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We consider the problem of representing arbitrary preferences in causal reasoning and planning systems. In planning, a preference may be seen as a goal or constraint that is desirable, but not necessary, to satisfy. To begin, we define a very general query language for histories, or interleaved sequences of world states and actions. Based on this, we specify a second language in which preferences are defined. A single preference defines a binary relation on histories, indicating that one history is preferred to the other. From this, one can define global preference orderings on the set of histories, the maximal elements of which are the preferred histories. The approach is very general and flexible; thus it constitutes a base language in terms of which higher-level preferences may be defined. To this end, we investigate two fundamental types of preferences that we call choice and temporal preferences. We consider concrete strategies for these types of preferences and encode them in terms of our framework. We suggest how to express aggregates in the approach, allowing, e.g. the expression of a preference for histories with lowest total action costs. Last, our approach can be used to express other approaches and so serves as a common framework in which such approaches can be expressed and compared. We illustrate this by indicating how an approach due to Son and Pontelli can be encoded in our approach, as well as the language PDDL3.
Multinuclear dynamic NMR spectroscopy of 3,5-bis(trifluoromethylsulfonyl)-1,3,5-oxadiazinane (3) revealed the existence of two conformers with differently oriented CF3 groups with respect to the ring, and two dynamic processes: ring inversion and restricted rotation about the N-S bond. Two transition states connecting the two conformers and corresponding to clockwise and counterclockwise rotations about the N-S bond were found; the calculated activation barriers of about 12 kcal/mol are in excellent agreement with those measured experimentally for the related molecule 1,3,5-tris(trifluoromethylsulfonyl)-1,3,5-triazinane (1). X-ray analysis proved the existence of the symmetric isomer of 3, which is the minor isomer in solutions but the only one in the crystal due to packing effects. The normal Perlin effect (JCHax < JCHeq)observed for 2(6)-CH2 in 3, whereas the reversed Perlin effect was found for the 4-CH2 group in 3 as well as for all CH2 groups in 1 both experimentally and theoretically. The latter effect in compounds 1, 3, and 1- (methylsulfonyl)-3,5-bis(trifluoromethylsulfonyl)-1,3,5-triazinane (2) can be considered as a genuine reverse Perlin effect since larger values of 1JCH are observed for longer C-H bonds.
A new synthetic approach to 2,3-dihydro-4H-1,3-thiazine derivatives based upon reductive rearrangement of 1,2- dithiole-3-ylidene thiones has been developed. In turn, the 1,2-dithiole derivatives were prepared by an efficient ring- opening-closing process of 2-alkylidene-4-oxothiazolidines, induced in the presence of Lawesson's reagent by intramolecular non-bonded 1,5-type S...O interactions in the 4-oxothiazolidine precursors.
Both the stoichiometry and complex stability constants of crown ether complexes with metal ions have been determined by examining gradual changes in their diffusional behavior in nonaqueous solution. Diffusion coefficients, D, were evaluated by pulsed field gradient (PFG) NMR titration experiments whilst complex stability constants were determined by nonlinear curve-fitting procedures, D versus csol., which also allow the treatment of multiple complexation equilibria (1:1 to 1:2 stoichiometries). Differences in the diffusion coefficients of the various free crown ethers with respect to their metal ion complexes indicate great sensitivity to both conformational changes and changes in molecular size upon complexation.
Dynamic 1H NMR (500 MHz) investigation of aryl-N-(arylsulfonyl)-N-(triphenylphosphoranylidene)imidocarbamates in CDCl3, CD3COCD3, and CD3OD at the temperature range of 183-298 K is reported. The observed free energy barriers (almost 12 kcal mol;1) are attributed to conformational isomerization about the NùS bond and these barriers show very little solvent dependence.
