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11.
12.
Alain Adenier Eva Cabet-Deliry Sophie Griveau Florence Mercier Christine Vautrin-Ul 《Surface science》2006,600(21):4801-4812
This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur. 相似文献
13.
Marie Vahter 《应用有机金属化学》1994,8(3):175-182
Humans are exposed via air, water and food to a number of different arsenic compounds, the physical, chemical, and toxicological properties of which may vary considerably. In people eating much fish and shellfish the intake of organic arsenic compounds, mainly arsenobetaine, may exceed 1000 μg As per day, while the average daily intake of inorganic arsenic is in the order of 10–20 μg in most countries. Arsenobetaine, and most other arsenic compounds in food of marine origin, e.g. arsenocholine, trimethylarsine oxide and methylarsenic acids, are rapidly excreted in the urine and there seem to be only minor differences in metabolism between animal species. Trivalent inorganic arsenic (AsIII) is the main form of arsenic interacting with tissue constituents, due to its strong affinity for sulfhydryl groups. However, a substantial part of the absorbed AsIII is methylated in the body to less reactive metabolities, methylarsonic acid (MMA) and dimethylarsinic acid (DMA), which are rapidly excreted in the urine. All the different steps in the arsenic biotransformation in mammals have not yet been elucidated, but it seems likely that the methylation takes place mainly in the liver by transfer of methyl groups from S-adenosylmethionine to arsenic in its trivalent oxidation state. A substantial part of absorbed arsenate (AsV) is reduced to AsIII before being methylated in the liver. There are marked species differences in the methylation of inorganic arsenic. In most animal species DMA is the main metabolite. Compared with human subjects, very little MMA is produced. The marmoset monkey is the only species which has been shown unable to methylate inorganic arsenic. In contrast to other species, the rat shows a marked binding of DMA to the hemoglobin, which results in a low rate of urinary excretion of arsenic. 相似文献
14.
Renate Naumann Christine Alexander-Weber Friedrich G. K. Bauche 《Analytical and bioanalytical chemistry》1994,350(3):119-121
Thermogravimetric and X-ray powder diffraction analyses revealed that the pH reference material sodium tetraborate decahydrate (“borax”) is not a stable substance but, loosing some of its water of crystallization, transforms slowly into the pentahydrate. The connected pH changes of the solutions are opposite to and larger than, those expected according to the dilution value of the decahydrate as shown by differential potentiometric measurements. The transformation rate depends on the storing time in the closed original container, the time of and after the first exposure of the material to the atmosphere, the frequency of and the relative humidity during subsequent exposures, and the temperature. The transformation reaction is not understood in detail. However, the experiments showed that sodium tetraborate decahydrate is a reliable pH reference material, whose pH is constant within ΔpH=±0.005 within at least two years after preparation, even if occasionally exposed to the atmosphere. Further work will show whether this time limit can be somewhat extended. 相似文献
15.
Marie‐France Llauro Julien Loiseau Fernande Boisson Frdric Delolme Catherine Ladavire J. Claverie 《Journal of polymer science. Part A, Polymer chemistry》2004,42(21):5439-5462
Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004 相似文献
16.
Alex M. Green David G. Gevaux Christine Roberts Chris C. Phillips 《Physica E: Low-dimensional Systems and Nanostructures》2004,20(3-4):531
In this paper we outline the use of resonant-cavity enhancement for increasing the exterior coupling efficiency of photodetectors and light-emitting diodes (LEDs) in the mid-infrared (MIR) spectral region. This method is potentially very important in the MIR because encapsulation is not presently feasible due to the lack of suitable materials. Among other potential applications, resonant-cavity-enhanced (RCE) photodetectors and LEDs could be particularly suitable for greenhouse gas detection because of their ‘pre-tunable’ spectrally narrowed resonantly enhanced peaks. We also present the optical characterization of an InAs RCE photodetector aimed at the detection of methane gas (λ≈3.3 μm), and an InAs/InAs0.91Sb0.09 resonant-cavity LED (RCLED) aimed at carbon dioxide gas (λ≈4.2 μm). The high peak responsivity of the RCE photodetector was 34.7 A/W at λ=3.14 μm, and the RCLED peaked at λ=3.96 μm. These are among the longest operating wavelengths for III–V RCE photodetectors and RCLEDs reported in the literature. 相似文献
17.
