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91.
92.
Fabian WM 《The Journal of organic chemistry》2002,67(21):7475-7482
The site of nucleophilic addition to five-membered heterocyclic 2,3-diones (4-iminomethylfuran-2,3-dione A1 and 4-formyl-pyrrole-2,3-dione B1) is studied by density functional theory calculations (B3LYP/6-31G) with water as the nucleophile. Both uncatalyzed and water-assisted 1,2-addition to the lactone (lactam) and the keto carbonyl group, and conjugate addition to C5 of the heterocycle and the heteroatom of the 4-iminomethyl (formyl) moiety are considered. In addition, concerted and stepwise ring fission of the lactone (lactam) ring is also treated. The effect of solvation (aqueous solution) is taken into account by the polarizable continuum model (PCM) and the Poisson-Boltzmann SCRF method (PB-SCRF), as well as explicit water molecules. Only this latter approach yields meaningful activation free energies. Barriers for addition of H2O increase in the order 1,4-addition to C5 < addition to the lactone (lactam) carbonyl < hydration of the 3-keto group. No reaction path for concerted water-assisted ring opening could be found. 相似文献
93.
We consider a one-dimensional charge density wave insulator formed by umklapp processes in a quarter-filled band. The spectrum of the model consists of gapless, uncharged excitations carrying spin +/- 1/2 (spinons) and gapped, spinless excitations carrying charge -/+ signe/2 (solitons and antisolitons). We calculate the low-energy behavior of the single-electron Green's function at zero temperature. The spectral function exhibits a featureless scattering continuum of two solitons and many spinons. The theory predicts that the gap observed by angle resolved photoemission is twice the activation gap in the dc conductivity. We comment on possible applications to PrBa(2)Cu(3)O(7) and to the Bechgaard salts. 相似文献
94.
Nontrivial steady flows have recently been found that capture the main structures of the turbulent buffer layer. We study the effects of polymer addition on these "exact coherent states" (ECS) in plane Couette flow. Despite the simplicity of the ECS flows, these effects closely mirror those observed experimentally: Structures shift to larger length scales, wall-normal fluctuations are suppressed while streamwise ones are enhanced, and drag is reduced. The mechanism underlying these effects is elucidated. These results suggest that the ECS are closely related to buffer layer turbulence. 相似文献
95.
96.
Litvinyuk IV Légaré F Dooley PW Villeneuve DM Corkum PB Zanghellini J Pegarkov A Fabian C Brabec T 《Physical review letters》2005,94(3):033003
Shakeup of a two-electron system is investigated in the strong infrared laser field limit, both theoretically and experimentally. During tunnel ionization the electron shakes up a second electron to an excited bound state. Theoretically, a complete analytical theory of shakeup in intense laser fields is developed. We predict that shakeup produces one excited sigma(u) D(+)(2) state in approximately 10(5) ionization events. Shakeup is measured experimentally by using the molecular clock provided by the internuclear motion. The number of measured events is found to be in excellent agreement with theory. 相似文献
97.
It is proved that a Banach space X is a subspace of a weaklycompactly generated Banach space if and only if, for every >0,X can be covered by a countable collection of bounded closedconvex symmetric sets where the weak* closure in X** of eachof them lies within the distance from X. A new short functional-analyticproof of the known result that a continuous image of an Eberleincompact is Eberlein is given as a corollary. 相似文献
98.
Fabian Jachmann 《Solid State Communications》2007,142(4):212-216
In a thin film of superconducting Y Ba2Cu3O7 the impact of surface acoustic waves (SAWs) traveling on the piezoelectric substrate is investigated. A pronounced interaction between the ultrasonic waves and the vortex system in the type II superconductor is observed. The occurrence of a SAW-induced dc voltage perpendicular to the sound path is interpreted as dragging of vortices by the piezoacoustic SAW, which acts as a conveyor for the flux quanta. The antisymmetry of this voltage with respect to the magnetic field directly evidences the induced, directed flux motion. This dynamic manipulation of vortices can be seen as an important step towards flux-based electronic devices. 相似文献
99.
Ahmed Al‐Harrasi Dr. Fabian Pfrengle Dipl.‐Chem. Vladimir Prisyazhnyuk Dr. Shahla Yekta Dr. Peter Koóš Dr. Hans‐Ulrich Reissig Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(43):11632-11641
1,3‐Dioxolanyl‐substituted 1,2‐oxazines, such as syn‐ 1 and anti‐ 1 , rearrange under Lewis acidic conditions to provide bicyclic products 2 – 5 . Subsequent reductive transformations afforded enantiopure 3‐aminopyran derivatives such as 7 and 9 or their protected diastereomers 16 and 18 , which can be regarded as carbohydrate mimetics. An alternative sequence of transformations including selective oxidation of the primary hydroxyl groups in 21 and 24 led to two protected β‐amino acid derivatives with carbohydrate‐like backbone (sugar amino acids). Treatment of bicyclic ester 23 with samarium diiodide cleaved the N? O bond and furnished the unusual β‐lactam 27 in excellent yield. Alternatively, γ‐amino acid derivative 29 was efficiently prepared in a few steps. Fairly simple transformations gave azides 32 and 35 or alkyne 30 which are suitable substrates for the construction of oligosaccharide mimetics such as 34 by copper iodide catalyzed cycloadditions. With this report we demonstrate that enantiopure rearrangement products 2 – 5 are protected precursors of a variety of polyfunctionalized pyran derivatives with great potential for chemical biology. 相似文献
100.
L. Nyulászi T. Pasinszki J. Réffy T. Veszprémi J. Fabian W. Thiel 《Structural chemistry》1990,1(4):367-370
The Hel UPS spectra of acetamidine, perimidine, and four 2-substituted perimidine derivatives have been recorded and interpreted using ab initio and MNDO quantum-chemical calculations. A large interaction between the naphthalene and amidine fragment was concluded from the lowest ionization energy. The color-determining band of these compounds is strongly affected by the intramolecular charge-transfer transitions, which are of low energy because of the low ionization energy of the perimidine moiety. 相似文献