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21.
We discuss recent observations of the heat capacity and magnetization of a fluid 3He monolayer adsorbed on graphite plated with a bilayer of HD. Approaching the density at which the monolayer solidifies into a
commensurate solid, we observe an apparent divergence of the effective mass. However, the inferred values of F0a tend to a constant. We interpret this in terms of a Mott–Hubbard transition between a 2D Fermi liquid and a magnetically disordered solid occurring via the Brinkman–Rice–Anderson–Vollhardt scenario. 相似文献
22.
23.
Glen Cowan Kyle Cranmer Eilam Gross Ofer Vitells 《The European Physical Journal C - Particles and Fields》2011,71(2):1554
We describe likelihood-based statistical tests for use in high energy physics for the discovery of new phenomena and for construction
of confidence intervals on model parameters. We focus on the properties of the test procedures that allow one to account for
systematic uncertainties. Explicit formulae for the asymptotic distributions of test statistics are derived using results
of Wilks and Wald. We motivate and justify the use of a representative data set, called the “Asimov data set”, which provides
a simple method to obtain the median experimental sensitivity of a search or measurement as well as fluctuations about this
expectation. 相似文献
24.
Richard Cowan 《Annals of the Institute of Statistical Mathematics》1987,39(1):103-111
Summary In this paper a new bivariate exponential distribution, arising naturally in the theory of Poisson line processes, is studied.
The distribution has some interesting and useful properties which renders it suitable for use in statistical modelling work.
It is presented in the spirit of adding to the repertoire of bivariate exponential forms. It joins other models, such as those
of Downton (1970,J. R. Statist. Soc., B,32, 408–417), Marshall and Olkin (1967,J. Appl. Prob.,4, 291–302) and Nagao and Kadoya (1971,Bulletin of the Disaster Prevention Research Institute,20, 3, 183–215), which have their origins in the theory of stochastic processes. 相似文献
25.
High Ethene/Ethane Selectivity in 2,2′‐Bipyridine‐Based Silver(I) Complexes by Removal of Coordinated Solvent
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Dr. Matthew G. Cowan William M. McDanel Prof. Hans H. Funke Dr. Yuki Kohno Prof. Douglas L. Gin Prof. Richard D. Noble 《Angewandte Chemie (International ed. in English)》2015,54(19):5740-5743
Following removal of coordinated CH3CN, the resulting complexes [AgI(2,2′‐bipyridine)][BF4] ( 1 ) and [AgI(6,6′‐dimethyl‐2,2′‐bipyridine)][OTf] ( 2 ) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g?1 when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2 , ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes. 相似文献
26.
Toward the Design of a Catalytic Metallodrug: Selective Cleavage of G‐Quadruplex Telomeric DNA by an Anticancer Copper–Acridine–ATCUN Complex
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Zhen Yu Menglu Han Dr. James A. Cowan 《Angewandte Chemie (International ed. in English)》2015,54(6):1901-1905
Telomeric DNA represents a novel target for the development of anticancer drugs. By application of a catalytic metallodrug strategy, a copper–acridine–ATCUN complex (CuGGHK‐Acr) has been designed that targets G‐quadruplex telomeric DNA. Both fluorescence solution assays and gel sequencing demonstrate the CuGGHK‐Acr catalyst to selectively bind and cleave the G‐quadruplex telomere sequence. The cleavage pathway has been mapped by matrix assisted laser desorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) experiments. CuGGHK‐Acr promotes significant inhibition of cancer cell proliferation and shortening of telomere length. Both senescence and apoptosis are induced in the breast cancer cell line MCF7. 相似文献
27.
