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994.
Anna Fryszkowska Dominik Koszelewski Ryszard Ostaszewski 《Tetrahedron: Asymmetry》2017,28(9):1127-1134
A novel asymmetric route to bicyclomycin analogues, 2-oxa-bicyclo[4.2.2]decane-8,10-diones, is described. The key chiral synthons 3-(ω-hydroxyalkyl)-2,5-diketopiperazines 3a-c were obtained via enzymatic kinetic resolution of their respective acetates 2a-c using hydrolases (up to >98% ee, E > 200). The chiral 2,5-diketopiperazines were then transformed into their bicyclic derivatives in a stereospecific manner. Circular dichroism and NMR studies were performed to determine the absolute and relative configuration of the obtained products. The biocatalytic approach gave high stereoselectivities in comparison to the chiral pool synthesis from glutamic acid (58% ee) and thus demonstrated the ability of hydrolases to discriminate a remote stereocenter. 相似文献
995.
J. Marx H. Huang I. Faus S. Rackwitz J. A. Wolny K. Schlage R. Ulber H. -C. Wille V. Schünemann 《Hyperfine Interactions》2014,226(1-3):661-665
Bovine serum albumin coated magnetic iron oxide nanoparticles (IONPs), which were synthesized using a co-precipitation method with 57Fe have been subject to a combined study using atomic force microscopy (AFM) and nuclear inelastic scattering (NIS). The obtained partial density of vibrational states (pDOS) shows evidence for lattice stiffening and a pronounced mode at 23 meV compared to thin film magnetite at room temperature. 相似文献
996.
The numerical simulation of quantum many-body dynamics is typically limited by the linear growth of entanglement with time. Recently numerical studies have shown that for 1D Bethe-integrable models the simulation of local operators in the Heisenberg picture can be efficient. Using the spin-1/2 XX chain as generic example of an integrable model that can be mapped to free fermions, we provide a simple explanation for this. We show furthermore that the same reduction of complexity applies to operators that have a high-temperature autocorrelation function which decays slower than exponential, i.e., with a power law. Thus efficient simulability may already be implied by a single conservation law as we will illustrate numerically for the spin-1 XXZ model. 相似文献
997.
Dominik J. Schwarz Benedict KalusMarina Seikel 《Progress in Particle and Nuclear Physics》2011,66(2):226-231
We present a short (and necessarily incomplete) review of the evidence for the accelerated expansion of the Universe. The most direct probe of acceleration relies on the detailed study of supernovae (SN) of type Ia. Assuming that these are standardizable candles and that they fairly sample a homogeneous and isotropic Universe, the evidence for acceleration can be tested in a model-independent and calibration-independent way. Various light-curve fitting procedures have been proposed and tested. While several fitters give consistent results for the so-called Constitution set, they lead to inconsistent results for the recently released SDSS SN. Adopting the SALT fitter and relying on the Union set, cosmic acceleration is detected by a purely kinematic test at 7σ when spatial flatness is assumed and at 4σ without any assumption on the spatial geometry. A weak point of the described method is the local set of SN (at z<0.2), as these SN are essential to anchor the Hubble diagram. These SN are drawn from a volume much smaller than the Hubble volume and could be affected by local structure. Without the assumption of homogeneity, there is no evidence for acceleration, as the effects of acceleration are degenerate with the effects of inhomogeneities. Unless we sit in the centre of the Universe, such inhomogeneities can be constrained by SN observations by means of tests of the isotropy of the Hubble flow. 相似文献
998.
The complex of cadmium with pyrrolidine dithiocarbamate Cd(pdtc)2 has been used as single source precursor for the synthesis of CdS nanoparticles. The formation of CdS nanostructures was achieved by thermal decomposition of the complex under microwave irradiation and conventional heating in presence of hexadecylamine. The CdS nanoparticles with disordered close-packed structure were obtained under microwave irradiation, whereas wurtzite hexagonal phase CdS nanorods were obtained by conventional heating method (up to 150 °C). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) studies also were carried out to study the structure and morphology of nanoparticles. The optical property of the CdS nanoparticles was studied by UV-visible and fluorescence emission spectral studies. Fluorescence measurements on the CdS nanoparticles show a strong emission spectrum with two sub bands that are attributed to band-edge and surface-defect emissions. The reduction of a suitable cadmium metal complex is considered to be one of the single pot methods to generate CdS semiconductor nanoparticles with different shapes and high yield. 相似文献
999.
Robert N. Wolf Markus Eritt Gerrit Marx Lutz Schweikhard 《Hyperfine Interactions》2011,199(1-3):115-122
A multi-reflection time-of-flight mass separator (MR-ToF-MS) for the enhancement of the performance of the Penning-trap mass spectrometer ISOLTRAP at the on-line isotope separator ISOLDE/CERN has been built and investigated at an off-line test facility. The MR-ToF-MS consists of two ion-optical mirrors between which oscillating ions are separated according to their different mass-over-charge ratios m/q. Flight paths of several hundreds of meters are folded to an apparatus length of less than one meter. Preliminary tests resulted in a mass-resolving power of up to m/??m????80,000, and the separation was demonstrated for the isobaric ions CO?+? and $\mathrm{N}_2^+$ . The MR-ToF-MS will support the existing purification methods of ISOLTRAP and will extend the access to nuclides produced with high isobaric contamination yields at the ISOLDE facility. 相似文献
1000.
Forbert H Masia M Kaczmarek-Kedziera A Nair NN Marx D 《Journal of the American Chemical Society》2011,133(11):4062-4072
Understanding chemical reactivity at ultracold conditions, thus enabling molecular syntheses via interstellar and atmospheric processes, is a key issue in cryochemistry. In particular, acid dissociation and proton transfer reactions are ubiquitous in aqueous microsolvation environments. Here, the full dissociation of a HCl molecule upon stepwise solvation by a small number of water molecules at low temperatures, as relevant to helium nanodroplet isolation (HENDI) spectroscopy, is analyzed in mechanistic detail. It is found that upon successive aggregation of HCl with H(2)O molecules, a series of cyclic heteromolecular structures, up to and including HCl(H(2)O)(3), are initially obtained before a precursor state for dissociation, HCl(H(2)O)(3)···H(2)O, is observed upon addition of a fourth water molecule. The latter partially aggregated structure can be viewed as an "activated species", which readily leads to dissociation of HCl and to the formation of a solvent-shared ion pair, H(3)O(+)(H(2)O)(3)Cl(-). Overall, the process is mostly downhill in potential energy, and, in addition, small remaining barriers are overcome by using kinetic energy released as a result of forming hydrogen bonds due to aggregation. The associated barrier is not ruled by thermal equilibrium but is generated by athermal non-equilibrium dynamics. These "aggregation-induced chemical reactions" are expected to be of broad relevance to chemistry at ultralow temperature much beyond HENDI spectroscopy. 相似文献