Analysis of methyl- and ethylmercury (MM and EM) halides in biological and environmental samples is generally performed by gas chromatography with electron capture detection. Tedious sample work-up protocols and poor chromatographic response (using packed columns) have, however, shown the need for the development of new methods in this field. This paper reports a sensitive method, free from these deficiencies, for the determination of methyl- and ethylmercury. The organomercury compounds (MM and EM) are first released from the sample matrix, by the combined action of acidic potassium bromide and cupric ions, and then extracted into dichloromethane. The initial extracts are subjected to thiosulfate clean-up and the organomercury species are isolated as their chloride derivatives by addition of cupric chloride, and subsequent extraction into a small volume of organic solvent. Capillary GC coupled with atomic fluorescence detection provided excellent separation efficiencies for methyl- and ethylmercury and proved to be a very selective and sensitive technique. The absolute detection limit for both MM and EM was found to be 0.2 pg. 相似文献
A simple preparation of the chloronitrosylcarbonylmolybdenum(0) complexes Mo(NO)(CO)4(AlCl4) and MoCl(NO)(CO)2(PPh3)2 is described. The homogeneous system MoCl(NO)(CO)2(PPh3)2/RAlCl2 (R = Et, Me) represents a new highly active long-living catalyst for the metathesis of 2-pentene. 相似文献
Formation of CoAl3Cl11 at higher Al2Cl6 Pressures The reaction of CoCl2,f with Al2Cl6,g (≈ 3 atm) is investigated considering every component of the gas phase (Al2Cl6, AlCl3, Al3Cl9, CoAlCl5, CoAl2Cl8, CoAl3Cl11) and the deviation from the ideal behaviour. The conclusion is derived that at 600 K from CoCl2,s and larger pressures of Al2Cl6 besides CoAl2Cl8 a small amount of CoAl3Cl11 is formed. 相似文献
In a comparative study the in vitro corrosion behavior of a selection of nickel- and cobalt-based alloys for application in
dentistry containing no noble metals was studied with slow scan cyclic voltammetry. The obtained breakthrough potentials,
the repassivation behavior and further typical features of the cyclic voltamograms are correlated with the chemical composition
as measured with electron beam microanalysis. Surface inhomogenities detected with the latter method are discussed with respect
to the electrochemical behavior. For all alloys stabilities in terms of breakthrough potential superior to previously reported
data for nickel-base alloys are found. 相似文献
We studied the spontaneous emulsification and droplet growth mechanism in trans-anethol/water/ethanol solutions, also known as the beverage ouzo, using dynamic light scattering spectroscopy. This simple ternary mixture is a generic example of a system that forms microemulsions spontaneously when brought into the two-phase region. The volume fraction of the dispersed phase was found to profoundly affect the growth rates of the droplets, which is a new finding that has not been predicted by the Lifshitz-Slyozov-Wagner theory. Time-dependent measurements show that the droplet growth is governed by Ostwald ripening (OR), and no coalescence was observed. Furthermore, the OR rates increase with increasing oil concentration at low alcohol content. We attribute this behavior to enhanced droplet-droplet interactions. At high ethanol concentrations, we found that the measured rates decreased as the oil concentration increased. The OR growth mechanism completely correlates with changes in droplet size. The kinetics of droplet growth shows that the ripening has a saturation limit at a droplet radius of about 1.5 mum. Thus, formed emulsions remain stable for months. 相似文献
Repeatable ring expansions by [2,3]-sigmatropic shifts in cyclic allylsulfonium allylides; synthesis of medium- and large-sized thiacycles Allylation of a 2-vinyl thiacyclus with allyl bromide in 2,2,2-trifluoroethanol followed by ylide generation by use of aqueous potassium hydroxide results in a [2,3]-sigmatropic rearrangement with formation of a new 2-vinyl thiacyclus enlarged by three carbon atoms (Scheme 1). In this way, starting from the 5-membered ring 1 , a series of four ring enlargement sequences leads to the 17-membered thiacycles 9 and 10 via the 8-, 11- and 14-membered rings 4 , 7 and 8 (Scheme 2). 相似文献