CAMPHOR: A GOOD MODEL FOR ILLUSTRATING NMR TECHNIQUES. The use of Nuclear Magnetic Resonance spectroscopy to establish the three-dimensional structures of molecules is an important component of modern Chemistry courses. The combination of techniques that can be used for this purpose is conveniently illustrated by their application to the camphor molecule. This paper presents applications of several techniques used in NMR spectral interpretation in an increasing order of complexity. The result of individual experiments is illustrated in order to familiarize the user with the way connectivity through bonds and through space is established from 1D/2D-NMR spectra and molecular stereochemistry is determined from different NMR experiments
The dynamic 1H NMR study of some primary carbamates in the solvents CDCl3 and CD3COCD3 between 183 and 298 K is reported. The free energies of activation, thus obtained (12.4 to 14.3 kcal mol-1), were attributed to the conformational isomerization about the N-C bond. These barriers to rotation show solvent dependence in contrast to the tertiary analogues and are lower in free energy by ca. 2-3 kcal mol-1.
The conformations of N-benzylideneani lines p-X-C6H4-CH=N-C6H4 p-Y (X, Y = NO2, CN, CF3, F, Cl, Br, H, Me, OMe, NMe2) have been studied by B3LYP density functional (DFT) hybrid method in combination with the 6-31G* or 6-311G* split valence basis set. The twist of the plane of the aniline ring with respect to the other part of the molecule (tau(2)) is systematically controlled by substituents X and Y, the effect of Y being larger. The value of the dihedral angle tau(2), correlates nicely with equation tau(2) = rho(F)(Y)(x)sigma(F)(Y)+rho(+R)(Y)(x)sigma(+)(R)(Y) + k(x) or tau(2) = rho(F)(X)(y)sigma(F)(X)+rho(-)(R)(X)(y)sigma(+)(R)(X) + k(y), respectively, when aniline or benzylidene substituent is varied. ED substituents X diminish the sensitivity of tau(2) to the aniline substituent Y[rho(F)(Y)(x) and rho(+)(R)(Y)(x)] while ED substituents Y increase the sensitivity Of T2 to the benzylidene substituent X[rho(F)(X)(y) and rho(+)(R)(X)(y)]. There seems to be two competitive conjugative interactions for the aniline ring n electrons: one with the nitrogen lone pair and one with the C=N unit. Substituents X and Y adjust the extent of these interactions and therefore the conformation of the molecule. A good correlation is observed between the dihedral angle tau(2) and the experimental C-13 NMR chemical shift of the C=N carbon of N-benzylideneanilines in CDCl3 (C) 2007 Elsevier B.V. All rights reserved.
Mono- and trans-1,4-dialkoxy substituted cyclohexanes (alkyl=Me, Et, i-Pr, t-Bu) were prepared using the solvomercuration-demercuration (SM-DM) procedure. The axialaxial and axial,axialequatorial, equatorial conformational equilibria of the products were studied by low temperature 1H and 13C NMR spectroscopy in CD2Cl2. The structures and relative energies of the participating conformers were calculated at both the B3LYP (6-311G*//6-311+G*) and MP2 (6-311+G*//6-311G*) levels of theory. In the case of DFT, good correlations of ;Gocalcd versus ;Goexptl were obtained. Both the structures and the energy differences of the conformers have been discussed with respect to established models of conformational analysis, viz. steric and hyperconjugative interactions. In addition, 1JH,C coupling constants were considered with respect to the hyperconjugation present.
Through space NMR shieldings of aromatic (benzene, mono-substituted and annelated benzenes, ferrocene, [14]- and [18]-annulenes, phenylenes and tetra- to heptahelicene) and anti-aromatic molecules (cyclobutadiene and pentalene) were assessed by ab initio molecular-orbital calculations. Employing the nucleus-independent chemical shifts (NICS) concept, these through space NMR shieldings were visualized as iso-chemical-shielding surfaces (ICSSs) and can be applied quantitatively to determine the stereochemistry of proximal nuclei. In addition, the distances in Å at ICSS values of ±0.1 ppm in-plane and perpendicular-to-center of the aromatic ring system were employed as a simple means to compare and estimate qualitatively the aromaticity of the systems at hand.
