and quantitative investigation of the dynamics of newly synthesized proteins provides unprecedented and valuable information about protein degradation, which leads to a better understanding of protein properties and cellular activities.Systematic quantification of the dynamics of newly synthesized proteins first reveals the degradation pathways of many proteins in human cells, and proteins degraded through each of the two major pathways have distinct properties and functions. 相似文献