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951.
Tauchert ME Incarvito CD Rheingold AL Bergman RG Ellman JA 《Journal of the American Chemical Society》2012,134(3):1482-1485
Rh(III)-catalyzed arylation of imines provides a new method for C-C bond formation while simultaneously introducing an α-branched amine as a functional group. This detailed mechanistic study provides insights for the rational future development of this new reaction. Relevant intermediate Rh(III) complexes have been isolated and characterized, and their reactivities in stoichiometric reactions with relevant substrates have been monitored. The reaction was found to be first order in the catalyst resting state and inverse first order in the C-H activation substrate. 相似文献
952.
Emory JM Peng Z Young B Hupert ML Rousselet A Patterson D Ellison B Soper SA 《The Analyst》2012,137(1):87-97
Single-molecule detection (SMD) has demonstrated some attractive benefits for many types of biomolecular analyses including enhanced processing speed by eliminating processing steps, elimination of ensemble averaging and single-molecule sensitivity. However, it's wide spread use has been hampered by the complex instrumentation required for its implementation when using fluorescence as the readout modality. We report herein a simple and compact fluorescence single-molecule instrument that is straightforward to operate and consisted of fiber optics directly coupled to a microfluidic device. The integrated fiber optics served as waveguides to deliver the laser excitation light to the sample and collecting the resulting emission, simplifying the optical requirements associated with traditional SMD instruments by eliminating the need for optical alignment and simplification of the optical train. Additionally, the use of a vertical cavity surface emitting laser and a single photon avalanche diode serving as the excitation source and photon transducer, respectively, as well as a field programmable gate array (FPGA) integrated into the processing electronics assisted in reducing the instrument footprint. This small footprint SMD platform was tested using fluorescent microspheres and single AlexaFluor 660 molecules to determine the optimal operating parameters and system performance. As a demonstration of the utility of this instrument for biomolecular analyses, molecular beacons (MBs) were designed to probe bacterial cells for the gene encoding Gram-positive species. The ability to monitor biomarkers using this simple and portable instrument will have a number of important applications, such as strain-specific detection of pathogenic bacteria or the molecular diagnosis of diseases requiring rapid turn-around-times directly at the point-of-use. 相似文献
953.
This paper presents rigorous filtering methods for continuous constraint satisfaction problems based on linear relaxations, designed to efficiently handle the linear inequalities coming from a linear relaxation of quadratic constraints. Filtering or pruning stands for reducing the search space of constraint satisfaction problems. Discussed are old and new approaches for rigorously enclosing the solution set of linear systems of inequalities, as well as different methods for computing linear relaxations. This allows custom combinations of relaxation and filtering. Care is taken to ensure that all methods correctly account for rounding errors in the computations. The methods are implemented in the GloptLab environment for solving quadratic constraint satisfaction problems. Demonstrative examples and tests comparing the different linear relaxation methods are also presented. 相似文献
954.
Although the pyramidal inversion barriers in diphosphines (R(2)P-PR(2)) are similar to those in phosphines (PR(3)), P-stereogenic chiral diphosphines have rarely been exploited as building blocks in asymmetric synthesis. The synthesis, reactivity, and resolution of the benzodiphosphetane trans-1,2-(P(t-Bu))(2)C(6)H(4) are reported. Alkylation with MeOTf followed by addition of a nucleophile gave the useful C(2)-symmetric P-stereogenic ligand BenzP* and novel analogues. 相似文献
955.
956.
Armin Feldhoff Julia Martynczuk Mirko Arnold Maxym Myndyk Ingo Bergmann Vladimir epelk Wolfgang Gruner Ulrich Vogt Angelika Hhnel Jrg Woltersdorf 《Journal of solid state chemistry》2009,182(11):2961-2971
The redox behavior of iron during heating of a high-performance perovskite for ceramic oxygen separation membranes was studied by combined electron energy-loss (EELS, esp. ELNES) and Mössbauer spectroscopical in situ methods. At room temperature, the iron in (Ba0.5Sr0.5)(Fe0.8Zn0.2)O3-δ (BSFZ) is in a mixed valence state of 75% Fe4+ in the high-spin state and 25% Fe3+ predominantly in the low-spin state. When heated to , a slight reduction of iron is observed that increases the quantity of Fe3+ species. However, the dominant occurrence is a gradual transition in the spin-state of trivalent iron from a mixed low-spin/high-spin to a pure high-spin configuration. In addition, a remarkable amount of hybridization is found in the Fe–O bonds that are highly polar rather than purely ionic. The coupled valence/spin-state transition correlates with anomalies in thermogravimetry and thermal expansion behavior observed by X-ray diffraction and dilatometry, respectively. Since the effective cationic radii depend not only on the valence but also on the spin-state, both have to be considered when estimating under which conditions a cubic perovskite will tolerate specific cations. It is concluded that an excellent phase stability of perovskite-based membrane materials demands a tailoring, which enables pure high-spin states under operational conditions, even if mixed valence states are present. The low spin-state transition temperature of BSFZ provides that all iron species are in a pure high-spin configuration already above ca. making this ceramic highly attractive for intermediate temperature applications (). 相似文献
957.
