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161.
Hanan Alatawi Anna Hogan Ibtihaj Albalawi Emma O'Sullivan-Carroll Yineng Wang Eric Moore 《Electrophoresis》2022,43(7-8):857-864
Paracetamol (PAC) is one of the most extensively used analgesics and antipyretic drugs to treat mild and moderate pain. P-aminophenol (PAP), the main hydrolytic degradation product of PAC, can be found in environmental water. Recently, CE has been developed for the detection of a wide variety of chemical substances. The purpose of this study is to develop a simple and fast method for the detection and separation of PAC and its main hydrolysis product PAP using CE and microchip electrophoresis with capacitively coupled contactless conductivity detection. The determination of these compounds using microchip electrophoresis with capacitively coupled contactless conductivity detection is being reported for the first time. The separation was run for all analytes using a BGE (20 mM β-alanine, pH 11) containing 14% (v/v) methanol. The RSDs obtained for migration time were less than 4%, and RSDs obtained for peak area were less than 7%. The detection limits (S/N = 3) that were achieved ranged from 0.3 to 0.6 mg/L without sample preconcentration. The presented method showed rapid analysis time (less than 1 min), high efficiency and precision, low cost, and a significant decrease in the consumption of reagents. The microchip system has proved to be an excellent analytical technique for fast and reliable environmental applications. 相似文献
162.
Mariz R Poater A Gatti M Drinkel E Bürgi JJ Luan X Blumentritt S Linden A Cavallo L Dorta R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(48):14335-14347
A family of chiral C(2)-symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X-ray crystallographic studies of all ligands and some of their rhodium complexes. Their synthesis, optical purity, electronic properties, and catalytic behavior in the prototypical rhodium-catalyzed 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one are presented through an in depth study of this ligand class. Density functional theory calculations on the step of the catalytic cycle that determines the enantioselectivity are presented and reinforce the first hypothetical explanations for the high levels of asymmetric induction observed. 相似文献
163.
János Kristóf Ray L. Frost Sara J. Palmer Erzsébet Horváth Emma Jakab 《Journal of Thermal Analysis and Calorimetry》2010,100(3):961-966
Dynamic and controlled rate thermal analysis (CRTA) has been used to characterise alunites of formula [M(Al)3(SO4)2(OH)6] where M+ is the cations K+, Na+ or NH4 +. Thermal decomposition occurs in a series of steps: (a) dehydration, (b) well-defined dehydroxylation and (c) desulphation. CRTA offers a better resolution and a more detailed interpretation of water formation processes via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of water formation reveal the subtle nature of dehydration and dehydroxylation. 相似文献
164.
Edwards EL Rodrigues JA Ferreira J Goodall DM Rauter AP Justino J Thomas-Oates J 《Electrophoresis》2006,27(11):2164-2170
Genista tenera is endemic to the Portuguese island of Madeira, where an infusion of the aerial parts of the plant is used in folk medicine as an antidiabetic agent. Consequently the medicinal properties of the secondary metabolites of this plant have been the subject of an ongoing study. A recently reported LC-MS method using a 100 min separation allowed identification of five flavonoid components in an extract of the aerial parts of this plant. In order to obtain additional information on the range and complexity of the plant's secondary metabolite components a CE-MS method has been developed and applied for the analysis of an extract of G. tenera. Twenty-six different components are distinguished in an analysis time of only 10 min. Results demonstrate that CE-MS/MS rapidly generates data complementary to those obtainable by LC-MS/MS and is particularly suited to the analysis of plant metabolites where concentration is not limiting. 相似文献
165.