An investigation of the conformational landscape of 1,3-dithian-2-yl bearing porphyrins and the rotational behavior of the dithianyl substituents in meso position was carried out by variable-temperature (VT) NMR spectroscopy. Additionally, theoretical results for alternative conformations and energy barriers were obtained by molecular modeling. The study revealed different NH trans tautomers with regard to the orientation of the dithianyl ligands for the free base porphyrins 1-3. Relatively ruffled porphyrin core conformations were established for the transition states of the dithianyl rotation, resulting in a lower rotational energy barrier for the nickel(II) complex 4 compared to that of the free base systems. The data obtained and the first depiction of a rotational transition state for the rotation of bulky meso-alkyl substituents illustrate the close structural interplay between meso-alkyl substituents and the macrocycle conformation in porphyrins.
We examined relations between eye movements (single-fixation durations) and RSVP-based event-related potentials (ERPs; N400s) recorded during reading the same sentences in two independent experiments. Longer fixation durations correlated with larger N400 amplitudes. Word frequency and predictability of the fixated word as well as the predictability of the upcoming word accounted for this covariance in a path-analytic model. Moreover, larger N400 amplitudes entailed longer fixation durations on the next word, a relation accounted for by word frequency. This pattern offers a neurophysiological correlate for the lag-word frequency effect on fixation durations: word processing is reliably expressed not only in fixation durations on currently fixated words, but also in those on subsequently fixated words.
Using the gaze-contingent boundary paradigm with the boundary placed after word n, the experiment manipulated preview of word n + 2 for fixations on word n. There was no preview benefit for 1st-pass reading on word n + 2, replicating the results of K. Rayner, B. J. Juhasz, and S. J. Brown (2007), but there was a preview benefit on the 3- letter word n + 1, that is, after the boundary but before word n + 2. Additionally, both word n + 1 and word n + 2 exhibited parafoveal-on-foveal effects on word n. Thus, during a fixation on word n and given a short word n + 1, some information is extracted from word n + 2, supporting the hypothesis of distributed processing in the perceptual span.
Fixation durations in reading are longer for within-word fixation positions close to word center than for positions near word boundaries. This counterintuitive result was termed the Inverted-Optimal Viewing Position (IOVP) effect. We proposed an explanation of the effect based on error-correction of mislocated fixations [Nuthmann, A., Engbert, R., & Kliegl, R. (2005). Mislocated fixations during reading and the inverted optimal viewing position effect. Vision Research, 45, 2201-2217], that suggests that the IOVP effect is not related to word processing. Here we demonstrate the existence of an IOVP effect in "mindless reading", a G-string scanning task. We compare the results from experimental data with results obtained from computer simulations of a simple model of the IOVP effect and discuss alternative accounts. We conclude that oculornotor errors, which often induce mislocalized fixations, represent the most important source of the IOVP effect. (c) 2006 Elsevier Ltd. All rights reserved.
An lterative algorithm for the estimation of the distribution of mislocated fixations during reading
(2007)
Gransee : Franziskaner
(2007)
We study possible interrelations between the 300-year record of the yearly sunspot numbers and the solar inertial motion (SIM) using the recently developed technique of synchronization analysis. Phase synchronization of the sunspot cycle and the SIM is found and statistically confirmed in three epochs (1734-1790, 1855-1875 and 1907-1960) of the whole period 1700-2000. These results give quantitative support to the hypothesis that there is a weak interaction between the solar activity and the SIM.
Ziesar : Franziskaner
(2007)
Die Aufhebung desselben vorgeschlagenermaßen beschlossen : die Säkularisation von Kloster Dalheim
(2007)
Prenzlau : Franziskaner
(2007)
Vorwort
(2007)
Berlin : Franziskaner
(2007)