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191.
Yousef A Shrestha S Viehland LA Lee EP Gray BR Ayles VL Wright TG Breckenridge WH 《The Journal of chemical physics》2007,127(15):154309
High-level ab initio calculations are performed on the coinage metal cations (Cu+, Ag+, and Au+) interacting with each of the rare gases [Rg (Rg=He to Rn)]. The RCCSD(T) procedure is employed, with basis sets being of approximately quintuple-zeta quality, but with the heavier species using relativistic effective core potentials. The interaction potentials are compared to experimental and theoretical data where they exist. In addition, transport coefficients for the mobility and diffusion of the cations in the rare gases are calculated. The latter have involved a rewriting of some of the programs used, and the required modifications are discussed. The mobility results indicate that, rather than being a rare occurrence, mobility minima may be common phenomena. Finally, a new estimate is put forward for the validity of zero-field mobilities in ion mobility spectrometry. 相似文献
192.
Plowright RJ Ayles VL Watkins MJ Gardner AM Wright RR Wright TG Breckenridge WH 《The Journal of chemical physics》2007,127(20):204308
The Au-Ar complex is reinvestigated employing resonance-enhanced multiphoton ionization spectroscopy. Spectra are reported, corresponding to the atomic transition Au(6p<--6s). This electronic excitation yields (2)Pi and (2)Sigma(+) states of Au-Ar, which interact under the influence of spin-orbit coupling. The spectra are consistent with strong sigma-pi mixing induced by the large spin-orbit coupling of Au, leading to strong interaction of the two Omega=12 states, which arise from the Ar((1)S(0))+Au((2)P(12,32)) asymptotes, and the consequent formation of a "shelf" on the outer wall of the lowest Omega=12 state. In addition, high-level ab initio calculations are reported on the ground electronic state, X (2)Sigma(+), including extrapolation to the basis set limit. 相似文献
193.
Benavente F Vescina MC Hernández E Sanz-Nebot V Barbosa J Guzman NA 《Journal of chromatography. A》2007,1140(1-2):205-212
The use of solid-phase extraction coupled on-line to capillary electrophoresis using electrospray mass spectrometry detection (SPE-CE-ESI-MS) is described for the analysis of peptides in dilute solutions. A SPE microcartridge or analyte concentrator containing C(18) derivatized silica particles as the extraction sorbent was easily constructed near the inlet of the separation capillary using commercially available materials. The reversed-phase sorbent selectively retained the target peptides, enabling large volumes of the sample to be introduced (>100muL). The captured analytes were eluted in a small volume of an appropriate solution (20-50nL). This resulted in sample clean-up and concentration enhancement, with minimum sample handling. As the SPE-CE conditions were compatible with on-line ESI-MS detection, the potential for identifying and characterizing the preconcentrated analytes by SPE-CE-ESI-MS using a sheath-flow CE-ESI-MS interface is also shown. Using separation electrolytes containing N-[carbamoylmethyl]-2-aminoethanesulfonic acid (ACES) at pH 7.4, an elution plug of 80:20 (v/v) (25mM of formic acid in MeCN):H(2)O and a sheath liquid of 20mM of acetic acid in 50:50 (v/v) methanol:H(2)O the concentration limits of detection for the analyzed peptides in the positive ion mode were lowered to nanogram per milliliter levels. The systematic optimization of the operational parameters involved in the development of the SPE-CE method is described in detail, in order to promote robust and quantitative SPE-CE-ESI-MS analysis and facilitate the widespread use of the technique. 相似文献
194.
The present work describes a new analytical method for direct immunoaffinity column clean-up of ochratoxin A (OTA) in milk samples followed by determination of the toxin using high-performance liquid chromatography with fluorescence detection (HPLC-FD). Two different immunoaffinity cartridges (IAC) were investigated, and Ochraprep columns were chosen because they showed the best results. An average recovery of 89.8% and a mean RSD of 5.8% for artificially contaminated cow's milk in the range of 5-100 ng/L were attained. The calculated limit of detection (LOD) and limit of quantitation (LOQ) were as low as 0.5 and 5 ng/L, respectively. This new easy and fast method avoids a previous liquid-liquid extraction step and therefore the use of toxic chlorinated solvents. Chromatograms of the final extracts were clean and OTA could be easily detected at a retention time of 8.4 min without interferences. To assess the presence of the toxin in cow's milk eight samples of skimmed and four samples of whole milk were analysed and OTA was not detected over the established detection limit. 相似文献
195.
