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81.
Qiang Xiao Aliou Sow Brian M. Maxwell Matei I. Radulescu 《Proceedings of the Combustion Institute》2021,38(3):3641-3649
We evaluate the effect of boundary layer losses on two-dimensional H2/O2/Ar cellular detonations obtained in narrow channels. The experiments provide the details of the cellular structure and the detonation speed deficits from the ideal CJ speed. We model the effect of the boundary layer losses by incorporating the flow divergence in the third dimension due to the negative boundary layer displacement thickness, modeled using Mirels’ theory. The cellular structures obtained numerically with the resulting quasi-2D formulation of the reactive Euler equations with two-step chain-branching chemistry are found in excellent agreement with experiment, both in terms of cell dynamics and velocity deficits, provided the boundary layer constant of Mirels is modified by a factor of 2. A significant increase in the cell size is found with increasing velocity deficit. This is found to be very well captured by the induction zone increase in slower detonations due to the lower temperatures in the induction zone. 相似文献
82.
Surfactant-induced wetting of hydrophobic nanopores is investigated. SDS micelles interact with the C18 layer on the nanopore walls with their hydrophobic tails, creating a charged wall lining with their head groups and inducing a breakthrough of the aqueous solution to wet the pores. The surface coverage of the surfactant molecules is evaluated electrophoretically. A surprising discovery is that pore wetting is achieved with 0.73 μmol/m(2) coverage of SDS surfactant, corresponding to only 18% of a monolayer on the walls of the nanopores. Clearly, the surfactant molecules cannot organize as a compact uninterrupted monolayer. Instead, formation of hemimicelles is thermodynamically favored. Modeling shows that, to be consistent with the experimental observations, the aggregation number of hemimicelles is lower than 25 and the size of hemimicelle is limited to a maximum radius of 11.7 ?. The hydrophobic tails of SDS thus penetrate into and intercalate with the C18 layer. The insight gained in the C18-surfactant interactions is essential in the surfactant-induced solubilization of hydrophobic nanoporous particles. The results have bearing on the understanding of the nature of hydrophobic interactions. 相似文献
83.
Wu C Schneider T Zeigler M Yu J Schiro PG Burnham DR McNeill JD Chiu DT 《Journal of the American Chemical Society》2010,132(43):15410-15417
Semiconducting polymer dots (Pdots) represent a new class of ultrabright fluorescent probes for biological imaging. They exhibit several important characteristics for experimentally demanding in vitro and in vivo fluorescence studies, such as their high brightness, fast emission rate, excellent photostability, nonblinking, and nontoxic feature. However, controlling the surface chemistry and bioconjugation of Pdots has been a challenging problem that prevented their widespread applications in biological studies. Here, we report a facile yet powerful conjugation method that overcomes this challenge. Our strategy for Pdot functionalization is based on entrapping heterogeneous polymer chains into a single dot, driven by hydrophobic interactions during nanoparticle formation. A small amount of amphiphilic polymer bearing functional groups is co-condensed with the majority of semiconducting polymers to modify and functionalize the nanoparticle surface for subsequent covalent conjugation to biomolecules, such as streptavidin and immunoglobulin G (IgG). The Pdot bioconjugates can effectively and specifically label cellular targets, such as cell surface marker in human breast cancer cells, without any detectable nonspecific binding. Single-particle imaging, cellular imaging, and flow cytometry experiments indicate a much higher fluorescence brightness of Pdots compared to those of Alexa dye and quantum dot probes. The successful bioconjugation of these ultrabright nanoparticles presents a novel opportunity to apply versatile semiconducting polymers to various fluorescence measurements in modern biology and biomedicine. 相似文献
84.
85.
