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71.
Fluorescence experiments on (1-butyl-4-(1H-inden-1-ylidene)-1,4-dihydropyridine (BIDP) are reported in liquid and glassy solutions. The data indicate a fast decay in the fluid nonpolar, nonprotic solutions (decay times approximately 10(-12) s) and rapid but considerably slower decay in polar ones. In frozen solutions (polar and nonpolar), the fluorescence quantum yield is much higher (near 0.5 and around 0.1 in polar and nonpolar glasses, respectively). The rapid nonradiative transitions in fluid solutions are assigned to internal conversion in both solvent classes, as intersystem crossing is much slower and no net reaction is observed. These results are in agreement with predictions made for the closely related (in terms of electronic structure) but simpler molecule cyclopentadienyl-1,4-dihydropyridine (CPDHP) for which an S1/S0 conical intersection was recently proposed [Int. J. Quant. Chem. 2005, 102, 961]. The crossing of the two lowest singlet states is calculated to vanish in polar solvents such as methyl cyanide, leading to longer lifetime of S1 of CPDHP. As BIDP has a very similar electronic structure, the model predicts a corresponding change in this larger molecule. The strong fluorescence observed in the glassy environments is rationalized by the hindering of the internal torsion required to reach the geometry of the conical intersection. 相似文献
72.
Kogan A Popov I Uvarov V Cohen S Aserin A Garti N 《Langmuir : the ACS journal of surfaces and colloids》2008,24(3):722-733
Crystallization of carbamazepine (CBZ), an antiepileptic drug, precipitated from confined spaces of nonionic microemulsions was investigated. The study was aimed to correlate the structure of the microemulsion [water-in-oil (W/O), bicontinuous, and oil-in-water (O/W)] with the crystalline structure and morphology of solid CBZ. The precipitated CBZ was studied by DSC, TGA, powder XRD, single-crystal XRD, SEM, and optical microscopy. The results suggest that the microstructure of the microemulsions influences the crystallization process and allows crystallizing polymorphs that exhibit different crystal structure and habits. W/O nanodroplets orient the crystallizing CBZ molecules to form a prismlike anhydrous polymorphic form with monoclinic unit cell and P21/n space group. Bicontinuous structures lead to platelike dihydrate crystals with orthorhombic unit cell and Cmca space group. The O/W nanodroplets cause the formation of needlelike dihydrate crystals with monoclinic unit cell and P21/c space group. The morphological features of solid CBZ remain predetermined by the basic symmetry and parameters of its unit cell. Precipitation of CBZ pseudopolymorphs from supersaturated microemulsion is discussed in terms of oriented attachment that provides perfect packing of numerous separately nucleated ordered nuclei of CBZ into microscale platelets and then into macroscopic crystals. Crystallization from microemulsion media enabling one to obtain the drug (CBZ) with predicted structure and morphology should be of great significance for pharmaceutical applications. 相似文献
73.
We continue the works of Gurevich-Shelah and Lifsches-Shelah by showing that it is consistent with ZFC that the first-order
theory of random graphs is not interpretable in the monadic theory of all chains. It is provable from ZFC that the theory
of random graphs is not interpretable in the monadic second order theory of short chains (hence, in the monadic theory of
the real line).
Received: 18 July 1996 相似文献
74.
A. O. Gattone D. Abriola F. T. Avignone R. L. Brodzinski J. I. Collar R. J. Creswick D. E. Di Gregorio H. A. Farach C. K. Gurard F. Hasenbalg H. Huck H. S. Miley A. Morales J. Morales S. Nussinov A. Ortiz de Solrzano J. H. Reeves J. A. Villar K. Zioutas The SOLAX Collaboration 《Nuclear Physics B - Proceedings Supplements》1999,70(1-3)
A new technique has been used to search for solar axions using a single crystal germanium detector. It exploits the coherent conversion of axions into photons when their angle of incidence satisfies a Bragg condition with a crystalline plane. The analysis of approximately 1.94 kg.yr of data from the 1 kg DEMOS detector in Sierra Grande, Argentina, yields a new laboratory bound on axion-photon coupling of gαγγ < 2.7 × 10−9GeV−1, independent of axion mass up to 1 keV. 相似文献
75.
