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111.
Time-resolved surface-enhanced Raman scattering (SERS) was applied to study the response of Raman bands from 4-cyanopyridine (PyCN) adsorbed on a Ag electrode to variation of the potential; the temporal resolution was 0.1 s. The response of the SERS signals of PyCN was instantaneous to the oxidation potential of Ag electrode. However, delay of the SERS signals was observed while AgCl was reducing. The decay and growth of the SERS bands look place within 1 s in the cases of desorption and adsorption of PyCN on the electrode. It took much longer for PyCN to alter from one adsorption geometry to another on the electrode. 相似文献
112.
113.
A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature. 相似文献
114.
Pro-oxidant properties of phenolic antioxidants, which are derived from their iron recycling reactivity, render the traditional deoxyribose degradation assay invalid to assess the hydroxyl radical-scavenging activity in Fenton-type reaction systems. In the present paper, we studied in detail the interactions between iron and phenolic compounds, and established a kinetic deoxyribose method by taking advantage of the distinct difference between the completion time of Fenton reaction and that of the iron-reducing process. With the newly established kinetic method, we investigated the effects of phenolics on hydroxyl radical formation in a Fenton-type system and determined successfully the second rate constants of hydroxyl radical-scavenging reactions. The site-specific and non-site-specific hydroxyl radical-scavenging ability suggested that both direct hydroxyl radical-scavenging potency and iron-chelating capacity accounted for their inhibitory effects on deoxyribose oxidation degradation. This method, more simple, time saving, and applicative than the traditional deoxyribose assay, produces as accurate results (RSD<0.05, with dynamic range from 7.5 to 575 μM) as typical methods, such as radiolysis technology, and may be of significance in evaluating and screen the hydroxyl radical-scavenging antioxidants. 相似文献
115.
Jin-Woong?Kim Jin-Gyu?Park Jee-Hyun?Ryu Ih-Seop?Chang Kyung-Do?SuhEmail author 《Colloid and polymer science》2005,283(11):1233-1240
This study presents a method to produce monodisperse chloromethyl-functionalized macroporous poly(styrene-co-divinylbenzene) polymer particles by seeded polymerization in aqueous media. We observed that the molecular structure of
polystyrene seed particles, the composition of the secondary monomer mixtures, and the type of solvents were very important
factors that determine the morphology and porosity of the final particles. This study proposes that the molecular chemistry
of polystyrene seed polymers, increasing molecular weight or crosslinking, is another factor that can control the porosity
of the final particles. Also, the selection of a poor solvent was effective in forming the larger surface area. In this study,
it was confirmed that the chloromethyl groups introduced on the surface of porous particles were quantified chemically and
their effective incorporation had a close relationship with the surface area. 相似文献
116.
The synthesis of '2('3)-O-(amino)acyl-pCpA derivatives is described and the products are characterized chemically and as substrates for T4 RNA ligase in the presence of E. coli tRNA phe-COH. The modified (N-acetylammo)acyl-tRNA's so derived are characterized by their chromatographic and biochemical properties, and by their ability to act as P-site tRNA donors in the peptidyltransferase reaction. 相似文献
117.
Synthesis of camphor derived chiral allenes and their hydroboration-oxidation reactions are described. Reaction of (1R)-(+)-camphor with alkynyllithium followed by the reduction of the resulted propargyl alcohol derivatives using AlH3 furnished chiral allenes 2a-g in excellent yields with high diastereoselectivity. Reduction of the propargyl alcohols with aluminum hydride proceeded through selective intermolecular anti-addition of hydride ion. The stereochemistry of the chiral allenes 2 was assigned based on lanthanide shift studies and chemical correlations. Diastereoselectivity was observed in the hydroboration-oxidation of 2 which produced a mixture of (E,R) and (E,S) stereoisomers in a ratio of 6:1 to 18:1. 相似文献
118.
A "one-step" procedure, that not only removes the color and blocking proteins used in the colorimetric immunodetection step but also stains the proteins originally on the blot, is presented. Following immunostaining and recording of immunoreactive spots, the blot was allowed to air-dry overnight (or longer) at room temperature and then counterstained with a colloidal gold solution. This "air-drying" process apparently altered the affinity of the blocking proteins (and possibly other proteins added subsequently to the blotting step) towards the nitrocellulose membrane causing them to be removed by the acidic colloidal gold solution while the "blotted" proteins were being stained. The sensitivity of this counterstained blot was comparable to that of the blot without going through the immunodetection process. Since both immunodetection and protein staining were carried out on the same blot, this allowed easy identification of many immunoreactive spots to their corresponding proteins when the two profiles were superimposed. Using this procedure, we have detected 25 immunoreactive spots (or allergens) from the whole body extract of the German cockroach (Blattella germanica) that contribute to asthma and assigned them to their corresponding proteins on a two-dimensional (2-D) protein map. The apparent Mr and pI for each of the allergens were determined. We have also located one of the major cockroach allergens, Bla g 5 (glutathione S-transferase). Two-dimensional zymography revealed the presence of ten gelatinase-type proteolytic enzymes. Only one of the ten proteases comigrated with the immunoreactive proteins indicating that unlike other allergen-producing systems, most of the cockroach allergens do not possess protease activity. 相似文献
119.
Zellner M Winkler W Hayden H Diestinger M Eliasen M Gesslbauer B Miller I Chang M Kungl A Roth E Oehler R 《Electrophoresis》2005,26(12):2481-2489
For the preparation of proteins for proteome analysis, precipitation is frequently used to concentrate proteins and to remove interfering compounds. Various methods for protein precipitation are applied, which rely on different chemical principles. This study compares the changes in the protein composition of human blood platelet extracts after precipitation with ethanol (EtOH) or trichloroacetic acid (TCA). Both methods yielded the same amount of proteins from the platelet preparations. However, the EtOH-precipitated samples had to be dialyzed because of the considerable salt content. To characterize single platelet proteins, samples were analyzed by two-dimensional fluorescence differential gel electrophoresis. More than 90% of all the spots were equally present in the EtOH- and TCA-precipitated samples. However, both precipitation methods showed a smaller correlation with nonprecipitated samples (EtOH 74.9%, TCA 79.2%). Several proteins were either reduced or relatively enriched in the precipitated samples. The proteins varied randomly in molecular weight and isoelectric point. This study shows that protein precipitation leads to specific changes in the protein composition of proteomics samples. This depends more on the specific structure of the protein than on the precipitating agent used in the experiment. 相似文献
120.
Nonlinear and nonequilibrium electrophoresis of spherical particles of radius a is shown to be possible when the solid surface allows field or current penetration. At low particle Peclet numbers, transient capacitative charging occurs until the surface polarization completely screens the external field. For a DC applied field [see text], the resulting electrokinetic velocity reaches Dukhin's maximum value of [formula: see text], where [see text] and mu are the liquid permittivity and viscosity. At high Peclet numbers, electroosmotic convection of the electroneutral bulk stops the transient charging before complete field-line exclusion. For an ion-selective and conducting spherical granule, the polarization is then determined by the steady-state Ohmic current driven by the penetrated external field. The high-Peclet electrokinetic velocity is lower, diffusivity-dependent and scales as [see text]. 相似文献