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71.
The effect of disjoining pressure between a rigid spherical probe particle (attached to an AFM cantilever) and a liquid interface (e.g., oil/water or air/water) is treated in an analytic manner to describe the total force F exerted on the probe as a function of the distance X of the probe from the rigid substrate (AFM stage) on which the liquid interface resides. Two cases (i) a flat interface under gravity and (ii) a drop whose size is sufficiently small that gravity can be neglected have been examined. A simple numerical algorithm is given for computing F(X) (the AFM observable) from a given form for the disjoining pressure. Numerical results are displayed for electrostatic probe/interface interactions which reveal the linear compliance regime experimentally observed in AFM experiments on these systems. The slope of the linear compliance regime is shown to be a function of the properties of the interface (capillary length, particle radius, drop size, contact angle of drop on rigid substrate etc.). Copyright 2001 Academic Press. 相似文献
72.
A new chiral aminophosphine ligand 6,6′-dimethoxy-2,2′-bis(diphenylphosphinoamino)biphenyl(DMBDPPABP) was prepared and its rhodium complex was found to be an effective catalyst for the asymmetric hydrogenation of amidoacrylic acid and its dervatives.The effects of solvent and reaction temperature on enantioselectivity were also studied. 相似文献
73.
Jin-Wan Huang Liang-Nian Ji An-Kong Hsich T. S. Andy Hor 《Transition Metal Chemistry》1992,17(4):280-282
Photolytic decarbonylation of Rh2(CO)4(TPP) (TPP=tetraphenylporphyrinato) with pyridine (Py) in benzene gives an unusual monomeric RhII radical complex Rh(TPP)(Py), which has been characterised by thermal and spectroscopic measurements and by vapour pressure
osmosis. 相似文献
74.
Chan Sik Cho Tae Kyung Kim Tae‐Jeong Kim Sang Chul Shim Nam Sik Yoon 《Journal of heterocyclic chemistry》2002,39(2):291-294
Nitroarenes are reductively cyclized with 3‐amino‐1‐propanols in dioxane/H2O in the presence of a ruthenium catalyst and tin(II) chloride dihydrate together with isopropanol to afford the corresponding quinolines. A reaction pathway involving initial reduction of nitroarenes to anilines, propanol group transfer from 3‐amino‐1‐propanols to anilines, N‐alkylation of anilines by 3‐anilino‐1‐propanols and heteroannulation of 1,3‐dianilinopropanes is proposed. 相似文献
75.
The trypsin digest of a mixture of two proteins, namely cytochrome c and myoglobin, was first separated in the first dimension by high-performance liquid chromatography (HPLC). Fractions from the HPLC were collected every 30s with the aid of a fraction collector into a 96-well microtiter plate. After concentration, all the collected fractions were analyzed simultaneaosly in the second dimension by a 96-array capillary electrophoresis system. The labeled peptides were detected by laser-induced fluorescence. An internal standard, allura red, was added to all the fractions, prior to capillary electrophoretic analysis. The internal standard serves two functions, migration time correction and signal intensity correction. The data are presented in two different formats, as an electropherogram of all the fractions and in a two-dimensional (2-D) format. The 2-D plot of the data shows the density of each spot, which corresponds to the concentration of the migrating peptides. The total experimental time for the HPLC and capillary electrophoretic analyses ist less than 1 h, which ist much faster than using 2-D slab-gel electrophoresis or single-capillary capillary electrophoresis. 相似文献
76.
77.
Self-assembly of functionalized nanoscale building blocks is a promising strategy for "bottom-up" materials design. Recent experiments have demonstrated that the self-assembly of polyhedral oligomeric silsesquioxane (POSS) "nanocubes" functionalized with organic tethers can be utilized to synthesize novel materials with highly ordered, complex nanostructures. We have performed molecular simulations for a simplified model of monotethered POSS nanocubes to investigate systematically how the parameters that control the assembly process and the resulting equilibrium structures, including concentration, temperature, tether lengths, and solvent conditions, can be manipulated to achieve useful structures via self-assembly. We report conventional lamellar and cylindrical structures that are typically found in block copolymer and surfactant systems, including a thermotropic order-order transition, but with interesting stabilization of the lamellar phase caused by the bulkiness and cubic geometry of the POSS nanocubes. 相似文献
78.
