This work presents the immobilization of cinchona squaramide organocatalysts on poly(glycidyl methacrylate) solid supports. Preparation of the well-defined monodisperse polymer microspheres was facilitated by comprehensive parameter optimization. By exploiting the reactive epoxy groups of the polymer support, three amino-functionalized cinchona derivatives were immobilized on this carrier. To explore the effect of the amino linker, these structurally varied precatalysts were synthesized by modifying the cinchona skeleton at different positions. The catalytic activities of the immobilized organocatalysts were tested in the Michael addition of pentane-2,4-dione and trans-β-nitrostyrene with excellent yields (up to 98 %) and enantioselectivities (up to 96 % ee). Finally, the catalysts were easily recovered five times by centrifugation without loss of activity. 相似文献
In voltammetric analysis the signal—in most cases—depends on transport processes. When getting concentration values of analytes from voltammetric calibrating curves, it is expected that the mass transport characteristics in sample solutions and in calibrating standards are identical. Standard addition methods are used in analytical practice when making calibrating standard with transport properties matching that of the samples would be difficult. Voltammetric measurements can also be carried out in soil—in sediment—or in gel samples. The mass transport conditions in these media, however, can considerably differ from those existing in aqueous solutions. The application of standard addition technique, however, is not an option there. In this work, a glassy carbon electrode was applied with a built-in diffusion layer on its measuring surface and chronoamperometric measurements were carried out. The current–time transients taken in aqueous solution and in tortuous, diffusion-hindered media were compared. Ascorbic acid and iodine as analytes as well as silica sand sediments and green pepper pulps as tortuous matrices were used. It was proved that if the modified electrode is used for analysis, then short time chronoamperometric transients taken in tortuous media can be evaluated by calibration data taken in aqueous standard solutions. 相似文献
Following the decarboxylation of acetoacetic acid by heating and the separation of acetone from milk matrix by steam distillation, acetone was allowed to react with bromine in the presence of nitric acid, causing the formation of bromoacetone and bromide; the latter was then quantified by means of a suitable ion-selective electrode applying the calibration principle. Based on checking reproducibility and on comparative analyses performed by a widely accepted photometric method, the potentiometric method developed was found to be adequate for the determination of the oxidized ketone bodies. 相似文献
Interactions among residues together with their interactions with the surrounding medium determine the unique structure of
globular proteins. An algorithm was recently developed to locate residues participating in cooperative long-range interactions,
called stabilization center residues, that are primarily responsible for preventing the decay of the 3D structure. While our
statistical analysis showed that interactions of stabilization center residues hardly influence the formation of the various
secondary structure elements, the distribution of the stabilization center residues is rather uneven among the secondary structure
elements. Here we analyzed the frequency and distribution of the stabilization center residues and their interacting pairs
in secondary structure classes to learn about the effect of secondary structure on the formation and properties of stabilization
centers and about the types of interactions responsible for stabilization of proteins of various secondary structure classes.
It was found that residues from the same secondary structure tend to interact with each other in the stabilization centers
of all classes. It is also suggested that the folding-unfolding equilibrium is governed by different principles for class
all-α than for the rest of the classes.
Received: 24 April 1998 / Accepted: 17 September 1998 / Published online: 7 December 1998 相似文献
In the course of our recent synthetic activity in the area of ring closure reactions we have found that relatively little had been published on azolopyridazines and related compounds, and this circumstance prompted us to explore novel pathways to such ring systems. In the present short review three such approaches from our laboratory leading to various fused azoles are discussed. 相似文献
Synthesis of new 2,3-diaryl-3H-pyrrolo[2,3-c]isoquinoline derivatives has been elaborated starting from isoquinoline-3-amine. Buchwald–Hartwig arylation and subsequent iodination in position 4 afforded 3-arylamino-4-iodoisoquinolines. These compounds were subjected to Sonogashira cross-coupling reactions with some selected acetylenes, and the resulting coupled products underwent cyclization in the presence of tetrabutylammonium fluoride to give title derivatives. 相似文献
The purpose of the study was to analyze the correlation between the quantity of eluted monomers from dental resin-based composite using reverse-phase HPLC and the degree of conversion (DC) using micro-Raman spectroscopy, and to evaluate the influence of the energy of polymerization delivered on the composite material and the applied resin layer thickness on these properties. There was direct proportion in degree of conversion and inverse proportion in monomer elution when the energy of light polymerization was increased from 20 to 40 J cm−2; however, further increase in energy density did not influence significantly the DC and the elution of monomers. Investigating the depth of cure significant differences could be measured both in DC and the elution of monomers. 1 mm layer increment up to 3 mm from the top led to 10 % decrease in DC and 30–35 % increase in monomer elution. Further increase in depth from 3 to 4 mm caused 30 % drop in DC and 55 % increase in the amount of leached monomers. The overall result of the findings indicates that direct correlation exists between DC of composite and the elution of unreacted monomers.
Crystallization kinetics of β-nucleated isotactic polypropylene (β-iPP) under isothermal conditions were investigated by differential
scanning calorimetry. iPP was nucleated by a trisamide derivative, namely tris-2,3-dimethyl-hexylamide of trimesic acid (TATA).
In the presence of TATA possessing dual nucleating ability, the formation of the α- and β-form occurs simultaneously. An isothermal
stepwise crystallization method is suggested in this study, which can separate the crystallization process of β- and α-iPP
and consequently their crystallization kinetics can be evaluated separately. The results indicated that the mechanism of crystallization
changes in temperature especially in the vicinity of the upper critical temperature of the formation of the β-phase. In addition,
it was found that the ratio of the growth rates of β- and α-modification determines the characteristics of crystallization
and influences the apparent rate constant of crystallization of both polymorphs. 相似文献