Pearson EL Kwan LC Turner CI Jones GA Willis AC Paddon-Row MN Sherburn MS 《The Journal of organic chemistry》2006,71(16):6099-6109
High cis (i.e., endo) diastereoselectivities are witnessed in heat-promoted intramolecular Diels-Alder (IMDA) reactions of ethylene-tethered hexadienyl acrylates. The cis stereoselectivity is improved by promotion with Et2AlCl. The first examples of Et2AlCl catalyzed intramolecular Diels-Alder reactions of ester-activated dienophiles are reported. In contrast, the corresponding benzo-tethered hexadienyl acrylates undergo moderately trans (i.e., exo) selective IMDA reactions. Very high trans stereoselection is obtained upon promotion with ATPH. The outcomes of these reactions are essentially insensitive to dienophile (C10) geometry and substitution. DFT (B3LYP/6-31+G(d)) computed cis/trans product distributions-based on Boltzmann transition structure populations-are in good agreement with the experimental results. These computational investigations provide useful insights into the origins of stereoselection in these systems. The stereoselectivity exhibited by the ethylene-tethered hexadienyl acrylates is ascribed to stabilizing secondary orbital interactions at play in the cis-transition structures (TSs). In the benzo-tethered series, this effect is overridden by stabilizing pi-conjugative interactions, between the benzo moiety and the 1,3-diene component, which are stronger in trans TSs, compared to the cis TSs. The computed TS geometries generally exhibit advanced peripheral bond forming asynchronicity, with the tether carbonyl group in conjugation with the dienophile. Such TS features significantly weaken the stereodirecting influence of terminal dienophile substituents. 相似文献
166.
Fox OD Cookson J Wilkinson EJ Drew MG MacLean EJ Teat SJ Beer PD 《Journal of the American Chemical Society》2006,128(21):6990-7002
Polymetallic nanodimensional assemblies have been prepared via metal directed assembly of dithiocarbamate functionalized cavitand structural frameworks with late transition metals (Ni, Pd, Cu, Au, Zn, and Cd). The coordination geometry about the metal centers is shown to dictate the architecture adopted. X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometries favor hexanuclear "molecular loop" structures. Both classes of complex are sterically and electronically complementary to the fullerenes (C(60) and C(70)). The strong binding of these guests occurred via favorable interactions with the sulfur atoms of multiple dithiocarbamate moieties of the hosts. In the case of the tetrameric copper(II) complexes, the lability of the copper(II)-dithiocarbamate bond enabled the fullerene guests to be encapsulated in the electron-rich cavity of the host, over time. The examination of the binding of fullerenes has been undertaken using spectroscopic and electrochemical methods, electrospray mass spectrometry, and molecular modeling. 相似文献
167.
Panagiotou and Stufler recently proved an important fact on their way to establish the scaling limits of random Pólya trees: a uniform random Pólya tree of size consists of a conditioned critical Galton–Watson tree and many small forests, where with probability tending to one, as tends to infinity, any forest , that is attached to a node in , is maximally of size . Their proof used the framework of a Boltzmann sampler and deviation inequalities.In this paper, first, we employ a unified framework in analytic combinatorics to prove this fact with additional improvements for , namely . Second, we give a combinatorial interpretation of the rational weights of these forests and the defining substitution process in terms of automorphisms associated to a given Pólya tree. Third, we derive the limit probability that for a random node the attached forest is of a given size. Moreover, structural properties of those forests like the number of their components are studied. Finally, we extend all results to other Pólya structures. 相似文献
168.
Comparatively little is known about commutative rings of partial differential operators, while in the ordinary case, concrete examples and an algebraic(-geometric) structure can be algorithmically determined for large classes. In this note, by the calculation of the partial μ-shifted differential resultant which we defined in a previous paper, we produce algebraic equations of spectral surfaces for commutative rings in two variables, and Darboux transformations of Airy-type operators that correspond to morphisms of surfaces. There are, however, many elementary differential-algebraic statements that we only observe experimentally, thus we offer open questions which seem to us quite significant in differential algebra, and access to Mathematica code to enable further experimentation. 相似文献
169.
Gatti M Drinkel E Wu L Pusterla I Gaggia F Dorta R 《Journal of the American Chemical Society》2010,132(43):15179-15181
We present the first productive ring-closing metathesis reaction that leads to the construction of cyclic alkenyl bromides. Efficient catalysis employing commercially available Grubbs II catalyst is possible through appropriate modification of the starting bromoalkene moiety. 相似文献
170.
Domínguez M Alvarez R Borràs E Farrés J Parés X de Lera AR 《Organic & biomolecular chemistry》2006,4(1):155-164
(R)-all-trans-3-hydroxyretinal 1, (S)-all-trans-4-hydroxyretinal and (R)-all-trans-4-hydroxyretinal have been synthesized stereoselectively by Horner-Wadsworth-Emmons and Stille cross-coupling as bond-forming reactions. The CBS method of ketone reduction was used in the enantioface-differentiation step to provide the precursors for the synthesis of the 4-hydroxyretinal enantiomers. The kinetic constants of Xenopus laevis ADH8 with these retinoids have been determined. 相似文献