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141.
Harvey SD Mong GM Ozanich RM McLean JS Goodwin SM Valentine NB Fredrickson JK 《Analytical and bioanalytical chemistry》2006,386(2):211-219
A novel, affinity-augmented, bacterial spore-imprinted, bead material was synthesized, based on a procedure developed for
vegetative bacteria. The imprinted beads were intended as a front-end spore capture/concentration stage of an integrated biological
detection system. Our approach involved embedding bead surfaces with Bacillus thuringiensis kurstaki (Bt) spores (as a surrogate for Bacillus anthracis) during synthesis. Subsequent steps involved lithographic deactivation using a perfluoroether; spore removal to create imprint
sites; and coating imprints with the lectin, concanavalin A, to provide general affinity. The synthesis of the intended material
with the desired imprints was verified by scanning electron and confocal laser-scanning microscopy. The material was evaluated
using spore-binding assays with either Bt or Bacillus subtilis (Bs) spores. The binding assays indicated strong spore-binding capability and a robust imprinting effect that accounted for 25%
additional binding over non-imprinted controls. The binding assay results also indicated that further refinement of the surface
deactivation procedure would enhance the performance of the imprinted substrate. 相似文献
142.
Design and fabrication of a multilayered polymer microfluidic chip with nanofluidic interconnects via adhesive contact printing 总被引:1,自引:0,他引:1
Flachsbart BR Wong K Iannacone JM Abante EN Vlach RL Rauchfuss PA Bohn PW Sweedler JV Shannon MA 《Lab on a chip》2006,6(5):667-674
The design and fabrication of a multilayered polymer micro-nanofluidic chip is described that consists of poly(methylmethacrylate) (PMMA) layers that contain microfluidic channels separated in the vertical direction by polycarbonate (PC) membranes that incorporate an array of nanometre diameter cylindrical pores. The materials are optically transparent to allow inspection of the fluids within the channels in the near UV and visible spectrum. The design architecture enables nanofluidic interconnections to be placed in the vertical direction between microfluidic channels. Such an architecture allows microchannel separations within the chip, as well as allowing unique operations that utilize nanocapillary interconnects: the separation of analytes based on molecular size, channel isolation, enhanced mixing, and sample concentration. Device fabrication is made possible by a transfer process of labile membranes and the development of a contact printing method for a thermally curable epoxy based adhesive. This adhesive is shown to have bond strengths that prevent leakage and delamination and channel rupture tests exceed 6 atm (0.6 MPa) under applied pressure. Channels 100 microm in width and 20 microm in depth are contact printed without the adhesive entering the microchannel. The chip is characterized in terms of resistivity measurements along the microfluidic channels, electroosmotic flow (EOF) measurements at different pH values and laser-induced-fluorescence (LIF) detection of green-fluorescent protein (GFP) plugs injected across the nanocapillary membrane and into a microfluidic channel. The results indicate that the mixed polymer micro-nanofluidic multilayer chip has electrical characteristics needed for use in microanalytical systems. 相似文献
143.
Shannon Bishop Christopher Heil Yoo Young Koo Jae Kun Lim 《Linear algebra and its applications》2010,432(6):1501-1514
This paper determines the exact relationships that hold among the major Paley-Wiener perturbation theorems for frame sequences. It is shown that major properties of a frame sequence such as excess, deficit, and rank remain invariant under Paley-Wiener perturbations, but need not be preserved by compact perturbations. For localized frames, which are frames with additional structure, it is shown that the frame measure function is also preserved by Paley-Wiener perturbations. 相似文献
144.
Chang Ji Shannon E. Day William C. Silvers 《Journal of Electroanalytical Chemistry》2008,622(1):15-21
A dinickel Schiff base complex (Ni2(II)L) containing two salen units has been synthesized and characterized by NMR and mass spectrometry. The complex was used for the catalytic reduction of 1- and 2-bromooctanes and its electrochemical behavior, which is similar to that of nickel salen, was studied by cyclic voltammetry and controlled-potential electrolysis. Due to the proximity of the two nickel centers, the yield of octyl dimers is slightly higher for the electrochemical reduction of 2-bromooctane catalyzed by the dinickel complex than that by nickel salen. However, the yield of hexadecane does not increase for the catalytic reduction of 1-bromooctane, which can give more reactive primary radicals. In addition to the formation of various products, octylation of the dinickel complex takes place to a further extent for the reduction of 2-bromooctane than 1-bromooctane. Compared with nickel salen-catalyzed reduction, the electrochemical data also indicate that more octyl groups may incorporate into the dinickel complex. Mechanistically, the catalytic reduction of the bromooctanes involves the intermediacy of primary or secondary octyl radicals. 相似文献
145.
M. Bentaleb E. Lubkiewicz N. Schulz J. L. Durell F. Lidén C. J. Pearson W. R. Phillips J. Shannon B. J. Varley C. J. Lister I. Ahmad L. R. Morss K. L. Nash C. W. Williams 《Zeitschrift für Physik A Hadrons and Nuclei》1994,348(4):245-246
High-spin structures in the neutron-rich nuclei138Xe and139Xe have been investigated by observing prompt γ -rays from the spontaneous fission of248Cm with the Eurogam spectrometer. The partial level schemes were constructed on the basis of double-, triple- and quadruple-γ coincidences. The ground state band in138Xe has been extended up to 5 MeV excitation energy. The structure of the newly observed medium-spin states in139Xe is similar to the one of heavier N=85 isotones where vf 7 2/3 , vh9/2f 7 2/2 and vf 7 2/3 ? 3? multiplets have been observed. 相似文献
146.