Mark Forster Richard J. Potter Yichuan Ling Yi Yang David R. Klug Yat Li Alexander J. Cowan 《Chemical science》2015,6(7):4009-4016
Intrinsic doping of hematite through the inclusion of oxygen vacancies (VO) is being increasingly explored as a simple, low temperature route to preparing active water splitting α-Fe2O3–x photoelectrodes. Whilst it is widely accepted that the introduction of VO leads to improved conductivities, little else is verified regarding the actual mechanism of enhancement. Here we employ transient absorption (TA) spectroscopy to build a comprehensive kinetic model for water oxidation on α-Fe2O3–x. In contrast to previous suggestions, the primary effect of introducing VO is to block very slow (ms) surface hole – bulk electron recombination pathways. In light of our mechanistic research we are also able to identify and address a cause of the high photocurrent onset potential, a common issue with this class of electrodes. Atomic layer deposition (ALD) of Al2O3 is found to be particularly effective with α-Fe2O3–x, leading to the photocurrent onset potential shifting by ca. 200 mV. Significantly TA measurements on these ALD passivated electrodes also provide important insights into the role of passivating layers, that are relevant to the wider development of α-Fe2O3 photoelectrodes. 相似文献
28.
Tessellations of that use convex polyhedral cells to fill the space can be extremely complicated, especially if they are not “facet‐to‐facet”, that is, if the facets of a cell do not necessarily coincide with the facets of that cell's neighbours. In a recent paper 15 , we have developed a theory which covers these complicated cases, at least with respect to their combinatorial topology. The theory required seven parameters, three of which suffice for facet‐to‐facet cases; the remaining four parameters are needed for the awkward adjacency concepts that arise in the general case. This current paper establishes constraints that apply to these seven parameters and so defines a permissible region within their seven‐dimensional space, a region which we discover is not bounded. Our constraints in the relatively simple facet‐to‐facet case are also new. 相似文献
29.
A library of complexes that included iron, cobalt, nickel, and copper chelates of cyclam, cyclen, DOTA, DTPA, EDTA, tripeptide GGH, tetrapeptide KGHK, NTA, and TACN was evaluated for DNA nuclease activity, ascorbate consumption, superoxide and hydroxyl radical generation, and reduction potential under physiologically relevant conditions. Plasmid DNA cleavage rates demonstrated by combinations of each complex and biological co-reactants were quantified by gel electrophoresis, yielding second-order rate constants for DNA(supercoiled) to DNA(nicked) conversion up to 2.5 × 10(6) M(-1) min(-1), and for DNA(nicked) to DNA(linear) up to 7 × 10(5) M(-1) min(-1). Relative rates of radical generation and characterization of radical species were determined by reaction with the fluorescent radical probes TEMPO-9-AC and rhodamine B. Ascorbate turnover rate constants ranging from 3 × 10(-4) to 0.13 min(-1) were determined, although many complexes demonstrated no measurable activity. Inhibition and Freifelder-Trumbo analysis of DNA cleavage supported concerted cleavage of dsDNA by a metal-associated reactive oxygen species (ROS) in the case of Cu(2+)(aq), Cu-KGHK, Co-KGHK, and Cu-NTA and stepwise cleavage for Fe(2+)(aq), Cu-cyclam, Cu-cyclen, Co-cyclen, Cu-EDTA, Ni-EDTA, Co-EDTA, Cu-GGH, and Co-NTA. Reduction potentials varied over the range from -362 to +1111 mV versus NHE, and complexes demonstrated optimal catalytic activity in the range of the physiological redox co-reactants ascorbate and peroxide (-66 to +380 mV). 相似文献
30.
Aminoglycosides are a family of molecules based on a 2-deoxystreptamine ring that is functionalized with a variety of sugar units that contain vicinal amine and hydroxyl functionality. These positively-charged amines promote selective high affinity binding to bacterial 16 s rRNA with resultant antibacterial activity. Aminoglycosides have also been shown to selectively target a variety of therapeutically relevant RNA motifs, and in combination with copper to promote irreversible degradation of the RNA target. The presence of multiple hydroxyl and amine groups on multiple rings creates many potential copper coordination sites. However, only a small subset of these sites actually bind copper, which have not been clearly defined experimentally, Herein we describe a more extensive structural characterization of the complexes of six aminoglycosides (kanamycin A, kanamycin B, neomycin B, neamine, tobramycin and paromomycin) that provide insights on the factors contributing to the coordination selectivity of aminoglycosides toward divalent copper. The presence of vicinal ligand donors capable of chelating the copper ion appears to be a prerequisite for stable metal binding, with charge density providing further tuning of the K(D). A possible role for metal coordination in antibacterial activity is also considered. 相似文献