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131.
Ko C Levine B Toniolo A Manohar L Olsen S Werner HJ Martínez TJ 《Journal of the American Chemical Society》2003,125(42):12710-12711
The photoisomerization mechanism of the neutral form of the photoactive yellow protein (PYP) chromophore is investigated using ab initio quantum chemistry and first-principles nonadiabatic molecular dynamics (ab initio multiple spawning or AIMS). We identify the nature of the two lowest-lying excited states, characterize the short-time behavior of molecules excited directly to S2, and explain the origin of the experimentally observed wavelength-dependent photoisomerization quantum yield. 相似文献
132.
133.
[reaction: see text] The first examples of free radical-mediated vinyl amination are described by nonconventional vinyl radical addition to azomethine nitrogen. This new vinyl amination protocol is mild and provides convenient synthetic access to nonstabilized N,N-dialkyl enamines and tandem bond-forming processes. 相似文献
134.
Zusammenfassung Die spektrometrische Analyse von weiß erstarrtem Roheisen (auf C, Si, Mn, P, S, Cu) ist mit der gleichen Anregung und in der gleichen Funkzeit wie diejenige von Stahl möglich. Eine spezielle Kalibriertechnik mit Stahlproben garantiert ein ausreichend reproduzierbares und richtiges Resultat in relativ kurzer Zeit (20 sec).
Wir sind Herrn T. Nientiedt für zahlreiche Anregungen und Diskussionen zu Dank verpflichtet. 相似文献
Emission-spectrometrical analysis of pig iron
The conditions of pig iron analysis by using a direct reading spectrometer for routine determination of C, Si, Mn, P, S and Cu, the influence of sampling and a new calibration technique of the instrument are described. The whole time needed for complete spectrometrical analysis is about 20 sec.
Wir sind Herrn T. Nientiedt für zahlreiche Anregungen und Diskussionen zu Dank verpflichtet. 相似文献
135.
Komaragiri V McCarter B Bililign S Hagebaum-Reignier D Ledentu V Jeung GH 《The Journal of chemical physics》2005,123(2):24303
Quenching mechanisms of the Li3p and Li4p states in collision with the nitrogen molecule are studied by laser-induced fluorescence spectroscopy and by a quantum chemical calculation. The Li3p state is observed to be efficiently quenched to the Li3s state detected as intense 3s-->2p emission. The Li4p state is efficiently quenched to the Li4s and Li3d states detected as 4s-2p and 3d-2p emissions, respectively. The potential-energy surfaces for the Li(2s-4p)N2 states show a large number of conical intersections and avoided crossings resulting from the couplings between the ionic [Li+(N2)-] and covalent configurations. There are a large number of stable excited states, and we give here the spectroscopic constants for the lowest two stable isomers correlating to Li2p+N2. 相似文献
136.
Stéphanie Etienne C. Becker D. Ruch B. Grignard G. Cartigny C. Detrembleur C. Calberg R. Jerome 《Journal of Thermal Analysis and Calorimetry》2007,87(1):101-104
Silica nanoparticles of various sizes have
been incorporated by melt compounding in a poly(methyl methacrylate) (PMMA)
matrix to enhance its thermal and mechanical properties. In order to improve
nanoparticles dispersion, PMMA grafted particles have been prepared by atom
transfer radical polymerization (ATRP) from well-defined silica nanoparticles.
This strategy was expected to ensure compatibility between both components
of the PMMA nanocomposites. TEM analysis have been performed to evaluate the
nanosilica dispersion whereas modified and non-modified silica/PMMA nanocomposites
thermal stability and mechanical properties have been investigated by both
thermogravimetric and dynamical mechanical analysis. 相似文献
137.
Trimethylsilyl Derivatives of Vb-Elements. VI. Synthesis, Molecular and Crystal Structure of Tetrakis(trimethylsilyl)distibine Compared with Tetraphenyldistibine Tetrakis(trimethylsilyl)distibine already isolated by Breunig et al. [9] from cleavage reactions of tris(trimethylsilyl)stibine may also be obtained in high yields from lithium bis(trimethylsilyl)antimonide · 2THF and 1,2-dibromoethane in n-pentane. This compound intensely red in the solid state, but only slightly yellow in solution or in the melt crystallizes in the monoclinic space group P21/c with a = 680.6(1); b = 1672.8(2); c = 1190.0(1) pm; β = 119.01(5)°; Z = 2 at +20°C. An X-ray structure determination (R = 0.017) shows the bis(trimethylsilyl)-stibino groups to be arranged in a transoid position. Characteristic bond lengths and angles are: Sb? Sb 286.7(1); Sb? Si 259.4 pm; Si? Sb? Si 94.46(3); Sb? Sb? Si 98.68(3) and 94.43(3)°. As in similiar 2,2′,5,5′-tetramethyldistibolyl published recently by Ashe III et al. [8] this crystal structure, too, is characterized by a nearly linear sequence of Sb? Sb groups. Compared with the sum of van-der-Waals radii the intermolecular Sb-Sb contact in such a chain is shortened from 440 to 399 pm. This probably allows electronic interactions of unknown type responsible for the colour of the crystals. In keeping with this assumption an analogous formation of chains is not found in solid, only yellow tetraphenyldistibine 5 the structure of which has already been studied by Rehder et al. [44]. 相似文献
138.
A method, named “cold oxidation” was developed, by which structures of isotropic looking pyrocarbon coatings of nuclear fuel particles can be made visible. It is based on a dry oxidation of the pyrocarbon at room temperature by highly excited oxygen. The amorphous parts of the pyrocarbon coatings burn off more quickly than the pyrocarbon itself and thereby a relief-like coating structure appears. It could be shown that a connection exists between the structure of the pyrocarbon coatings after “cold oxidation” and their behaviour under fast neutron irradiation. 相似文献
139.
Benjamin Esquivel Lawrence Nicholson Linda Peerey Michael Fazio 《Journal of separation science》1991,14(12):816-823
Factors influencing the stereoisomeric resolution of underivatized dipeptides and a representative tripeptide on Crownpak (CR) columns have been investigated. The elution order and relative retention suggest that a combination of chiral, steric, and hydrophobic interactions effects the extent of chiral recognition and the retention achieved during separations. Some dipeptides whose amine terminus is located three atoms from the asymmetric center (such as dipeptides of D ,L -glycine) were resolved, but the elution order was the opposite of that expected for the type of Crownpak column used (CR(+)). Peptides containing hydrophobic substituents were strongly retained, but their retention times could be significantly reduced, and detectability improved, by use of gradient elution. Analysis of a commercial sample of D ,L -leucine-D ,L -alanine revealed the stereoisomers to be present in an unexpected quantitative ratio and demonstrated the utility of these separations for quality assurance and quantitative analyses. 相似文献
140.
Two macrocyclic aminoglycosides were prepared from a 1,4-butanediol linked 2-deoxy-L-rhamnal which was O-allylated at the 4- and 4'-positions via the precursor allyl 3,4-di-O-acetyl-2,6-dideoxy-alpha-L-arabino-hexoside employing olefin metathesis and ring closing metathesis in a sequential manner. The macrocycles were 15N-labelled at all four amino groups in order to study interactions with regulatory RNA structures in solution by NMR spectroscopy. A key step for the introduction of the 15N-label was a reductive amination step using commercially available 15NH4OAc. The reductive amination proceeds with excellent stereocontrol. As a by-product the unusual acyclic amino nitrile was isolated which originated from intramolecular imine formation followed by cyanide addition to the intermediate C=N double bond. 相似文献