[structure: see text] The total synthesis of the proposed structure for spirofungin B (2) is described. The data for the synthetic material did not compare with that for the natural product leading to the conclusion that the structure 2 assigned for spirofungin B is incorrect. Analysis of the NMR data reported for spirofungins A and B as well as related spiroketals allowed for the reassignment of the stereochemistry of spirofungin B to be that corresponding to 15-epi-spirofungin A (27). 相似文献
147.
Popp BV Thorman JL Morales CM Landis CR Stahl SS 《Journal of the American Chemical Society》2004,126(45):14832-14842
The mechanism of olefin substitution at palladium(0) has been studied, and the results provide unique insights into the fundamental reactivity of electron-rich late transition metals. A systematic series of bathocuproine-palladium(0) complexes bearing trans-beta-nitrostyrene ligands (ns(X) = X-C(6)H(4)CH=CHNO(2); X = OCH(3), CH(3), H, Br, CF(3)), (bc)Pd(0)ns(X) (3(X)), was prepared and characterized, and olefin-substitution reactions of these complexes were found to proceed by an associative mechanism. In cross-reactions between (bc)Pd(ns(CH)()3) and ns(X) (X = OCH(3), H, Br, CF(3)), more-electron-deficient olefins react more rapidly (relative rate: ns(CF)()3 > ns(Br) > ns(H) > ns(OCH)()3). Density functional theory calculations of model alkene-substitution reactions at a diimine-palladium(0) center reveal that the palladium center reacts as a nucleophile via attack of a metal-based lone pair on the empty pi orbital of the incoming olefin. This orbital picture contrasts that of traditional ligand-substitution reactions, in which the incoming ligand donates electron density into an acceptor orbital on the metal. On the basis of these results, olefin substitution at palladium(0) is classified as an "inverse-electron-demand" ligand-substitution reaction. 相似文献
148.
Santanu Roy Shobha Sharma Waruni V. Karunaratne Fei Wu Ruchi Gakhar Dmitry S. Maltsev Phillip Halstenberg Milinda Abeykoon Simerjeet K. Gill Yuanpeng Zhang Shannon M. Mahurin Sheng Dai Vyacheslav S. Bryantsev Claudio J. Margulis Alexander S. Ivanov 《Chemical science》2021,12(23):8026
Enhancing the solar energy storage and power delivery afforded by emerging molten salt-based technologies requires a fundamental understanding of the complex interplay between structure and dynamics of the ions in the high-temperature media. Here we report results from a comprehensive study integrating synchrotron X-ray scattering experiments, ab initio molecular dynamics simulations and rate theory concepts to investigate the behavior of dilute Cr3+ metal ions in a molten KCl–MgCl2 salt. Our analysis of experimental results assisted by a hybrid transition state-Marcus theory model reveals unexpected clustering of chromium species leading to the formation of persistent octahedral Cr–Cr dimers in the high-temperature low Cr3+ concentration melt. Furthermore, our integrated approach shows that dynamical processes in the molten salt system are primarily governed by the charge density of the constituent ions, with Cr3+ exhibiting the slowest short-time dynamics. These findings challenge several assumptions regarding specific ionic interactions and transport in molten salts, where aggregation of dilute species is not statistically expected, particularly at high temperature.Ion clustering of dilute chromium species was unexpectedly revealed in a high-temperature molten chloride salt, challenging several long-held assumptions regarding specific ionic interactions and transport in molten ionic media. 相似文献
149.
Michael J. Lacey Colin G. Macdonald James S. Shannon 《Journal of mass spectrometry : JMS》1978,13(4):188-191
Metal(I) hydrides are eliminated as neutral species in the electron impact ionization mass spectra of copper(II) and palladium(II) complexes of ethylene-N,N′-3-benzoylprop-2-en-2-amine. Deuterium labelling shows that the hydrogen atom of the metal(I) hydride is derived predominantly from the ethylene bridge both for ion source reactions and for metastable ion transitions. Evidence supporting the proposed rationalization for elimination of metal(I) hydride is provided by the observation of an analogous reaction in the mass spectrum of (ethylene-N,N′-salicylaldiminato)copper(II). The mass spectrum of ethylene-d4-N,N′-3-benzoylprop-2-en-2-amine shows an unusual rearrangement to give [C7H5D2]+ ions involving a formal phenyl-to-methylene transfer. 相似文献
150.
[reaction: see text] Lithium aminoborohydride (LAB) reagents promote the amination of 2-fluoropyridine under mild reaction conditions, providing 2-(dialkylamino)pyridines in excellent yield and purity. Treatment of 2-fluoropyridine with 1.1 equiv of lithium aminoborohydride at room temperature affords complete conversion after 1 h. This is the first general way by which 2-(dialkylamino)pyridines may be directly obtained from fluoropyridines under ambient reaction conditions. 2-Chloropyridine can also be converted to 2-(dialkylamino)pyridine by simply increasing the number of LAB equivalents and the reaction temperature. 相似文献