A SPME-HPLC-post-column fluorescent derivatization method for the direct determination of saxitoxin (STX), the most potent paralytic shellfish poisoning (PSP) toxin, in water has been developed. Commercially available SPME devices with 50 microm Carbowax templated resin (CW/TPR) coating was found to be able to pre-concentrate STX from aqueous media. A special pre-conditioning treatment of soaking the SPME coating in 0.1 M NaOH solution significantly improved the extraction efficiency. The optimal pH for the SPME process is 8.1 and the equilibration time is 40 min. The partition coefficient, K, of the distribution of STX between the SPME coating and the aqueous media was measured to be 2.99 +/- 0.04 x 10(3). Extracted toxin on the SPME stationary phase was difficult to be desorbed by the HPLC mobile phase under dynamic desorption mode. A static ion-pairing desorption technique using a desorption solvent mixture of 20 mM sodium 1-heptanesulfonate in 30% aqueous acetonitrile acidified with 50 mM sulfuric acid was developed to overcome this problem. The method detection limit and repeatability achieved by this SPME-HPLC method were 0.11 ng ml(-1) and 3.7%, respectively, with a sample volume of just 5 ml of water. This analytical method is adequate for the monitoring of the PSP toxin in fresh/drinking waters. However, serious interference was observed when this technique was applied to saline water samples. This is probably due to competition of sodium ions with the cationic STX for absorption into the SPME stationary phase. 相似文献
79.
Tleugabulova D Duft AM Zhang Z Chen Y Brook MA Brennan JD 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5924-5932
At present, there is no direct experimental evidence that primary silica particles, which exist only transiently for a few seconds during the St?ber silica synthesis, can be stable in aqueous solutions. In the present work, we show that primary silica particles are formed spontaneously after the dissolution of diglycerylsilane (DGS) in aqueous solutions and remain stable for prolonged periods of time. By using time-resolved fluorescence anisotropy (TRFA), we demonstrate that this unique property of DGS is ascribed to the slow kinetics of silica particle growth in diluted sols at pH approximately 9.0. The anisotropy decay of the cationic dye rhodamine 6G (R6G), which strongly adsorbs to silica oligomers and nanoparticles in DGS sols, could be fit to three components: a fast (picosecond) scale component associated with free R6G, a slower (nanosecond) rotational component associated with R6G bound to primary silica particles, and a residual (nondecaying) anisotropy component associated with R6G that was bound to secondary or larger particles that were unable to rotate on the time scale of the R6G emission lifetime (4 ns). The data show that, under conditions where fast hydrolysis is obtained, the initial size of the nuclei depends on the silica concentration, with larger nuclei being present in more concentrated sols, while the rate of growth of primary particles depends on both silica concentration and solution pH. At low silica concentrations and high pHs, it was possible to observe the growth of stable, nonaggregating primary silica particles by a mechanism involving rapid nucleation followed by monomer addition. The presence of stable primary particles was confirmed by atomic force microscopy (AFM) imaging. At higher silica concentrations and lower pHs, there was an increase in the initial size of the nuclei formed, which subsequently grew to a larger radius (> 4.5 nm) or aggregated with time, and in such cases, nucleation and aggregation occurred simultaneously in the early stage of silica formation. The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the growth of silica colloids and show that this method is useful for elucidating the mechanism of particle formation and growth in situ. 相似文献
80.
Ionic-liquid-supported peptide synthesis demonstrated by the synthesis of Leu(5)-enkephalin 总被引:1,自引:0,他引:1
A new strategy for the synthesis of oligopeptides was developed using an ionic liquid as a soluble support. The efficiency of this ionic liquid-phase approach was demonstrated by the synthesis of a bioactive pentapeptide, Leu(5)-enkephalin, in good yield and reasonable purity. The structures and purities of the reaction intermediates in each step were verified easily by routine spectroscopic analysis, and no chromatographic procedures were needed during the synthesis. 相似文献