Albert Cohen Sidi Mahmoud Kaber Siegfried Mü ller Marie Postel. 《Mathematics of Computation》2003,72(241):183-225
The use of multiresolution decompositions in the context of finite volume schemes for conservation laws was first proposed by A. Harten for the purpose of accelerating the evaluation of numerical fluxes through an adaptive computation. In this approach the solution is still represented at each time step on the finest grid, resulting in an inherent limitation of the potential gain in memory space and computational time. The present paper is concerned with the development and the numerical analysis of fully adaptive multiresolution schemes, in which the solution is represented and computed in a dynamically evolved adaptive grid. A crucial problem is then the accurate computation of the flux without the full knowledge of fine grid cell averages. Several solutions to this problem are proposed, analyzed, and compared in terms of accuracy and complexity.
18.
19.
Summary NAD(P)H fluorescence emission spectra are recorded from single living cells, by a recently developed multichannel microspectrofluorometric technique, in correlation with the intracellular microelectrophoretic addition of substrate (i. e., glucose-6-P). These spectra may be used as a reference basis in establishing the critical parameters to be followed when the same studies are extended to a variety of cells, submitted to various drug effects or physical treatments. The sum-spectra corresponding to channel by channel (wavelength by wavelength) summation of spectra obtained from various cells within a series, before and after addition of substrate, and their difference spectrum may be normalized and evaluated comparatively. The NAD(P)H emission maximum prior to addition of substrate seems to present a mixture of dehydrogenase-bound and free coenzyme. There is a suggestion that immediately after substrate, i. e., at 5 sec, an increase in free NADH is first observed. While the overall changes in fluorescence intensity associated with substrate are quite large (50–150% increase), the counts (i. e., an expression of photons) associated with shifts in the emission maximum (free vs. bound NAD(P)H changes) are at times barely above noise. Rapid microspectrofluorometry provides in principle the most direct approach for the identification of coenzyme bound to various dehydrogenases in single living cells, but further improvements in spectral resolution and signal-to-noise ratio are required, for a better definition of the spectral shifts which may be observed.
Zusammenfassung Mit Hilfe einer kürzlich entwickelten Mehrkanal-Mikrospektrofluorometer-Methode wurden von einzelnen lebenden Zellen nach intrazellulär mikroelektrophoretischer Substratzugabe (z. B. Glucose-6-P) NAD(P)H Fluoreszenz-Emissionsspektren aufgenommen. Diese Spektren können als Vergleichsbasis bei der Festsetzung der entscheidenden Parameter verwendet werden, wenn die gleichen Untersuchungen auf eine Reihe von Zellen ausgedehnt werden sollen, die verschiedenen Medikamenteffekten oder physikalischer Behandlung ausgesetzt werden. Die Summenspektren, die der kanalmäßigen (wellenlängenmäßigen) Summierung der Spektren von verschiedenen Zellen innerhalb einer Serie, vor und nach Substratzugabe entsprechen, sowie ihre Differenzspektren können normalisiert und vergleichsweise ausgewertet werden. Das NAD(P)H-Emissionsmaximum vor der Substratzugabe scheint ein Gemisch von freiem und dehydrogenasegebundenem Coenzym darzustellen. Unmittelbar nach Substratzugabe (d. h. nach 5 sec) ist ein Anstieg an freiem NADH das erste Mal zu beobachten. Während die mit dem Substrat einhergehenden Gesamtveränderungen der Fluoreszenzintensität recht groß sind (50–150% Anstieg), sind die Impulse (als Effekt der Photonen), die mit einer Verschiebung im Emissionsmaximum verbunden sind (Veränderungen von freiem und gebundenem NAD(P)H) zu manchen Zeiten kaum höher als das Rauschen. Die rasche Mikrospektrofluorometrie stellt im Prinzip die direkteste Methode zur Identifizierung von Coenzymen dar, die an verschiedenen Dehydrogenasen in einzelnen lebenden Zellen gebunden sind. Weitere Verbesserungen der Spektralauflösung und der Empfindlichkeit (signal-to-noise ratio) sind notwendig, um die Spektralverschiebungen, die beobachtet werden, besser auswerten zu können.相似文献
20.
Demetrio De Calle García M. Reichenbächer Klaus Danzer Christian Hurlbeck Christine Bartzsch Karl-Heinz Feller 《Analytical and bioanalytical chemistry》1998,360(7-8):784-787
The extraction of wine aroma compounds was studied by direct-SPME (DI/SPME), headspace-SPME (HS/SPME) and multiple-headspace-extraction-SPME
(MHE/SPME). The aromagrams obtained by HS/SPME-CGC were evaluated with chemometrical methods for the varietal classification
of wines.
Received: 25 July 1997 / Revised: 24 September 1997 / Accepted: 7 October 1997 相似文献