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61.
Beitone L Marrot J Loiseau T Férey G Henry M Huguenard C Gansmuller A Taulelle F 《Journal of the American Chemical Society》2003,125(7):1912-1922
A new fluorinated gallium phosphate, MIL-50, has been synthesized under mild hydrothermal conditions using 1,6-diaminohexane. The chemical formula of MIL-50 is Rb(2)Ga(9)(PO(4))(8)(HPO(4))(OH)F(6).2N(2)C(6)H(18).7H(2)O. The structure is a network of hexameric units of Ga(3)(PO(4))(3)F(2) and Ga(3)(PO(4))(2)(HPO(4))F(3) via corner sharing. It creates a three-dimensional open-framework delimiting 6- and 18-ring channels running along the c axis. The diprotonated 1,6-diaminohexane and water molecules are trapped within the 18-ring pores, whereas the rubidium cations reside in the 6-ring ones. A double quantum (31)P NMR experiment and partial charge calculations indicate that water molecules are present under the form of periodic small clusters, lowering the multiplicity of one phosphorus site, P3. Though water hops within the clusters, the motion leaves the water pattern periodic. Rubidium is so tightly embedded into the framework that water moving in the large 18-ring channels does not reach it, leaving it therefore dry. The crystal framework may be ascribed to the orthorhombic space group Cmc2(1) (n degrees 36), a = 32.1510(2), b = 17.2290(3), c = 10.2120(1) A. The periodic water pattern has a different symmetry than that of the framework. A method has been devised to superpose the two sublattices that coexist in the same unit cell in order to have full occupancy of each site and to perform Madelung summations. This original method is of general interest for most zeolitic materials exhibiting a different symmetry for the framework and the template sublattices. 相似文献
62.
Volker Strauss Huize Wang Simon Delacroix Marc Ledendecker Pablo Wessig 《Chemical science》2020,11(31):8256
Luminescent compounds obtained from the thermal reaction of citric acid and urea have been studied and utilized in different applications in the past few years. The identified reaction products range from carbon nitrides over graphitic carbon to distinct molecular fluorophores. On the other hand, the solid, non-fluorescent reaction product produced at higher temperatures has been found to be a valuable precursor for the CO2-laser-assisted carbonization reaction in carbon laser-patterning. This work addresses the question of structural identification of both, the fluorescent and non-fluorescent reaction products obtained in the thermal reaction of citric acid and urea. The reaction products produced during autoclave–microwave reactions in the melt were thoroughly investigated as a function of the reaction temperature and the reaction products were subsequently separated by a series of solvent extractions and column chromatography. The evolution of a green molecular fluorophore, namely HPPT, was confirmed and a full characterization study on its structure and photophysical properties was conducted. The additional blue fluorescence is attributed to oligomeric ureas, which was confirmed by complementary optical and structural characterization. These two components form strong hydrogen-bond networks which eventually react to form solid, semi-crystalline particles with a size of ∼7 nm and an elemental composition of 46% C, 22% N, and 29% O. The structural features and properties of all three main components were investigated in a comprehensive characterization study.Products of the thermal reaction of citric acid and urea have been identified as a complex mixture of fluorophores and particles. 相似文献
63.
We study methods for reducing chemical master equations using the Michaelis-Menten mechanism as an example. The master equation consists of a set of linear ordinary differential equations whose variables are probabilities that the realizable states exist. For a master equation with s(0) initial substrate molecules and e(0) initial enzyme molecules, the manifold can be parametrized by s(0) of the probability variables. Fraser's functional iteration method is found to be difficult to use for master equations of high dimension. Building on the insights gained from Fraser's method, techniques are developed to produce s(0)-dimensional manifolds of larger systems directly from the eigenvectors. We also develop a simple, but surprisingly effective way to generate initial conditions for the reduced models. 相似文献
64.
Grotjahn DB Van S Combs D Lev DA Schneider C Incarvito CD Lam KC Rossi G Rheingold AL Rideout M Meyer C Hernandez G Mejorado L 《Inorganic chemistry》2003,42(10):3347-3355
Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions. 相似文献
65.