It is the aim of this paper to introduce two new notions of discrepancy. They are defined by the formulas $$\begin{gathered} \Delta _N^r \left( {\omega ;f} \right) = \mathop {\sup }\limits_{\left| z \right| = r} \left| {\left( {{1 \mathord{\left/ {\vphantom {1 N}} \right. \kern-\nulldelimiterspace} N}} \right)\sum\limits_{n = 1}^N {f\left( {z e^2 \pi i\omega \left( n \right)} \right)} - f\left( 0 \right)} \right|, and \hfill \\ \delta _N^r \left( {\omega ;f} \right) = \mathop {\sup }\limits_{\left| z \right| = r} \left| {\left( {{1 \mathord{\left/ {\vphantom {1 N}} \right. \kern-\nulldelimiterspace} N}} \right)\sum\limits_{n = 1}^N {f\left( {z \omega \left( n \right)} \right)} \cdot z - \int\limits_0^z {f\left( \zeta \right)d\zeta } } \right|, \hfill \\ \end{gathered} $$ wheref is a holomorphic function defined in the unit disc withf(k)(0)≠0 for allk∈?,r<1 is a positive number, and ω is a sequence in [0, 1]. The first of these discrepancies can be generalized for multidimensional sequences. ω is uniform distributed if and only if limN→∞ΔNr(ω;f)=0 resp. limN→∞δNr(ω;f)=0. These results are proved in a quantitative way by estimating the classical discrepancyDN(ω) by means ofΔNr(ω;f) and δNr(ω;f): $$\begin{gathered} \Delta _N^r \left( {\omega ;f} \right) \ll D_N \left( \omega \right) \ll \Phi \left( {\Delta _N^r \left( {\omega ;f} \right)} \right), \hfill \\ \delta _N^r \left( {\omega ;f} \right) \ll D_N \left( \omega \right) \ll \Psi \left( {\delta _N^r \left( {\omega ;f} \right)} \right). \hfill \\ \end{gathered} $$ The functions Φ and Ψ only depend onf andr. These estimations are based on the inequalities ofKoksma-Hlawka andErdös-Turán. 相似文献
The diphosphate ester (ThDP) of thiamin (vitamin B1) is an important cofactor of enzymes within the carbohydrate metabolism. The initial reaction step shared by all ThDP-dependent enzymes is the deprotonation of the C2–H of the thiazolium ring. The replacement of the 4′-amino group by a hydroxyl one in the pyrimidine ring leads to the oxy-ThDP analogue which is known as an antagonist in thiamin catalysis.
Ab initio and DFT calculations on the MP2/6-31G* and B3LYP/6-31G* level were performed to study the proton relay function in thiamin and oxythiamin systems. Both MP2 and B3LYP calculations show significant differences of the reaction coordinate of the ylide formation in the systems. Tautomers, protonated and deprotonated species of both systems show different trends regarding their stability. The influence of correlation effects on the results is discussed by comparison with the HF-SCF/6-31G* data. Frequency calculations on the B3LYP/6-31G* level were performed to characterize the minima and transition state structures, respectively. 相似文献
Reaction of ,,,-[9]annulene anion () with electrophiles (-) leads to substituted ,,,-1,3,5,7-cyclononatetraenes (-) which are precursors for the preparation of 10- and 10,10′-donor-substituted nonafulvenes (e.g. ). The influence of solvent and temperature on the 1H-nmr spectra of the nonafulvenes - has been investigated. 相似文献
Several mono- and bicyclic 6-methoxy-2-pyrones having substituents at C4 and C5 can be prepared regiospecifically by either of two routes: (1) regiospecific construction of a glutaconic half-ester followed by dehydrative cyclization, and (2)regiospecific Friedel-Crafts acylation of 6-methoxy-2-pyrones at C5. These pyrones undergo clean and regiospecific Diels-Alder cycloadditions with various unsymmetrical dienophiles, e.g., quinones, unsaturated esters, etc, with subsequent loss of carbon dioxide. In this manner several polycyclic aromatic natural products have been prepared such as chrysophanol, helminthosporin, pachybasin, 2-acetylemodin and the purported structure for orientalone. The utility of this approach for the synthesis of the anthracyclines is demonstrated by its use in the preparation of various tetracyclic intermediates for anthracycline synthesis. 相似文献