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1.
van Duynhoven JP Broekmann I Sein A van Kempen GM Goudappel GJ Veeman WS 《Journal of colloid and interface science》2005,285(2):703-710
Monoglyceride coagels consist of a network of plate-like crystals and are formed from a swollen gel state (alpha-gel). In order to resolve the transition mechanism, coagels were prepared with monoglycerides that differ in fatty acid composition (monomyristate and palmitate/stearate, respectively). Rheology provided information on kinetics of coagel formation and the strength of the resulting crystal network. From NMR measurements, the surface-to-volume ratio, tortuosity, and dimensionality of the network were obtained. These findings were in line with qualitative and quantitative structural information obtained from CryoSEM. As a model for the behaviour of non-monoglyceride species, the dynamics of (perdeuterated) palmitic acid was monitored in both alpha-gels and coagels. The experimental data support a two-stage mechanism. In the first stage, two-dimensional separation of D- and L-isomers in the monoglyceride bilayers of the alpha-gel occurs. This process depends primarily on lateral diffusion rate of the monoglycerides. Palmitic acid can be accommodated in the alpha-gel bilayer, but in the coagels it is separated into relative mobile and mechanically weak junction zones between the crystal plates. In the second stage of coagel formation, the crystal plates also grow in the third dimension. Both monoglyceride type and concentration determine the kinetics of this process. 相似文献
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Hans Bock Claudia Arad Christian Nther Zdenek Havlas Ilka Gbel Andreas John Markus Kleine 《Helvetica chimica acta》1995,78(4):866-878
Electron Transfer and Ion Pair Formation Single Crystal Structure of Bis(sodium 1,1′-biphenyl-2-thiolate-diglyme): An Intermediate in the Reductive Ring Opening of Dibenzothiophene On Na-metal reduction of dibenzothiophene, the five-membered sulfur ring opens to form a colorless 1,1′-biphenyl-2-thiolate sodium salt, which, according to its single-crystal structure determination, is a dimer containing a four-membered, twice diglyme-solvated ring (diglyme···Na⊕?SR)2. Additional measurements provide the following information: cyclic voltammetry in aprotic MeCN solution shows one quasi-reversible electron transfer at E = ?2.58 V. The dibenzothiophene radical anion can be generated in aprotic THF solution at a K mirror and characterized by an 81-line ESR spectrum and its simulation. This blue species is also the first UV/VIS detectable one before the solution changes via green (due to blue + yellow color mixing) to yellow, yielding across an isosbestic point a second and diamagnetic compound. All of the above results suggest a consecutive two-electron reduction followed by an intersystem protonation, M + (e?) → M.? (blue) + (e?) → (M??, yellow?) + (H⊕) → MH? (colorless), to yield the crystallized and structurally characterized reaction intermediate. The diglyme-solvated sodium-salt dimer provides a basis for a quantum-chemical discussion of some facets of the most likely microscopic reduction pathway. 相似文献
3.
Ilka Agricola 《Communications in Mathematical Physics》2003,232(3):535-563
Given a reductive homogeneous space M=G/H endowed with a naturally reductive metric, we study the one-parameter family of connections ∇
t
joining the canonical and the Levi-Civita connection (t=0, 1/2). We show that the Dirac operator D
t
corresponding to t=1/3 is the so-called ``cubic' Dirac operator recently introduced by B. Kostant, and derive the formula for its square for
any t, thus generalizing the classical Parthasarathy formula on symmetric spaces. Applications include the existence of a new G-invariant first order differential operator on spinors and an eigenvalue estimate for the first eigenvalue of D
1/3. This geometric situation can be used for constructing Riemannian manifolds which are Ricci flat and admit a parallel spinor
with respect to some metric connection ∇ whose torsion T≠ 0 is a 3-form, the geometric model for the common sector of string theories. We present some results about solutions to
the string equations and a detailed discussion of a 5-dimensional example.
Received: 19 February 2002 / Accepted: 26 August 2002 Published online: 22 November 2002
RID="*"
ID="*" This work was supported by the SFB 288 ``Differential geometry and quantum physics' of the Deutsche Forschungsgemeinschaft
and the Max-Planck Society. 相似文献
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The Geodesics of Metric Connections with Vectorial Torsion 总被引:1,自引:0,他引:1
The present note deals with the dynamics of metric connections with vectorial torsion, as already described by E. Cartan in 1925. We show that the geodesics of metric connections with vectorial torsion defined by gradient vector fields coincide with the Levi-Civita geodesics of a conformally equivalent metric. By pullback, this yields a systematic way of constructing invariants of motion for such connections from isometries of the conformally equivalent metric, and we explain in as much this result generalizes the Mercator projection which maps sphere loxodromes to straight lines in the plane. An example shows that Beltrami's theorem fails for this class of connections. We then study the system of differential equations describing geodesics in the plane for vector fields which are not gradients, and show among others that the Hopf–Rinow theorem does also not hold in general. 相似文献
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Gerhard Quinkert Stefan Scherer Dietmar Reichert Hans-Peter Nestler Helma Wennemers Andreas Ebel Klaus Urbahns Klaus Wagner Klaus-Peter Michaelis Gerhard Wiech Günter Prescher Bernd Bronstert Bernd-Jürgen Freitag Ilka Wicke Dietmar Lisch Pavel Belik Thorsten Crecelius Dirk Hrstermann Gottfried Zimmermann Jan W. Bats Gerd Dürner Dieter Rehm 《Helvetica chimica acta》1997,80(6):1683-1772
The two conformers of a cyclohexa-2, 4-dienone with different substituents at C(6) on irradiation are believed to undergo ring opening stereospecifically affording a mixture of two configurationally isomeric diene-ketenes (and descendents thereof)- Exceptions are generally found for those dienones with one C and one O substituent or even with two C substituents, if one of them carries a polar group at a site able to interact through space with the ring C?O group. In these cases, only one of the two anticipated diene-ketenes (and descendents thereof) is produced. A thorough investigation of the photochemistry of a series of structurally different cyclohexa-2, 4-dienones on analytical as well as on preparative scale extends our mechanistic knowledge of the various routes from diene-ketenes into a variety of compound classes. Novel compound classes accessible to diene-ketenes are seven-membered carbocycles (by intramolecular aldolization of the zwitterion of appropriately substituted, transiently formed diene-(N, O)-ketene acetals) and β-lactams (by Staudinger reaction). 相似文献