Shmuel Zilberg Yehuda Haas David Danovich Sason Shaik 《Angewandte Chemie (International ed. in English)》1998,37(10):1394-1397
A twin of the transition state , which can be investigated spectroscopically and can thus supply information about the structure of the transition state, has now been characterized for the Cope rearrangement of semibullvalene (shown below). It involves an excited state with B2 symmetry and results from a linear combination of the ground-state wave functions of (mirror-image) reactant and product. 相似文献
76.
Inspection games in arms control 总被引:1,自引:0,他引:1
Rudolf Avenhaus Morton Canty D. Marc Kilgour Bernhard von Stengel Shmuel Zamir 《European Journal of Operational Research》1996,90(3):383
An inspection game is a mathematical model of a situation in which an inspector verifies the adherence of an inspectee to some legal obligation, such as an arms control treaty, where the inspectee may have an interest in violating that obligation. The mathematical analysis seeks to determine an optimal inspection scheme, ideally one which will induce legal behavior, under the assumption that the potential illegal action is carried out strategically; thus a non-cooperative game with two players, inspector and inspectee, is defined. Three phases of development in the application of such models to arms control and disarmament may be identified. In the first of these, roughly from 1961 through 1968, studies that focused on inspecting a nuclear test ban treaty emphasized game theory, with less consideration given to statistical aspects associated with data acquisition and measurement uncertainty. The second phase, from 1968 to about 1985, involves work stimulated by the Treaty on the Non-Proliferation of Nuclear Weapons (NPT). Here, the verification principle of material accountancy came to the fore, along with the need to include the formalism of statistical decision theory within the inspection models. The third phase, 1985 to the present, has been dominated by challenges posed by such far-reaching verification agreements as the Intermediate Range Nuclear Forces Agreement (INF), the Treaty on Conventional Forces in Europe (CFE) and the Chemical Weapons Convention (CWC), as well as perceived failures of the NPT system in Iraq and North Korea. In this connection, the interface between the political and technical aspects of verification is being examined from the game-theoretic viewpoint. 相似文献
77.
Jesús A. De Loera Edward D. Kim Shmuel Onn Francisco Santos 《Journal of Combinatorial Theory, Series A》2009,116(8):1306-1325
This paper discusses properties of the graphs of 2-way and 3-way transportation polytopes, in particular, their possible numbers of vertices and their diameters. Our main results include a quadratic bound on the diameter of axial 3-way transportation polytopes and a catalogue of non-degenerate transportation polytopes of small sizes. The catalogue disproves five conjectures about these polyhedra stated in the monograph by Yemelichev et al. (1984). It also allowed us to discover some new results. For example, we prove that the number of vertices of an m×n transportation polytope is a multiple of the greatest common divisor of m and n. 相似文献
78.
Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115 degrees ) M2(mu-Cl2) cores with very closely spanned metal centers (less than 3 A) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd2(mu-Cl)2Cl2(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well. 相似文献
79.
80.
Siddiqua A Luo Y Meyer V Swanson MA Yu X Wei G Zheng J Eaton GR Ma B Nussinov R Eaton SS Margittai M 《Journal of the American Chemical Society》2012,134(24):10271-10278
Tau pathology in Alzheimer's disease is intimately linked to the deposition of proteinacious filaments, which akin to infectious prions, have been proposed to spread via seeded conversion. Here we use double electron-electron resonance (DEER) spectroscopy in combination with extensive computational analysis to show that filaments of three- (3R) and four-repeat (4R) tau are conformationally distinct. Distance measurements between spin labels in the third repeat, reveal tau amyloid filaments as ensembles of known β-strand-turn-β-strand U-turn motifs. Whereas filaments seeded with 3R tau are structurally homogeneous, filaments seeded with 4R tau are heterogeneous, composed of at least three distinct conformers. These findings establish a molecular basis for the seeding barrier between different tau isoforms and offer a new powerful approach for investigating the composition and dynamics of amyloid fibril ensembles. 相似文献