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排序方式: 共有259条查询结果,搜索用时 31 毫秒
51.
Zhang TG Zhao Y Song K Asselberghs I Persoons A Clays K Therien MJ 《Inorganic chemistry》2006,45(24):9703-9712
A series of conjugated (porphinato)zinc(II)-based chromophores structurally related to [5-(4-dimethylaminophenylethynyl)-15-(5-nitrothienyl-2-ethynyl)-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)]zinc(II) were synthesized using metal-catalyzed cross-coupling reactions involving [5-bromo-15-triisopropylsilylethynyl-10,20-diarylporphinato]zinc(II), [5-bromo-15-(4-dimethylaminophenylethynyl)-10,20-diarylporphinato]zinc(II), [5-(4-dimethylaminophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II), and [5-(4-nitrophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II), along with appropriately functionalized aryl, thienyl (or thiophenyl), thiazolyl, benzothiazolyl, and carbazolyl precursors. The linear and nonlinear optical properties of these asymmetrically 5,15-substitued-(10,20-diarylporphinato)zinc(II) chromophores that bear either 2-(9H-carbazol-9-yl)-thiophen-5-yl-ethynyl, 4-dimethylaminophenylethynyl, or 2-(N,N-diphenylamino)thiophen-5-yl-ethynyl electron-releasing groups and an electron-withdrawing group selected from 2-formyl-thiophen-5-yl-ethynyl, 2-(2,2-dicyanovinyl)-thiophen-5-yl-ethynyl, 4-nitrophenylethynyl, 6-nitrobenzothiazol-2-yl-ethynyl, or 5-nitrothiazol-2-yl-ethynyl are reported. The dynamic hyperpolarizabilities of these compounds were determined from hyper-Rayleigh light scattering measurements carried out at a fundamental incident irradiation wavelength (lambda(inc)) of 1300 nm; these measured beta1300 values ranged from 690 --> 1400 x 10(-30) esu. These data (i) show that these neutral dipolar molecules express substantial beta1300 values, (ii) highlight that reductions in the magnitude of the aromatic stabilization energy of (porphinato)metal-pendant arylethynyl groups have a significant impact upon the magnitude of the molecular hyperpolarizability, and (iii) provide insights into advantageous design modifications for closely related structures having potential utility in long-wavelength electrooptic applications. 相似文献
52.
Sinkeldam RW Hoeben FJ Pouderoijen MJ De Cat I Zhang J Furukawa S De Feyter S Vekemans JA Meijer EW 《Journal of the American Chemical Society》2006,128(50):16113-16121
The ability of foldamers to adopt a secondary structure in solution has been exploited to organize peripheral functionality. Our previously reported poly(ureidophthalimide) foldamer proved to be an excellent scaffold for the chiral organization of peripherally positioned oligo(p-phenylenevinylene) (OPV) chromophores. Facile high-yielding synthesis gave access to the required OPV-decorated building blocks. A condensation polymerization provided polymers of sufficient length to allow construction of a helical architecture comprising several turns. Short and long chains were separated by chromatography. Circular dichroism studies in THF of the longer chains indicate the presence of helically arranged OPVs. However, such an effect is not observed in CHCl3. Remarkable are the measurements of the OPV foldamers in heptane. A bisignate Cotton effect is observed in heptane of a sample with a THF history. No Cotton effect is observed in heptane of a sample with a CHCl3 history. In this example of supramolecular synthesis, the solvent dictates the expression of supramolecular chirality in a secondary structure. The short-chain oligomeric fractions that are unable to create a full turn revealed on scanning tunneling microscopy analysis the presence of circular architectures at the graphite/1-phenyloctane interface. This is in full agreement with the proposed conformation of the decorated foldamers. 相似文献
53.
