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111.
Zones SI Burton AW Lee GS Olmstead MM 《Journal of the American Chemical Society》2007,129(29):9066-9079
This study is a continuation of our efforts to understand the interplay in the self-assembly chemistry for formation of molecular sieves from guest organocations and inorganic silicon oxide. In this particular study we focus on the competitive interplay of the organocations and the synthesis cofactor fluoride anion. The anions play a key role in structure determination, as a function of net solution concentration. They compete with the role for the space-filling organocation in determining which molecular sieve host structure will be specified. In this study we look at this competition in the synthesis for a series of 33 different organocations derived from the piperidine ring system. Derivatives were prepared which both fixed substituents on the carbon and nitrogen centers on the ring. Results were discussed in terms of product selectivity from synthesis as a function of solution concentration for the reactants. A total of 17 different host topologies were found in this series, and a correlation was seen for (a) open-framework lattices (low framework densities) under the most concentrated reaction conditions and then (b) high framework density products once the conditions were more dilute. Some surprising synthesis differences are seen in comparing the performance of these structure directing agents (SDAs) in fluoride media vs hydroxide media (the more conventional environment for zeolite/molecular sieve syntheses involving silicate chemistry). Finally molecular modeling was used to understand some of the trends in product selectivity for closely related guest (SDA) candidates. 相似文献
112.
Hydrogen generation from weak acids: electrochemical and computational studies of a diiron hydrogenase mimic 总被引:1,自引:0,他引:1
Felton GA Vannucci AK Chen J Lockett LT Okumura N Petro BJ Zakai UI Evans DH Glass RS Lichtenberger DL 《Journal of the American Chemical Society》2007,129(41):12521-12530
Extended investigation of electrocatalytic generation of dihydrogen using [(mu-1,2-benzenedithiolato)][Fe(CO)3]2 has revealed that weak acids, such as acetic acid, can be used. The catalytic reduction producing dihydrogen occurs at approximately -2 V for several carboxylic acids and phenols resulting in overpotentials of only -0.44 to -0.71 V depending on the weak acid used. This unusual catalytic reduction occurs at a potential at which the starting material, in the absence of a proton source, does not show a reduction peak. The mechanism for this process and structures for the intermediates have been discerned by electrochemical and computational analysis. These studies reveal that the catalyst is the monoanion of the starting material and an ECEC mechanism occurs. 相似文献
113.
Pollock N Fowler G Twyman LJ McArthur SL 《Chemical communications (Cambridge, England)》2007,(24):2482-2484
This communication describes the synthesis and characterization of immobilized PAMAM dendrons onto a surface modified silicon wafer substrate (functionalized using plasma polymerized PAA) using a "growing from" strategy. 相似文献
114.
Sibert JW Forshee PB Hundt GR Sargent AL Bott SG Lynch V 《Inorganic chemistry》2007,46(25):10913-10925
Two series of isomeric, redox-responsive azacrown ethers based on ortho- and para-phenylenediamine (Wurster's crowns) have been synthesized and their properties explored through 13C NMR spectroscopy, electrospray ionization mass spectrometry, cyclic voltammetry, and X-ray crystallography. These crowns display strong affinity for alkali metal cations while maintaining comparable selectivity profiles to the parent crown ethers from which they are derived. Like Wurster's reagent (N,N,N',N'-tetramethyl-p-phenylenediamine or para-TMPD), the para-Wurster's crowns undergo two reversible one-electron oxidations. The integrity of the alkali metal ion complexes is maintained in the neutral and singly oxidized ligand states but not after removal of two electrons. In contrast, the oxidation of ortho-Wurster's crowns is scan rate dependent, occurring at potentials substantially higher than their para counterparts, with their complexes oxidizing irreversibly. X-ray crystal structures of representative complexes show, in all cases, participation of the redox-active phenylenediamine subunits in complex formation via direct bonding to the guest cation. 相似文献
115.
He J Yang R Zhou T Tsao R Young JC Zhu H Li XZ Boland GJ 《Journal of chromatography. A》2007,1151(1-2):187-192
Deoxynivalenol (DON) is a mycotoxin produced by several Fusarium species and is toxic to a wide range of organisms, including human beings and livestock. To produce large amounts of pure DON for research purposes, a novel method using high-speed counter-current chromatography (HSCCC) was developed. Rice cultured with Fusarium graminearum and field mouldy corn infected by F. graminearum were extracted with methanol and found to contain 1.16 and 1.30 mg DON/g, respectively. The extracts were concentrated and then separated using a biphasic solvent system consisting of ethyl acetate-water (1:1, v/v). Collected fractions were analyzed by high-performance liquid chromatography (HPLC) and identified by congruent retention time and UV/vis spectrum and mass spectrometric data. Fractions containing DON were combined and freeze-dried. This method produced 116 mg and 65 mg DON with a purity of greater than 94.9% from 200 g of the rice culture and the mouldy corn, respectively. The HSCCC method had a recovery rate of DON at 88% from the crude extracts of both samples. This one-step purification method provided a simple and effective tool for obtaining a large amount of DON, an essential material for studies related to toxicology and detoxification of this mycotoxin. 相似文献
116.
