The crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. 相似文献
The benzamide-derived P,O-ligands efficiently promoted the Pd-catalyzed Suzuki cross-coupling reactions of aryl bromides with phenylboronic acid at 0.01 mol % of Pd loading at 60-80 °C to form biaryls in excellent yields. A sterically hindered arylboronic acid gave a quantitative yield of the coupling product at 110 °C with 1 mol % Pd. 相似文献
A rapid, selective method that utilize 4-(2-Pyridylazo)-resorcinol (PAR)-modified nanometer SiO2 (nanometer SiO2–PAR) as a new solid-phase extractant for preconcentration of trace mercury (II) has been developed. The adsorption property
of nanometer SiO2–PAR for metal ions was studied by selectively extracting different metal ions from aqueous solutions. The results revealed
an excellent affinity of the nanometer SiO2–PAR for mercury (II) in presence of interfering metal ions at pH 4. The main parameters of solid-phase extraction such as
shaking time, elution and sample dilution effect were studied. The extractant shows rapid kinetic sorption, and the adsorption
equilibrium of mercury (II) on nanometer SiO2–PAR was achieved in less than 2 min. The adsorbed mercury (II) was easily eluted by 4 mL of 6 mol L−1 HCl. The maximum preconcentration factor was 50. The maximum static adsorption capacity was 276 μmol g−1 at pH 4. The detection limit (3σ) was 0.43 μg L−1 for cold vapor atomic absorption spectrometry (CVAAS), and the relative standard deviation of the eight replicate determinations
was 2.4% for the determination of 2.0 μg of Hg(II) in 100 mL water sample. The method was applied to the determination of
trace mercury (II) in sample solutions with satisfactory results. 相似文献
An automated spray-and-trap (ST) chromatographic system was constructed for fast and efficient extraction of volatile organic compounds (VOCs) in aqueous samples with the capability to be deployed in the field for unattended continuous monitoring of surface or ground water. This system was built upon a commercial gas chromatograph with full automation capability using self-developed hardware and software. For sample analysis, fine droplets of the aqueous solution were generated in the extraction chamber by pressure expansion of a clean air stream through a spray nozzle. A portion of the VOCs distributed into the gas phase was retained by a multi-sorbent micro-trap kept at ambient temperature. Flash heating of the sorbent trap desorbed the enriched VOCs onto the gas chromatography (GC) with flame ionization detection (FID) for hydrocarbons or electron-capture detection (ECD) for halocarbons. In order to validate the performance of the ST method. it was compared with a more conventional method, i.e., a purge-and-trap (PT), by analyzing a serious of standard solutions containing benzene, toluene, ethylene. and o-, m-xylenes. Using a purge-and-trap method as a reference for complete extraction, the ST method showed less sensitivity. Extraction recoveries are in consistent with Henry's law constants. To test response time the ST-GC-ECD was periodically switched between tap and underground waters. Negligible carry-over of halogenated species and reproducibility better than 2% relative standard deviation (R.S.D.) can be achieved regardless of large concentration difference between the two sources, thus demonstrating applicability of the ST system for on-site monitoring. 相似文献
The Brownian-type molecular dynamics simulation is revisited and applied to study the thermal and geometric properties of four mono- and two polyvalent metallic clusters. For the thermal property, we report the specific heat at constant volume CV and study the solid-liquid-like transition by scrutinizing its characteristic. For the geometric property, we calculate the root mean square relative bond-length fluctuation delta as a function of increasing temperature. The thermal change in delta reflects the movement of atoms and hence is a relevant parameter in understanding the phase transition in clusters. The simulated results for the CV of alkali and aluminum clusters whose ground state structures exhibit icosahedral symmetry generally show one phase transition. In contrast, the tetravalent lead is quite often seen to exhibit two phase transitions, a premelting process followed by a progressive melting. In connection with the premelting scenario, it is found here that those (magic number) clusters identified to be of lesser stability (among other stable ones) according to the second energy difference are clusters showing a greater possibility of undergoing premelting process. This energy criterion applies to aluminum clusters nAl=28 and 38. To delve further into the thermal behavior of clusters, we have analyzed also the thermal variation of deltaT and attempted to correlate it with CV(T). It turns out that the premelting (if exist) and melting temperatures of the smaller size clusters (n less, similar 50) extracted from CV do not always agree quantitatively with that deduced from delta. 相似文献
The historical importance of pregastric enzymes in cheese-making is reviewed and the potential for extending their use is discussed in terms of requiring an understanding of their physicochemical parameters. Commericial extracts from the tongues and epiglotti of suckling lambs and calves and adult goats have been processed to yield partially purified samples of the primary pregastric lipase (PGL). The N-terminal sequence and molecular weight of lamb PGL have been determined.
