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41.
This paper develops a mathematical model of the ring-spinning process that takes into account its non-stationary nature. A complex system of differential equations is obtained, which from a mathematical point of view constitutes a ‘free-boundary’ problem. Its solution involves definition of suitable boundary conditions related to the mechanical characteristics of the process and of the spinning machine itself. The boundary conditions which determine the solution are pointed out. A numerical solution of the system of differential equations can be obtained by the Finite-Segments method, as shown in an example. 相似文献
42.
Dunsmore CJ Carr R Fleming T Turner NJ 《Journal of the American Chemical Society》2006,128(7):2224-2225
Deracemization of racemic chiral tertiary amines has been achieved by combination of an enantioselective amine oxidase, obtained through directed evolution, and ammonia borane in a one-pot process. 相似文献
43.
Marta De Toni Romain Jonchiere Dr. Pluton Pullumbi Dr. François‐Xavier Coudert Prof. Dr. Alain H. Fuchs 《Chemphyschem》2012,13(15):3497-3503
We report an ab initio molecular dynamics study of the hydration process in a model IRMOF material. At low water content (one molecule per unit cell), water physisorption is observed on the zinc cation but the free?bound equilibrium strongly favors the free state. This is consistent with the hydrophobic nature of the host matrix and its type‐V isotherm observed in a classical Monte Carlo simulation. At higher loading, a water cluster can be formed at the Zn4O site and this is shown to stabilize the water‐bound state. This structure rapidly transforms into a linker‐displaced state, where water has fully displaced one arm of a linker and which corresponds to the loss of the material’s fully ordered structure. Thus an overall hydrophobic MOF material can also become water unstable, a feature that has not been fully understood until now. 相似文献
44.
In recent years single molecule force spectroscopy has emerged as a powerful new tool to explore the mechanical stability and folding pathways of individual proteins. This technique is used to apply a stretching force between two points of a protein, unfolding the protein to an extended state. By measuring the unfolding and folding trajectories of individual proteins, insight can be gained into the physical mechanisms of protein folding. In this tutorial review we introduce the reader to single molecule force spectroscopy using the atomic force microscope (AFM), and explain the two main modes of operation of the AFM for force spectroscopy: force-extension and force-clamp. We introduce the approach of using polyproteins to obtain a clear mechanical fingerprint for monitoring the response of proteins to an applied mechanical force. In addition, we provide an informative and representative review of recent research on proteins using single molecule force spectroscopy. We focus on areas which have made a significant contribution to the single molecule protein folding field and highlight emerging areas of research which have wider implications for the general scientific community. 相似文献
45.
46.
Cordes J Calo F Anderson K Pfaffeneder T Laclef S White AJ Barrett AG 《The Journal of organic chemistry》2012,77(1):652-657
A five-step synthesis of the natural product angelicoin A using a late stage highly regioselective palladium(0)-catalyzed decarboxylative prenyl migration and aromatization sequence as the key step is reported. The method was extended with geranyl migration in eight-step total syntheses of hericenone J and hericenol A from geraniol. 相似文献
47.
Cells continuously produce reactive oxidative species that can modify all cellular components. In proteins, for example, cysteine, methionine, tryptophan (Trp), and tyrosine residues are particularly prone to oxidation. Here, we report two new approaches to distinguish two isomeric oxidation products of Trp residues, i.e. 5‐hydroxytryptophan (5‐HTP) and oxindolylalanine (Oia) residues, in peptides. First, 2‐nitrobenzenesulfenyl chloride, known to derivatize Trp residues in position 2 of the indole ring, was used to label 5‐HTP residues. The mass shift of 152.98 m/z units allowed identifying 5‐HTP‐ besides Trp‐containing peptides by mass spectrometry, whereas Oia residues were not labeled. Second, fragmentation of the Oia‐ and 5‐HTP‐derived immonium ions at m/z 175.08 produced ions characteristic for each residue that allowed their identification even in the presence of y1 ions at m/z 175.12 derived from peptides with C‐terminal arginine residues. The pseudo MS3 spectra acquired on a quadrupole time‐of‐flight hybrid mass spectrometer displayed two signals at m/z 130.05 and m/z 132.05 characteristic for Oia‐containing peptides and a group of six signals (m/z 103.04, 120.04, 130.04, 133.03, 146.04, and 148.04) for 5‐HTP‐cointaining peptides. In both cases, the relative signal intensities appeared to be independent of the sequence providing a specific fingerprint of each oxidative modification. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
48.
49.
The breathing mechanism of a transversely cracked rotor and its influence on a rotor system that appears due to the shaft weight is studied. This breathing mechanism is based on experimental and simulation result for the crack shape reported in the literature. If the crack depth is small, the crack closure line is a straight line while for larger crack depths the crack closure becomes more curved. For both cases, a method is proposed for the evaluation of the stiffness losses in the cross section that contains the crack. This method is based on a cohesive zone model (CZM) instead of linear elastic fracture mechanics (LEFM) approach, because LEFM is valid only for the fully open crack and cannot be extended to other intermediate situations. As the crack is closed, the stress intensity factor (SIF) will not appear at the boundary between the closed cracked areas and the open cracked areas. The CZM is developed for mode-I plane strain conditions and accounts explicitly for triaxiality of the stress state by using constitutive relations. The proposed model gives more realistic results than models based on LEFM for the stiffness losses of the crack rotor system for a wide range of the crack depth. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
50.
Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out to study the interaction between xenon atom and iodine molecule in a solid krypton matrix. Interference between the CARS polarizations of the "free" and complexed iodine molecules is observed, while the quantum beats of the complex are not detected due to low concentration. Vibrational analysis based on the polarization beats yields accurate molecular constants for the I2-Xe complex. The harmonic frequency of the I2-Xe complex is found to be redshifted by 0.90 cm-1 when compared to the free I2, whereas the anharmonicity is approximately the same. The dephasing rate of the complex is found to be somewhat higher than that of the free iodine molecule in solid Kr, showing that the complexation affects dephasing, although not dramatically. Molecular dynamics simulations are carried out to find the conformation of the complex, and wave packet simulations are used to reproduce the CARS signal to confirm the assignments of the observed beatings as quantum and polarization beats. The results show that the polarization beats are a useful tool for investigating weak interactions in condensed phase. 相似文献