Urade VN Bollmann L Kowalski JD Tate MP Hillhouse HW 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4268-4278
The double-gyroid phase of nanoporous silica films has been shown to possess facile mass-transport properties and may be used as a mold to fabricate a variety of highly ordered inverse double-gyroid metal and semiconductor films. This phase exists only over a very small region of the binary phase diagram for most surfactants, and it has been very difficult to synthesize metal oxide films with this structure by evaporation-induced self-assembly (EISA). Here, we show the interplay of the key parameters needed to synthesize these structures reproducibly and show that the interfacial curvature may be systematically controlled. Grazing angle of incidence small-angle X-ray scattering (GISAXS) is used to determine the structure and orientation of nanostructured silica films formed by EISA from dilute silica/(poly(ethylene oxide)-b-poly(propylene oxide)-b-alkyl) surfactant solutions. Four different highly ordered film structures are observed by changing only the concentration of the surfactant, the relative humidity during dip-coating, and the aging time of the solution prior to coating. The highly ordered films progress from rhombohedral (Rm) to 2D rectangular (c2m) to double-gyroid (distorted Iad) to lamellar systematically as interfacial curvature decreases. Under all experimental conditions investigated, increasing the aging time of the coating solution was found to decrease the interfacial curvature. In particular, this parameter was critical to being able to synthesize highly ordered, pure-phase double-gyroid films. The key role of the aging time is shown via processing diagrams that map out the interplay between the aging time, composition, and relative humidity. 29Si nuclear magnetic resonance (NMR) spectroscopy and solution-phase small-angle X-ray scattering (SAXS) of the aged coating solutions presented in part I of this series are then used to interpret the effects of aging prior to dip-coating. Specifically, it was found that a predictive model based on volume fractions and the silica cluster stoichiometry obtained from 29Si NMR qualitatively explains the trends observed with composition and aging. However, apart from the effects of relative humidity, a quantitative comparison of the predicted phase with the experimental processing diagram suggests that less-condensed silica clusters are more effective at swelling the EO blocks at early aging times. This enhanced swelling decreases with aging time and results in lower-curvature nanostructures such as the double-gyroid. The decrease in swelling is attributed to the decreased thermodynamic driving force for the more-condensed silica clusters to mix with the EO block of the surfactant. 相似文献
117.
Anomaly detection in a mobile communication network 总被引:1,自引:0,他引:1
Alec Pawling Nitesh V. Chawla Greg Madey 《Computational & Mathematical Organization Theory》2007,13(4):407-422
Mobile communication networks produce massive amounts of data which may be useful in identifying the location of an emergency
situation and the area it affects. We propose a one pass clustering algorithm for quickly identifying anomalous data points.
We evaluate this algorithm’s ability to detect outliers in a data set and describe how such an algorithm may be used as a
component of an emergency response management system.
相似文献
Greg MadeyEmail: |
118.
Greg N Frederickson Roberto Solis-Oba 《Journal of Algorithms in Cognition, Informatics and Logic》1999,33(2):244
The problems of computing the maximum increase in the weight of the minimum spanning trees of a graph caused by the removal of a given number of edges, or by finite increases in the weights of the edges, are investigated. For the case of edge removals, the problem is shown to be NP-hard and an Ω(1/log k)-approximation algorithm is presented for it, where (input parameter) k > 1 is the number of edges to be removed. The second problem is studied, assuming that the increase in the weight of an edge has an associated cost proportional to the magnitude of the change. An O(n3m2 log(n2/m)) time algorithm is presented to solve it. 相似文献
119.
Xuezhong Jiang Greg Philan Brenden Carlson Sen Liu Larry Dalton Alex K-Y. Jen 《Macromolecular Symposia》2002,186(1):171-176
Pure and efficient red light-emitting diodes based on novel europium (Eu) and osmium (Os) complexes were demonstrated. The Eu complex, with dendron substituted diketone ligands, exhibits high photoluminescence efficiency of 45%. When a copolymer containing carbazole and 1,3,4-oxadiazole groups was used as the host, narrow electroluminescence at 617 nm was achieved, with a full width at half maximum of 4 nm and a maximum external quantum efficiency (η) of 0.80%. The Os complex shows pure red emission peaking at 650 nm. The Commission Internationale de l'Eclairage (CIE) chromaticity coordinates (x, y) are (0.65, 0.33). Maximum η and brightness achieved were 0.82% and 590 cd/m2, respectively. 相似文献
120.
Mark R. VanLandingham John S. Villarrubia William F. Guthrie Greg F. Meyers 《Macromolecular Symposia》2001,167(1):15-44
In this paper, the application of instrumented indentation devices to the measurement of the elastic modulus of polymeric materials is reviewed. This review includes a summary of traditional analyses of load‐penetration data and a discussion of associated uncertainties. Also, the use of scanning probe microscopes to measure the nanoscale mechanical response of polymers is discussed, particularly with regard to the associated limitations. The application of these methods to polymers often leads to measurements of elastic modulus that are somewhat high relative to bulk measurements with potentially artificial trends in modulus as a function of penetration depth. Also, power law fits to indentation unloading curves are often a poor representation of the actual data, and the power law exponents tend to fall outside the theoretical range. These problems are likely caused by viscoelasticity, the effects of which have only been studied recently. Advancement of nanoindentation testing toward quantitative characterization of polymer properties will require material‐independent calibration procedures, polymer reference materials, advances in instrumentation, and new testing and analysis procedures that account for viscoelastic and viscoplastic polymer behavior. 相似文献