The activity of lamb and goat PGLs against tributyrin has been determined over a range of pH and temperature values. Optimum conditions were pH 6.4, 43°C, and pH 6.0, 52°C, for lamb and goat PGL respectively. The possible influence of the development of a ruminant multi-chambered stomach on the difference in optimal temperature is discussed. A lengthening of the carboxylic acid chain of homoacid triglycerides causes a decrease in hydrolytic activity of lamb PGL but in all cases only a single free fatty acid was released. Against a series of 4-nitrophenylalkanoate esters, maximum activity was observed against the decanoate ester but, in contrast to hydrolysis of the acetate ester which exhibited full Michaelis-Menten kinetics with increasing substrate concentration, activity against the decanoate ester was restricted to the monomeric substrate. Taurocholate inhibits the activity of lamb PGL at concentrations >8 mM. Values of pK2 equal to 6.69 and 7.92 respectively have been determined for lamb PGL.
Attempts to interesterify coconut oil and cocoa butter, and tributyrin and tricaprylin, catalysed by calf PGL were unsuccessful, although positive results obtained using Candida cylindracea encourage further investigation of alternative methods for immobilizing the PGL. Finally, anhydrous milk fat has been hydrolysed by calf, lamb and goat PGLs and the differences in relative amounts of released free fatty acids have been used to explain the differences in taste which arise when Parmesan cheese is produced using different sources of PGL. 相似文献
A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film. 相似文献
Single nucleotide polymorphism (SNP) arrays were used to detect chromosomal regions with DNA copy number alterations. Current statistical methods for microarray-based comparative genomic hybridization (array-CGH) analysis generally assume certain relationships among adjacent markers on the same chromosome, and these assumptions may be questionable. For an SNP-array-based CGH study, multiple normal reference SNP arrays were collected. In order to utilize these normal reference SNP arrays, we derived an empirical distribution of signal ratios for each SNP marker. With an assumed threshold value for the overall error rate control and the defined signal ratio ranges for chromosomal amplification and deletion, we proposed a procedure to identify chromosomal alteration regions based on several bootstrapped one-sample t-tests and the false discovery rate control. When we have multiple arrays for different individuals with the same disease, our method can also be used to detect SNP markers for chromosomal alteration regions that are common among these individuals. We applied our method to a published SNP array data set for breast carcinoma cell lines. For an individual with breast cancer, numerous chromosomal alteration regions were identified. Compared to results of previous studies, our method identified more chromosomal alteration regions, with some being implicated in the literature to harbor genes associated with breast cancer. For multiple cancer arrays, our results suggested the existence of common chromosomal alteration regions. However, a high proportion of false positives also indicated that genetic variations among different individuals with breast cancer can be present. 相似文献
This paper describes the effect of particle size on the process of paraquat adsorption from aqueous solution onto an activated clay surface at 25 degrees C and initial pH 11.0. Measurements of the pore properties of the clay adsorbents with three different particle sizes (0.053-0.074 mm, 0.037-0.053 mm, and <0.037 mm) were carried out. The rates and isotherms of adsorption have been also investigated by batch methods under the controlled conditions. From the experimental results obtained, the adsorption process can be well described with the pseudo-second order model and Freundlich model for adsorption kinetics and adsorption isotherm, respectively. In addition, the effect of the particle size of the clay adsorbent on the adsorption kinetics was found to be of considerable significance; namely, the rate constant (k) of paraquat adsorption by the clay adsorbent decreased with increasing particle size. It was concluded that the pore properties (i.e., surface area and total pore volume) and particle size of the clay adsorbent played a significant role in determining adsorption capacity and adsorption rate, respectively. 相似文献