排序方式: 共有110条查询结果,搜索用时 15 毫秒
11.
Dunn ME Shields GC Takahashi K Skodje RT Vaida V 《The journal of physical chemistry. A》2008,112(41):10226-10235
In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the nu = 1-5 vibrational states of the OH stretching transitions. Cross sections for nu = 1, 2, 4 and 5 of the OH stretching vibrational transitions are derived on the basis of the vapor pressure data obtained for vinylacetic acid. Ab initio calculations are used to assist in the band assignments of the experimental spectra, and to determine the threshold for the decarboxylation of vinylacetic acid. When compared to the theoretical energy barrier to decarboxylation, it is found that the nu OH = 4 transition with thermal excitation of low frequency modes or rotational motion and nu OH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation. 相似文献
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Sharma PK Reilly MJ Bhatia SK Sakhitab N Archambault JD Bhatia SR 《Colloids and surfaces. B, Biointerfaces》2008,64(2):229-235
Pluronic F127, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), has generated considerable interest as a drug delivery vehicle due to its ability to gel at physiological temperatures. This work examines the gelation behavior of Pluronic F127 in the presence of a series of hydrophobic pharmaceuticals, to determine whether there is any correlation between gelation and physicochemical parameters of drug solutes. The study includes the local anesthetics dibucaine, lidocaine, and tetracaine; the pharmaceutical additives methyl paraben, ethyl paraben, and propyl paraben; the anti-cancer agents paclitaxel and baccatin III; and the anti-inflammatory agent sulindac. The results indicate that the presence of local anesthetics and pharmaceutical additives allows F127 solutions to form gels at lower copolymer concentrations; local anesthetics and pharmaceutical additives also shift gelation down to a lower gelation temperature. This behavior is strongly dependent on drug solubility; poorly soluble drugs (paclitaxel, baccatin III, sulindac) do not change the lower gelation temperature or minimum F127 concentration for gelation. An equation relating the decrease in gelation temperature to drug solubility is presented, and the equation fits the data well. The results have significant positive implications on the toxicity and economic issues related to use of Pluronic F127 in drug delivery. 相似文献
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Sharma PK Reilly MJ Jones DN Robinson PM Bhatia SR 《Colloids and surfaces. B, Biointerfaces》2008,61(1):53-60
We present results on the effects of various hydrophobic drugs and additives on the micellar structure of Pluronic F127 solutions. Small-angle neutron scattering experiments on 5wt% F127 solutions were used to measure micelle core size (R(1)), micelle corona size (R(2)), intermicellar interaction distance (R(int)), polydispersity (sigma), and aggregation number (N(agg)); dynamic light scattering was used to measure critical micelle concentration (CMC); and ultraviolet spectroscopy was used to measure drug solubility and apparent micelle-water partition coefficient (K(mw)). The core and corona size were found to generally increase in the presence of the drugs, as did R(int). Both sigma and N(agg) were found to decrease in the presence of most of the drugs, and the CMC was found to vary considerably with no clear correlation. A design of experiments (DOE) approach was used to analyze the results and build empirical correlations. All of the parameters from the SANS experiments were found to depend strongly on drug solubility, with a weak dependence on K(mw) in most cases. The aggregation number, however, was found to depend strongly on both K(mw) and solubility. The correlations can be used to roughly predict the structural parameters of F127 micelles for other hydrophobic drugs. 相似文献
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Fathi F Schlitt M Pedersen DB Kraatz HB 《Langmuir : the ACS journal of surfaces and colloids》2011,27(19):12098-12105
A simple electrochemical method has been proposed for the preparation of silver nanoparticles that can be used for the detection of cyanide. Both the electrochemical behavior and morphology of the Ag nanoparticles have been characterized in the presence of KCN or diethyl cyanophosphonate (DECP) as well as in alkaline media. These were investigated by cyclic voltammetry and scanning electron microscopy (SEM). DECP is a simulant of the chemical warfare agent tabun. 相似文献
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Fuerstman MJ Lai A Thurlow ME Shevkoplyas SS Stone HA Whitesides GM 《Lab on a chip》2007,7(11):1479-1489