Andrew C. Benniston Dr. Graeme Copley Dr. Helge Lemmetyinen Dr. Nikolai V. Tkachenko Dr. 《Chemphyschem》2010,11(8):1685-1692
Two series of geometrically‐related dyads are discussed based on the difluoroborondipyrromethene (Bodipy) unit, and incorporating covalently attached hydroquinone/quinone groups. These units are anchored directly, or via a phenylene spacer, to the Bodipy core at the meso position in one series ( BD‐MHQ , BD‐MQ , BD‐MPHQ , BD‐MPQ ), but for the second series the attachment site is the 2‐position ( BD‐SHQ , BD‐SQ , BD‐SPHQ , BD‐SPQ ). The compounds show various levels of fluorescence depending on the oxidation state of the appended group and the substitution pattern. In non‐polar solvents such as toluene, diethyl ether and dichlorobenzene, the S1 state deactivation of the Bodipy unit in BD‐SPQ and BD‐MPQ is dominated by 1, 3exciplex formation, which has not been reported for Bodipy derivatives so far. In the latter molecule, the decay of the exciplex is divided between population of the Bodipy triplet state (13 %–21 %) and ground state reformation. This partitioning is not seen for the side‐on substituted derivative, BD‐SPQ , and only ground state reformation is observed following decay of the exciplex. This difference in behavior is explained by the radical‐pair inter‐system‐crossing mechanism, which more effectively operates in BD‐MPQ because of the orthogonality of the donor‐acceptor units. In the more polar solvent CH3CN all the quinone derivatives show fast formation of the charge‐separated state (kCS) followed by slower charge recombination (kCR). The ratio kCS/kCR≤80. 相似文献
86.
Li R Zeitler JA Tomerini D Parrott EP Gladden LF Day GM 《Physical chemistry chemical physics : PCCP》2010,12(20):5329-5340
The phonon modes of crystalline benzoic acid have been investigated using terahertz time-domain spectroscopy, rigid molecule atom-atom model potential and plane-wave density functional theory lattice dynamics calculations. The simulation results show good agreement with the measured terahertz spectra and an assignment of the terahertz absorption features of benzoic acid is made with the help of both computational methods. Focussing on the strongest interactions in the crystal, we describe each vibration in terms of distortions of the benzoic acid hydrogen bonded dimers that are present in the crystal structure. The terahertz spectrum is also shown to be highly sensitive to the location of the carboxylic acid hydrogen atoms in the cyclic hydrogen-bonded dimers and we have systematically explored the influence of the observed disorder in the hydrogen atom positions on the lattice dynamics. 相似文献
87.
Graeme J. Gainsford Richard H. Furneaux Peter C. Tyler Anthony Sauve Vern L. Shramm 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(3):m65-m68
The sodium salt of [immucillin‐A–CO2H]− (Imm‐A), namely catena‐poly[[[triaquadisodium(I)](μ‐aqua)[μ‐(1S)‐N‐carboxylato‐1‐(9‐deazaadenin‐9‐yl)‐1,4‐dideoxy‐1,4‐imino‐d ‐ribitol][triaquadisodium(I)][μ‐(1S)‐N‐carboxylato‐1‐(9‐deazaadenin‐9‐yl)‐1,4‐dideoxy‐1,4‐imino‐d ‐ribitol]] tetrahydrate], {[Na2(C12H13N4O6)2(H2O)7]·4H2O}n, (I), forms a polymeric chain via Na+—O interactions involving the carboxylate and keto O atoms of two independent Imm‐A molecules. Extensive N,O—H...O hydrogen bonding utilizing all water H atoms, including four waters of crystallization, provides crystal packing. The structural definition of this novel compound was made possible through the use of synchrotron radiation utilizing a minute fragment (volume ∼2.4 × 10−5 mm−3) on a beamline optimized for protein data collection. A summary of intra‐ring conformations for immucillin structures indicates considerable flexibility while retaining similar intra‐ring orientations. 相似文献
88.
It is not known whether or not there exists an odd perfect number. We describe an algorithmic approach for showing that if there is an odd perfect number then it has t distinct prime factors, and we discuss its application towards showing that t9. 相似文献
89.
90.