The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to one of the intermediates, but we now highlight the interplay and competition between them.The combination of potassium tert-butoxide and triethylsilane provides simultaneous access to multiple reactive intermediates, radicals, H-atom donors, hydride donors and electron donors, giving scope for unprecedented reaction outcomes.相似文献
A new and fast high-performance liquid chromatography (HPLC) method using technology of fused-core columns for separation of fenoxycarb and cis-, trans-permethrin has been developed and used for their determination in antiparasitic veterinary shampoo. Separation of insecticides and internal standard sudan II was achieved on the fused-core column Ascentis Express RP-Amide (100 × 3.0 mm), particle size 2.7 μm, with mobile phase acetonitrile/water (55:45, v/v) at a flow rate of 1.0 mL min−1 and at temperature 60 °C. The detection wavelength of detector was set at 225 nm for both compounds and internal standard sudan II. Under the optimum chromatographic conditions standard calibration curves were measured with good linearity [r2 = 0.99991 for fenoxycarb, r2 = 0.99987 for trans-permethrin, and r2 = 0.99984 for cis-permethrin (n = 8)]. Commercial samples of antiparasitic veterinary shampoo were extracted with ethanol in ultrasound bath for 5 min. A 2-μL sample volume of the filtered solution was directly injected into the HPLC system. Accuracy of the method defined as a mean recovery of insecticides from shampoo matrix was in the range 100.43–103.85 % for both insecticides.
The present study focuses on predicting the concentration of intracellular storage polymers in enhanced biological phosphorus removal (EBPR) systems. For that purpose, quantitative image analysis techniques were developed for determining the intracellular concentrations of PHA (PHB and PHV) with Nile blue and glycogen with aniline blue staining. Partial least squares (PLS) were used to predict the standard analytical values of these polymers by the proposed methodology. Identification of the aerobic and anaerobic stages proved to be crucial for improving the assessment of PHA, PHB and PHV intracellular concentrations. Current Nile blue based methodology can be seen as a feasible starting point for further enhancement. Glycogen detection based on the developed aniline blue staining methodology combined with the image analysis data proved to be a promising technique, toward the elimination of the need for analytical off-line measurements. 相似文献
Various methods which lead to the control of molecular weight and polydispersities, and which allow for the preparation of block copolymers by radical polymerization are discussed. Thermal polymerizationof styrenes in the presence of stable radicals, polymerization of vinyl acetate and methyl methacrylate in the presence of chromium complexed by macrocyclic ligands polymerization of vinyl acetate initiated by organoaluminum compounds complexed by dipyridyl and activated by stable radicals, as well as in the presence of phosphites, are described in detail. 相似文献
The new ligand HPDO3MA [(R,R,R,R)-10-(2-hydroxypropyl)-α,α′,α′′-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid] was designed to combine and optimize the chemical properties of the macrocyclic ligands HPDO3A and DOTMA. The presence of the methyl groups on the acetic pendant arms of HPDO3A is expected to rigidify the structure of the ligand and favor an increase of the kinetic inertness of the Ln complexes. 1H NMR spectra of Eu(HPDO3MA) displayed the presence of two pairs of diastereoisomers: SAP (square antiprismatic) and TSAP (twisted square antiprismatic) isomers (56 and 44 %, respectively). In addition, 1H and 17O relaxometric NMR studies of Gd(HPDO3MA) showed approximately a 10 % increase in relaxivity and a faster water exchange rate with respect to Gd(HPDO3A). Moreover, a detailed chemical exchange saturation transfer (CEST) characterization of Yb(HPDO3MA) displayed a sensitivity about two times larger than that of Yb(HPDO3A) both in phantom and in cell labeling experiments. Finally, the kinetic inertness of Yb(HPDO3MA) was measured to be twice as high as that of Yb(HPDO3A), with a dissociation half-life at physiological pH of about 2500 years. 相似文献
Complex data such as those where each statistical unit under study is described not by a single observation (or vector variable), but by a unit-specific sample of several or even many observations, are becoming more and more popular. Reducing these sample data by summary statistics, like the average or the median, implies that most inherent information (about variability, skewness or multi-modality) gets lost. Full information is preserved only if each unit is described by a whole distribution. This new kind of data, a.k.a. “distribution-valued data”, require the development of adequate statistical methods. This paper presents a method to group a set of probability density functions (pdfs) into homogeneous clusters, provided that the pdfs have to be estimated nonparametrically from the unit-specific data. Since elements belonging to the same cluster are naturally thought of as samples from the same probability model, the idea is to tackle the clustering problem by defining and estimating a proper mixture model on the space of pdfs. The issue of model building is challenging here because of the infinite-dimensionality and the non-Euclidean geometry of the domain space. By adopting a wavelet-based representation for the elements in the space, the task is accomplished by using mixture models for hyper-spherical data. The proposed solution is illustrated through a simulation experiment and on two real data sets. 相似文献
This paper describes a Brazilian interlaboratory program study on anion measurement in synthetic water. The program described is promoted regularly since 2007 and recommended the use of ion chromatography as analytical technique for all participant laboratories. Two samples (X and Y) with different anion (fluoride, chloride, nitrite-N, nitrate-N, sulfate and phosphate-P) concentration levels were twice distributed in 2011. Each sample on each round had the homogeneity, and the stability tested for a period of 15 days. Upon ensuring the homogeneity and stability, the samples were distributed to 39 laboratories located around the country. The aim of this study was to verify the laboratories’ precision and to establish the measurement comparability among Brazilian laboratories that routinely use ion chromatography for water sample analysis. It was also possible to identify the most frequent sources of systematic and random errors for each measured anion, related to the ion chromatography technique. Some specific metrological issues related to the geographical region are discussed. 相似文献
We have investigated the formation and development of memory states in polymer dispersed liquid crystals induced by the application of a strong electric field. Both the optical transmittance and polarization field have been followed as functions of time. We have been able to distinguish between the contributions to the memory states arising from the surface anchoring of the liquid crystal at the droplet interface and from the electrical reorientation of the mesogenic molecules. The dependence of both residual transmittance and polarization field on temperature is reported and a simple model is proposed. 相似文献
With the public availability of large data sources such as ChEMBLdb and the Open PHACTS Discovery Platform, retrieval of data sets for certain protein targets of interest with consistent assay conditions is no longer a time consuming process. Especially the use of workflow engines such as KNIME or Pipeline Pilot allows complex queries and enables to simultaneously search for several targets. Data can then directly be used as input to various ligand- and structure-based studies. In this contribution, using in-house projects on P-gp inhibition, transporter selectivity, and TRPV1 modulation we outline how the incorporation of linked life science data in the daily execution of projects allowed to expand our approaches from conventional Hansch analysis to complex, integrated multilayer models. 相似文献