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991.
Dupin D Schmid A Balmer JA Armes SP 《Langmuir : the ACS journal of surfaces and colloids》2007,23(23):11812-11818
Colloidal poly(2-vinylpyridine)-silica nanocomposite particles can be efficiently prepared by emulsion polymerization at 60 degrees C using a commercial 20 nm aqueous silica sol as the sole stabilizing agent. Unlike previously reported colloidal nanocomposite syntheses, transmission electron microscopy studies indicate very high silica aggregation efficiencies (88-99%). The key to success is simply the selection of a suitable cationic azo initiator. In contrast, the use of an anionic persulfate initiator leads to substantial contamination of the nanocomposite particles with excess silica sol. The cationic azo initiator is electrostatically adsorbed onto the anionic silica sol at submonolayer coverage, which suggests that surface polymerization may be important for successful nanocomposite formation. Moreover, the 2-vinylpyridine can be partially replaced with either styrene or methacrylic comonomers to produce a range of copolymer-silica nanocomposite particles. The poly(2-vinylpyridine)-silica nanocomposite particles have a well-defined core-shell morphology, with poly(2-vinylpyridine) cores and silica shells; mean diameters typically vary from 180 to 220 nm, and mean silica contents range from 27 to 35% by mass. 相似文献
992.
Kettlewell SL Schmid A Fujii S Dupin D Armes SP 《Langmuir : the ACS journal of surfaces and colloids》2007,23(23):11381-11386
We describe the facile production of highly stable foams stabilized solely by cationic polystyrene latex particles. Three model polystyrene latexes were synthesized using either a cationic 2,2'-azobis(2-diisobutyramidine) dihydrochloride (AIBA) or an anionic ammonium persulfate (APS) radical initiator: a 724 +/- 81 nm charge-stabilized cationic polystyrene latex [AIBA-PS], an 800 +/- 138 nm sterically stabilized cationic latex prepared using a poly(ethylene glycol) monomethacrylate macromonomer [PEGMA-AIBA-PS], and a 904 +/- 131 nm charge-stabilized anionic polystyrene latex [APS-PS], respectively. The effect of particle surface charge, latex concentration, and solution pH on foam stability was studied in detail. The PEGMA-AIBA-PS latex proved to be the best foam stabilizer even at relatively low latex concentrations (3.0 wt %), with long-term foam stabilities being obtained after drying. The AIBA-PS latex also produced stable foams, albeit only at higher latex concentrations. However, the APS-PS latex proved to be an ineffective foam stabilizer. This is believed to be primarily due to the anionic surface character of this latter latex, which prevents its adsorption at the anionic air-water interface. This hypothesis is supported by the observation that the AIBA-PS latex no longer acts as an effective foam stabilizer above its isoelectric point (pH 7.04). Scanning electron microscopy studies revealed the formation of well-defined latex bilayers within dried foams, which indicates that the wet air bubbles are stabilized by latex monolayers prior to drying. However, little or no long-range ordering of the latex particles was observed on the surface of the bubbles, which is presumably related to the latex polydispersity. 相似文献
993.
Lee H Finckbeiner S Yu JS Wiemer DF Eisner T Attygalle AB 《Journal of chromatography. A》2007,1165(1-2):136-143
Several volatile compounds, including terpenoids, fatty alcohols, fatty acids and some of their esters, were identified from solvent extracts prepared from anal scent glands of nutria (a.k.a. coypu), a serious rodent pest ravaging wetlands in the USA. The major terpenoid constituents were identified as (E,E)-farnesol and its esters by a comparison of their gas chromatographic retention times, and electron-ionization (EI) and chemical-ionization (CI) mass spectra with those of authentic compounds. EI mass spectra of the four farnesol isomers are very similar, however, the ChemStation (Agilent) and GC-MS Solution (Shimadzu) software algorithms were able to identify the natural compound as the (E,E)-isomer, when a high-quality mass spectral library was compiled from reference samples and used for searching. Similarly, the esters were identified as those of (E,E)-farnesol. In contrast to EI spectra, the CI spectra of the (E,E)- and (E,Z)-isomers are distinctly different from those of the (Z,E)- and (Z,Z)-isomers. The intensities (I) of the peaks for the m/z 137 and 121 ions in the CI spectra offer a way of determining the configuration of the C-2 double bond of farnesols (for 2E isomers I(137)>I(121), whereas for 2Z isomers I(137)相似文献
994.