Marc Soret 《Annals of Global Analysis and Geometry》1995,13(2):101-116
The main result of this paper is the following maximum principle at infinity:Theorem.Let M
1
and M
2
be two disjoint properly embedded complete minimal surfaces with nonempty boundaries, that are stable in a complete flat 3-manifold. Then dist(M
1,M
2)=min(dist(M
1,M
2), dist(M
2,M
1)).In case one boundary is empty, e.g. M
1,then dist(M
1,M
2)=dist(M
2,M
1).If both boundaries are empty, then M
1
and M
2
are flat. 相似文献
66.
For classical polynomials orthogonal with respect to a positive measure supported on the real line, the moment matrix is Hankel and positive definite. The polynomials satisfy a three term recurrence relation. When the measure is supported on the complex unit circle, the moment matrix is positive definite and Toeplitz. Then they satisfy a coupled Szeg recurrence relation but also a three term recurrence relation. In this paper we study the generalization for formal polynomials orthogonal with respect to an arbitrary moment matrix and consider arbitrary Hankel and Toeplitz matrices as special cases. The relation with Padé approximation and with Krylov subspace iterative methods is also outlined.This research was supported by the National Fund for Scientific Research (NFWO), project Lanczos, grant #2.0042.93. 相似文献
67.
Marc Jumelet 《Archive for Mathematical Logic》1995,34(3):197-209
It is demonstrated that we can represent Euler's -function by means of a 0-formula in such a way that the theory I
0 proves the recursion equations that are characteristic for this function. 相似文献
68.
Marc A. Rieffel 《Communications in Mathematical Physics》1995,171(1):181-201
LetG be a Lie group. For any Abelian subalgebra
of the Lie algebra g ofG, and any
, the difference of the left and right translates ofr gives a compatible Poisson bracket onG. We show how to construct the corresponding quantum group, in theC
*-algebra setting. The main tool used is the general deformation quantization construction developed earlier by the author for actions of vector groups onC
*-algebras.The research reported on here was supported in part by National Science Foundation grant DMS-9303386. 相似文献
69.
A time-parallel simulation obtains parallelism by partitioning the time domain of the simulation. An approximate time-parallel simulation algorithm named GG1K is developed for acyclic networks of loss FCFSG/G/1/K queues. The GG1K algorithm requires two phases. In the first phase, a similar system (i.e. aG/G/1/ queue) is simulated using the GLM algorithm. Then the resultant trajectory is transformed into an approximateG/G/1/K trajectory in the second phase. The closeness of the approximation is investigated theoretically and experimentally. Our results show that the approximation is highly accurate except whenK is very small (e.g. 5) in certain models. The algorithm exploits unbounded parallelism and can achieve near-linear speedup when the number of arrivals simulated is sufficiently large. 相似文献
70.
Uulke A. van der Heide Marc A. M. J. Zandvoort Ernst van Faassen Gijs van Ginkel Yehudi K. Levine 《Journal of fluorescence》1993,3(4):271-279
Measurements of fluorescence depolarization decays are widely used to obtain information about the molecular order and rotational dynamics of fluorescent probe molecules in membrane systems. This information is obtained by least-squares fits of the experimental data to the predictions of physical models for motion. Here we present a critical review of the ways and means of the data analysis and address the question how and why totally different models such as Brownian rotational diffusion and wobble-in-cone provide such convincing fits to the fluorescence anistropy decay curves. We show that while these models are useful for investigating the general trends in the behavior of the probe molecules, they fail to describe the underlying motional processes. We propose to remedy this situation with a model in which the probe molecules undergo fast, though restricted local motions within a slowly rotating cage in the lipid bilayer structure. The cage may be envisaged as a free volume cavity between the lipid molecules, so that its position and orientation change with the internal conformational motions of the lipid chains. This approach may be considered to be a synthesis of the wobble-in-cone and Brownian rotational diffusion models. Importantly, this compound motion model appears to provide a consistent picture of fluorescent probe behavior in both oriented lipid bilayers and lipid vesicle systems. 相似文献