The goal of this research was to study wetting and adhesion processes between various petroleum products and solid surfaces. When a liquid interacts with a solid surface, wetting, spreading and adhesion processes determine its behavior. These processes are of great importance for understanding oil spill response as well as oil spill behavior on land and in near shore environments, and oil extraction from the reservoir rock. The current study aimed at analyzing oil affinity and adhesion to surfaces used in the mechanical recovery of oil spills. A number of crude oils and petroleum products were tested with the surface materials that are used or may potentially be used to recover oil spills. Through the study of contact angles and recovered mass, it was found that the behavior of the oils at the solid surface is largely determined by the roughness of the solid. For smooth solids, contact angle hysteresis is a good indicator of the ability of the solid to retain oil. For rougher elastomers, the advancing contact angle can be used to predict wetting and adhesion processes between oil and solid. This study showed that oleophilic elastomers (e.g., Neoprene and Hypalon) have higher oil recovery potential than smooth polymers. 相似文献
196.
Victoria L. Luck David P. Richards Ashif Y. Shaikh Henrik Franzyk Ian R. Mellor 《Molecules (Basel, Switzerland)》2021,26(22)
Alterations in the polyamine and amino acid (tyrosine) moieties of philanthotoxin-343 (PhTX-343) were investigated for their effects on the antagonism of nicotinic acetylcholine receptors (nAChRs) isolated from the locust (Schistocerca gregaria) mushroom body. Through whole-cell patch-clamp recordings, the philanthotoxin analogues in this study were shown to cause inhibition of the inward current when co-applied with acetylcholine (ACh). PhTX-343 (IC50 = 0.80 μM at −75 mV) antagonised locust nAChRs in a use-dependent manner, suggesting that it acts as an open-channel blocker. The analogue in which both the secondary amine functionalities were replaced with methylene groups (i.e., PhTX-12) was ~6-fold more potent (IC50 (half-maximal inhibitory concentration) = 0.13 μM at −75 mV) than PhTX-343. The analogue containing cyclohexylalanine as a substitute for the tyrosine moiety of PhTX-343 (i.e., Cha-PhTX-343) was also more potent (IC50 = 0.44 μM at −75 mV). A combination of both alterations to PhTX-343 generated the most potent analogue, i.e., Cha-PhTX-12 (IC50 = 1.71 nM at −75 mV). Modulation by PhTX-343 and Cha-PhTX-343 fell into two distinct groups, indicating the presence of two pharmacologically distinct nAChR groups in the locust mushroom body. In the first group, all concentrations of PhTX-343 and Cha-PhTX-343 inhibited responses to ACh. In the second group, application of PhTX-343 or Cha-PhTX-343 at concentrations ≤100 nM caused potentiation, while concentrations ≥ 1 μM inhibited responses to ACh. Cha-PhTX-12 may have potential to be developed into insecticidal compounds with a novel mode of action. 相似文献
197.
Matthew Brewis Guy J. Clarkson Victoria Goddard Madeleine Helliwell Andrea M. Holder Neil. B. McKeown 《Angewandte Chemie (International ed. in English)》1998,37(8):1092-1094
Nonscattering glasses that are indefinitely stable with respect to crystallization can be prepared from the title compounds. In these solid solutions, the dendritic substituents effectively suppress interactions between the phthalocyanine units (see the structure depicted on the right). 相似文献
198.
Gabriela Rocha‐Botello Roberto Olvera‐Guillen Jorge Herrera‐Ordonez Martha Cruz‐Soto David Victoria‐Valenzuela 《大分子反应工程》2019,13(5)
Kinetic aspects of the vinyl acetate ab initio batch emulsion polymerization using poly(vinyl alcohol) to produce polymer nanoparticles are studied. The initial nucleation step is followed by limited coagulation and then by the generation of new particles. It seems that this is the first report of secondary nucleation phenomenon occurring in the system under study in batch mode. To explain this phenomenon, a mathematical model that allows to determine whether certain polymerization conditions and the presence/absence of a steric barrier, can lead or not to significant secondary nucleation is developed. It is deduced that the effect of such steric barrier on the free‐radical entry process plays a key role on the observed phenomenon. 相似文献
199.
Letters in Mathematical Physics - We consider the trigonometric classical r-matrix for $$\mathfrak {gl}_N$$ and the associated quantum Gaudin model. We produce higher Hamiltonians in an explicit... 相似文献
200.
Andrew N. Cammidge Victoria H.M. Goddard Geoffrey Will Michael J Cook 《Tetrahedron letters》2009,50(25):3013-321
Mixed cyclisations have been performed to give phthalocyanine-naphthalocyanine hybrids bearing solubilising substituents. Reactivity differences between the two phthalonitrile precursors result in inefficient mixed-macrocyclisation under standard, non-templating conditions leading to predominant formation of symmetrical phthalocyanine. Templated mixed-macrocyclisation leads to the hybrids. However, the reaction proceeds with unexpected selectivity with only one of the possible 2:2 products observed. 相似文献