Chen X Ma C Kwok WM Guan X Du Y Phillips DL 《The journal of physical chemistry. B》2007,111(40):11832-11842
Complete active-space self-consistent field (CASSCF) calculations with a (14,11) active space and density functional theory calculations followed by Car-Parrinello molecular dynamic simulations are reported for the p-hydroxyphenacyl acetate, diethyl phosphate, and diphenyl phosphate phototrigger compounds. These calculations considered the explicit hydrogen bonding of water molecules to the phototrigger compound and help reveal the role of water in promoting the photodeprotection and subsequent rearrangement reactions for the p-hydroxyphenacyl caged phototrigger compounds experimentally observed in the presence of appreciable amounts of water but not observed in neat nonproton solvents like acetonitrile. The 267 nm excitation of the phototrigger compounds leads to an instantaneous population of the S3(1pipi*) state Franck-Condon region, which is followed by an internal conversion deactivation route to the S1(1npi*) state via a 1pipi*/1npi* vibronic coupling. The shorter lifetime of the S1(1npi*) state (approximately 1 ps) starting from the FC geometry is terminated by a fast intersystem crossing at a 3pipi*/3npi* intersection with a structure of mixed pipi*/npi* excitation in the triplet state. The deprotection reaction is triggered by a proton (or hydrogen atom) transfer assisted by water bridges and emanates from this pipi*/npi* triplet state intersection. With the departure of the leaving group, the reaction evolves into a water-mediated post-deprotection phase where the spin inversion of pQM (X, 3A) leads to a spiroketone in the ground state by a cyclization process that is followed by an attack of water to produce a 1,1'-di-hydroxyl-spiroketone. Finally, the H atom of the hydroxyl in 1,1'-di-hydroxyl-spiroketon transfers back to the p-O atom aided by water molecules to generate the p-hydroxyphenyl-acetic acid final rearrangement product. 相似文献
995.
Kumarn S Oelke AJ Shaw DM Longbottom DA Ley SV 《Organic & biomolecular chemistry》2007,5(16):2678-2689
A sequential, organocatalysed asymmetric reaction to access chiral 1,2-oxazines and chiral pyridazines is reported, which proceeds in moderate to good yields and good to excellent enantioselectivities. 相似文献
996.
Stevenson S Mackey MA Thompson MC Coumbe HL Madasu PK Coumbe CE Phillips JP 《Chemical communications (Cambridge, England)》2007,(41):4263-4265
The yield of Sc3N@C80 metallofullerene and fullerene extract is dramatically increased via filling cored graphite rods with copper and Sc2O3 only; when compared to 100% Sc2O3 packed rods, improvements of factors of approximately 3 and approximately 5 have been achieved for Sc3N@C80 and fullerene extract produced, respectively, with the weight percent of Cu added to the rod affecting the type and amount of fullerene produced. 相似文献
997.
Analysis and modeling of spatial data are of considerable interest in many applications. However, the prediction of geographical features from a set of chemical measurements on a set of geographically distinct samples has never been explored. We report a new, tree‐structured hierarchical model for the estimation of geographical location of spatially distributed samples from their chemical measurements. The tree‐structured hierarchical modeling used in this study involves a set of geographic regions stored in a hierarchical tree structure, with each nonterminal node representing a classifier and each terminal node representing a regression model. Once the tree‐structured model is constructed, given a sample with only chemical measurements available, the predicted regional location of the sample is gradually restricted as it is passed through a series of classification steps. The geographic location of the sample can be predicted using a regression model within the terminal subregion. We show that the tree‐structured modeling approach provides reasonable estimates of geographical region and geographic location for surface water samples taken across the entire USA. Further, the location uncertainty, an estimate of a probability that a test sample could be located within a pre‐estimated, joint prediction interval that is much smaller than the terminal subregion, can also be assessed. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
998.
999.
The covalent addition of nitric oxide (NO) to protein thiols, a posttranslational modification termed S-nitrosation, is a ubiquitous event that modulates diverse cellular processes. The in vivo addition of NO to protein amines (N-nitrosation) has also been described and may similarly modify protein structure and function. While mass spectrometry has been employed for identification of nitrosoproteins, little is known about how S- and N-nitrosopeptides fragment. Such knowledge is important for its potential to inform on sites of protein nitrosation. Here we used electrospray tandem mass spectrometry to elucidate collision-induced dissociation (CID) features of S- and N-nitrosopeptide ions. We show that S- and N-nitrosopeptide ions readily lose NO, giving rise to species that contain thiyl and aminyl radicals, respectively. Fragmentation (MS3) of these radical peptide ions revealed an atypical pattern, characterized by the cleavage of select alphaCC and NalphaC bonds, rather than the more usual cleavage of amide bonds that result in b- and y-ions. These unanticipated fragmentation patterns are reconciled by radical-mediated abstraction of hydrogen from beta-carbon followed by beta-fragmentation. For thiyl radical peptides, we also observed dominant loss of SH and CH2SH from the Cys side-chain. Our findings provide new insights into the gas-phase chemistry of NO-modified peptide ions and suggest an unusual fragmentation pattern that may aid in future MS-based attempts to define the nitrosoproteome. 相似文献
1000.
To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments. 相似文献