Jean-François Arnold Nicolas Langlois Houcine Chafouk 《European Journal of Operational Research》2009
In this paper a fuzzy controller is proposed to regulate the intake manifold pressure and the fresh mass airflow of diesel engines simultaneously. The instrumentation set usually embedded in a mass-produced passenger car has been considered. Unlike many multi-variable controllers, the proposed structure requires neither an internal model nor identification algorithms. In comparison to controllers embedded at present in standard engine control units (ECUs), it improves the trajectory tracking of desired outputs during simulation of EURO cycles. Because of its performance, the fuzzy controller has been implemented in an electronics control unit. Some real-time results are presented. 相似文献
958.
Daniel Mendoza-Espinosa Bernat A. Martinez-Ortega Mauricio Quiroz-Guzman James A. Golen Arnold L. Rheingold Tracy A. Hanna 《Journal of organometallic chemistry》2009,694(9-10):1509-1523
The synthesis, complete characterization, and solid state conformation of a new series of p-tert-butylcalix[5]arene (ButC5) mono-, di-, tri- and pentaanions are reported. X-ray structures of the alkali metal salts illustrate the strong influence of the alkali metal ion on the structure of the calixanion. The strength of the alkali metal base and its reaction stoichiometry play an important role in the conformation and level of deprotonation of the resulting anion. Reaction of ButC5 in a 2:1 molar ratio with alkali metal bases M2CO3 (M = Rb, Cs), or in a 1:1 ratio with M2CO3 (M = Na, K), MOH (M = Na, K, Rb, Cs) or MH (M = Li, Na) produces ButC5 monoanions, but ButC5 reacts in a 1:1 molar ratio with M2CO3 (M = Rb, Cs) or a 1:2 molar ratio with MOC(CH3)3 (M = Na, K) to afford ButC5 dianions. Due to the steric bulkiness of the But group no polymeric structures are observed. Alkali metal salts of trianionic ButC5 were obtained in high yields from reactions of ButC5 with MOC(CH3)3 (M = Li, Na, K), BunLi, LiH and LiOH in a 1:3 molar ratio. Pentaanionic ButC5 salts were obtained by the reaction with MOC(CH3)3 (M = Li, Na, K) or BunLi in a 5:1 ratio. X-ray crystal structures of ButC5 · Na and ButC5 · Cs indicate that the size of the alkali metal influences the level of cation-π arene interactions and therefore the conformation of the ButC5 unit; for example, ButC5 · Na has a cone conformation while ButC5 · Cs shows a flattened cone conformation. Cation-π arene interactions are observed in most of the calixarene salts. 相似文献
959.
Mitchell R. Malachowski Ashraf S. Kasto Mark E. Adams Arnold L. Rheingold Lev N. Zakharov Lawrence D. Margerum Matthew Greaney 《Polyhedron》2009
The novel pyrazole-containing tetradentate ligand 2,2′-bis[[(3,5-dimethylpyrazol-1-yl)methyl]amino]-1,1′-biphenyl (N4-mpz), 1, was synthesized and three Cu(II) complexes, 2–4, were prepared from this compound. These complexes were characterized by a combination of elemental analysis, FAB-MS and electrochemistry and were shown to have the structure of [Cu(N4-mpz)(Pz)]X2 where X = BF4 or ClO4 or [Cu(N4-mpz)(Cl)]Cl. The X-ray structure of [Cu(N4-mpz)(Pz)] (ClO4)2 · CH3OH, 2, was determined and it showed the Cu(II) coordinated by the four nitrogen donors from the ligand along with an exogenous pyrazole donor that had been extracted from another molecule of the ligand. Cyclic voltammetry studies indicated that the complexes undergo quasi-reversible one-electron reductions in acetonitrile at potentials between 396 and 422 mV versus Ag/AgCl. 相似文献
960.
Vladimir I. Arnold 《Functional Analysis and Other Mathematics》2009,2(2-4):139-149
Kolmogorov discovered in 1933 that the empirical statistics of several independent values of any random variable differs from the true distribution function of this variable in some universal way: the random distribution of the distance of one of these statistics from the other verifies (asymptotically) some stochastic distribution law (called later “Kolmogorov’s distribution”). The present paper compares the Kolmogorov’s distribution with a similar object, provided by the chain of observations of a nonrandom, deterministic dynamical system, formed by the consecutive members of a geometrical progression. Say, the Kolmogorov’s distribution is observed for the distribution of the last pairs of digits of the powers of integer 3, that is, for the sequence 01,03,09,27,81,43,29,87,… (which is not random at all and does not verify the Kolmogorov’s theorem conditions). 相似文献