This paper derives the difference in pressure between the beginning and the end of a rectangular microchannel through which a flowing liquid (water, with or without surfactant, and mixtures of water and glycerol) carries bubbles that contact all four walls of the channel. It uses an indirect method to derive the pressure in the channel. The pressure drop depends predominantly on the number of bubbles in the channel at both low and high concentrations of surfactant. At intermediate concentrations of surfactant, if the channel contains bubbles (of the same or different lengths), the total, aggregated length of the bubbles in the channel is the dominant contributor to the pressure drop. The difference between these two cases stems from increased flow of liquid through the "gutters"-the regions of the system bounded by the curved body of the bubble and the corners of the channel-in the presence of intermediate concentrations of surfactant. This paper presents a systematic and quantitative investigation of the influence of surfactants on the flow of fluids in microchannels containing bubbles. It derives the contributions to the overall pressure drop from three regions of the channel: (i) the slugs of liquid between the bubbles (and separated from the bubbles), in which liquid flows as though no bubbles were present; (ii) the gutters along the corners of the microchannels; and (iii) the curved caps at the ends of the bubble. 相似文献
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Pickard FC Shepherd RL Gillis AE Dunn ME Feldgus S Kirschner KN Shields GC Manoharan M Alabugin IV 《The journal of physical chemistry. A》2006,110(7):2517-2526
We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an sigma framework. 相似文献
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The molecular recognition of peptides and proteins in aqueous solution by designed molecules remains an elusive goal with broad implications for basic biochemical research and for sensors and separations technologies. This paper describes the recognition of N-terminal tryptophan in aqueous solution by the synthetic host cucurbit[8]uril (Q8). Q8 is known to form 1:1:1 heteroternary complexes with methyl viologen (MV) and a second aromatic guest. Here, the complexes of Q8.MV with (i) the four natural aromatic alpha-amino acids, (ii) four singly charged tryptophan derivatives, and (iii) four tryptophan-containing tripeptides were characterized by isothermal titration calorimetry, mass spectrometry, and UV-visible, fluorescence, and (1)H NMR spectroscopy. We find that Q8.MV binds Trp-Gly-Gly with high affinity (K(a) = 1.3 x 10(5) M(-1)), with 6-fold specificity over Gly-Trp-Gly, and with 40-fold specificity over Gly-Gly-Trp. Analysis of the nine indole-containing compounds suggests that peptide recognition is mediated by the electrostatic charge(s) proximal to the indole, and that the mode of binding is consistent for these compounds. Complex formation is accompanied by the growth of a visible charge-transfer band and the quenching of indole fluorescence. These optical properties, combined with the stability and selectivity of this system, are promising for applications in sensing and separating specific peptides. 相似文献
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Leventis A. Verganelakis D. A. Halse M. R. Webber J. B. Strange J. H. 《Transport in Porous Media》2000,39(2):143-157
The kinetics of capillary imbibition in ordinary Portland cement pastes has been studied experimentally and theoretically. Nuclear magnetic resonance stray field imaging (STRAFI) has been used to record water concentration profiles for various ingress times. The profiles follow a t law and thus a master curve can be formed using the Boltzmann transformation. The distribution of pore sizes within the sample as measured by NMR cryoporometry shows a prominent peak at 100Å. A computer model of the pore structure was developed consisting of a lattice of interconnecting pores with a size distribution consistent with the cryoporometry results. The Hagen–Poiseuille law was used to describe the kinetics of the water in this pore structure. The best agreement between the computer simulations and the experimental master curve was obtained by using a narrower range of pore sizes than indicated by the cryoporometry results. 相似文献
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Dureen MA Lough A Gilbert TM Stephan DW 《Chemical communications (Cambridge, England)》2008,(36):4303-4305
Catechol borane reacts with the frustrated Lewis pairs tBu2RP (R = tBu, 2-C6H4(C6H5)) and B(C6F5)3 to give the species [(C6H4O2)BPtBu2R][HB(C6F5)3] that can formally be described as either borenium cation or boryl-phosphonium salts; the nature of these species was probed with DFT calculations. 相似文献