The phase-field method has already proven its usefulness to simulate microstructural evolution for several applications, e.g., during solidification, solid-state phase transformations, fracture, etc. This wide variety of applications follows from its diffuse-interface approach. Moreover, it is straightforward to take different driving forces into account. The purpose of this paper is to give an introduction to the phase-field modelling technique with particular attention for models describing phenomena important in extractive metallurgy. The concept of diffuse interfaces, the phase-field variables, the thermodynamic driving force for microstructure evolution and the phase-field equations are discussed. Some of the possibilities to solve the equations describing microstructural evolution are also described, followed by possibilities to make the phase-field models quantitative and the phase-field modelling of the microstructural phenomena important in extractive metallurgy, i.e., multiphase field models. Finally, this paper illustrates how the phase-field method can be applied to simulate several processes taking place in extractive metallurgy and how the models can contribute to the further development or improvement of these processes. 相似文献
54.
JV Georgieva RP Brinkhuis K Stojanov CA Weijers H Zuilhof FP Rutjes D Hoekstra JC van Hest IS Zuhorn 《Angewandte Chemie (International ed. in English)》2012,51(33):8339-8342
A polymeric nanocarrier: Polymersomes tagged with a dodecamer peptide that recognizes gangliosides GM1 and GT1b are shown to cross the blood-brain barrier, both in an in?vitro model and in?vivo. The combination of polymeric vesicles with a small GM1-binding peptide and GM1/GT1b gangliosides as targeting sites for blood-brain barrier transport is unprecedented. 相似文献
55.
We consider a subproblem in parameter estimation using the Gauss-Newton algorithm with regularization for NURBS curve fitting. The NURBS curve is fitted to a set of data points in least-squares sense, where the sum of squared orthogonal distances is minimized. Control-points and weights are estimated. The knot-vector and the degree of the NURBS curve are kept constant. In the Gauss-Newton algorithm, a search direction is obtained from a linear overdetermined system with a Jacobian and a residual vector. Because of the properties of our problem, the Jacobian has a particular sparse structure which is suitable for performing a splitting of variables. We are handling the computational problems and report the obtained accuracy using different methods, and the elapsed real computational time. The splitting of variables is a two times faster method than using plain normal equations. 相似文献
56.
57.
Inge Cosemans Jimmy Wouters Thomas Cleij Laurence Lutsen Wouter Maes Thomas Junkers Dirk Vanderzande 《Macromolecular rapid communications》2012,33(3):242-247
The anionic polymerization of PPV via the sulfinyl precursor route is further investigated. When LHMDS is employed as the base to form the actively propagating quinodimethane system and THF as the solvent, anionic polymerizations can be observed. With the use of tert‐ butyl‐substituted anionic initiators, specific functional groups can be built in the polymer chain and the chain length can be efficiently controlled, which is demonstrated here for the first time. With introduction of branched side chains on the aromatic core, soluble conjugated PPV material can be obtained with molecular weights in the range of 5000–16 000 g mol−1. 相似文献
58.
Bent Natvig J?rund Inge G?semyr Trond Reitan 《Methodology and Computing in Applied Probability》2012,14(4):1075-1095
In the present paper we consider a multistate monotone system of multistate components. Following a Bayesian approach, the ambition is to arrive at the posterior distributions of the system availabilities and unavailabilities to the various levels in a fixed time interval based on both prior information and data on both the components and the system. We argue that a realistic approach is to start out by describing our uncertainty on the component availabilities and unavailabilities to the various levels in a fixed time interval, based on both prior information and data on the components, by the moments up till order m of their marginal distributions. From these moments analytic bounds on the corresponding moments of the system availabilities and unavailabilities to the various levels in a fixed time interval are arrived at. Applying these bounds and prior system information we may then fit prior distributions of the system availabilities and unavailabilities to the various levels in a fixed time interval. These can in turn be updated by relevant data on the system. This generalizes results given in Natvig and Eide (Scand J Statist 14:319?C327, 1987) considering a binary monotone system of binary components at a fixed point of time. Furthermore, considering a simple network system, we show that the analytic bounds can be slightly improved by straightforward simulation techniques. 相似文献
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