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981.
In the characterization of materials by field-flow fractionation (FFF), the experienced analyst understands the importance of incorporating additives in the carrier liquid that minimize or eliminate interactions between the analyte and accumulation wall, particularly in aqueous systems. However, as FFF is applied to more difficult samples, such as those with high surface energies, it is increasingly difficult to find additives that completely eliminate particle-wall interactions. Furthermore, the analyst may wish to use specific conditions that preserve the high surface energy of particles, to study their interaction with other materials through their behavior in the FFF channel. With this in mind, Williams and co-workers developed a model that quantifies the effect of particle-wall interactions in FFF using an empirically determined interaction parameter. In this work, the model is evaluated for the application of flow FFF in carrier liquids of low ionic strength, where particle-wall interactions are magnified. The retention of particles ranging in size from 64 to 1000 nm is measured using a wide range of field strengths and retention levels. The model is found to be generally valid over the entire range, except for minor discrepancies at lower levels of retention. Although retention levels are dramatically affected by particle-wall interactions, the point of steric inversion (500 nm), where the size-based elution order reverses, is not affected. When particle-wall interactions are not accounted for, they lead to a bias in particle sizes calculated from standard retention theory of up to 70%. The model can also be used to refine the measurement of channel thickness, which is important for the accurate conversion of retention parameters to particle sizes. In this work, for example, errors in channel thickness led to systematic errors on the order of 10% in particle diameter. 相似文献
982.
In-channel electrochemical detection for microchip capillary electrophoresis using an electrically isolated potentiostat 总被引:3,自引:0,他引:3
A new electrode configuration for microchip capillary electrophoresis (CE) with electrochemical (EC) detection is described. This approach makes it possible to place the working electrode directly in the separation channel. The "in-channel" EC detection was accomplished without the use of a decoupler through the utilization of a specially designed, electrically isolated potentiostat. The effect of the working electrode position on the separation performance (in terms of plate height and peak skew) of poly(dimethylsiloxane)-based microchip CEEC devices was evaluated by comparing the more commonly used end-channel configuration with this new in-channel approach. Using catechol as the test analyte, it was found that in-channel EC detection decreased the total plate height by a factor of 4.6 and lowered the peak skew by a factor of 1.3. A similar trend was observed for the small, inorganic ion nitrite. Furthermore, a fluorescent and electrochemically active amino acid derivative was used to directly compare the separation performance of in-channel EC detection to that of a widely used laser-induced fluorescence (LIF) detection scheme. In this case, it was found that the plate height and peak skew for both detection schemes were essentially equal, and the separation performance of in-channel EC detection is comparable to LIF detection. 相似文献
983.
An aspartame optical biosensor has been fabricated by employing a bienzyme system composed of alpha-chymotrypsin and alcohol oxidase immobilized onto an eggshell membrane and an oxygen-sensitive optode membrane as the transducer. The detection schemes involve the enzymatic reactions of aspartame leading to the depletion of the oxygen level of the medium with a concomitant enhancement of the fluorescence intensity of the oxygen-sensitive membrane. The scanning electron and transmission electron micrographs show the microstructure of the eggshell membrane which is successfully immobilized with bienzyme. Using this novel immobilization technique, the aspartame biosensor shows extremely good stability with a shelf life of at least 8 months. The rate change of the fluorescence intensity in 4 min is found to be linearly related to the concentration of aspartame. The useful analytical working range of the biosensor is from 0.056 to 3.07 mM aspartame. The effects of temperature, pH, and ionic strength on the response of the aspartame biosensor are investigated in detail. Citric acid, cyclamic acid, D-fructose, D-galactose, D-glucose, hydrogen peroxide, DL-malic acid, L-phenylalanine, saccharin, sodium benzoate, and sucrose show no interferences but ethanol interferes strongly. The aspartame biosensor has been applied to determine aspartame contents in some commercial products. 相似文献
984.
This paper reports on a microfluidic device for the screening of organophosphonate nerve agent degradation products. The miniaturized system relies on an efficient chip-based separation of alkyl methylphosphonic acids (breakdown products of Sarin, Soman, and VX nerve agents) followed by their sensitive contactless conductivity detection. Experimental parameters relevant to the separation and detection processes have been optimized to yield high sensitivity (with 48-86 microg L(-1) detection limits), fast response (50 s for a three alkyl methylphosphonic acid mixture), high precision (RSD = 3.8-5.0%), and good linearity (over the 0.3-100 mg L(-1) range). Applicability to natural (river) water samples is demonstrated. The new microsystem offers promise for monitoring degradation products of chemical warfare agents, with advantages of speed/warning, efficiency, portability, sample size, and cost compared to conventional ion chromatography or capillary electrophoresis systems. 相似文献
985.
4-Nitro-7-piperazino-2,1,3-benzoxadiazole (NBDPZ) is presented as a new reagent for the determination of mono- and diisocyanates in air samples. NBDPZ readily reacts with the airborne analytes, thus yielding the corresponding urea derivatives, which are subsequently separated by means of reversed-phase liquid chromatography. On a phenyl-modified stationary phase, excellent baseline separation for numerous mono- and diisocyanate derivatives is obtained. Both diode array and fluorescence detection are performed with limits of detection of 11-35 and 5-9 nmol/L for the individual derivatives, respectively. In contrast to established derivatizing agents for the analysis of isocyanates, NBDPZ provides for increased selectivity due to the favorable detection wavelengths in the visible range (UV/visible, absorption maximums approximately 480 nm; fluorescence, excitation maximums approximately 470 nm, emission maximums approximately 535 nm). In addition, the high molar absorptivities of the reagent and the derivatives provide excellent sensitivity that is superior to most literature-known methods. Finally, air sampling methods comprising both the use of impingers and test tubes are developed and successfully applied to the determination of isocyanates in gaseous samples. Excellent recovery reaching values of >90% is observed for each of the two techniques investigated. 相似文献
986.
A diffractive optical element is described that can be used to implement a very simple self-aligning electronic speckle-pattern interferometer and holographic interferometer that requires only a laser source and a camera in the optical setup. 相似文献
987.
Lenoble J Martin T Blumthaler M Philipona R Albold A Cabot T de La Casinière A Gröbner J Masserot D Müller M Pichler T Seckmeyer G Schmucki D Touré ML Yvon A 《Applied optics》2002,41(9):1629-1639
A measurement campaign was organized in March 1999 in the Bavarian Alps as part of the European project, Characteristics of the UV Radiation Field in the Alps (CUVRA), to analyze the effect of altitude, aerosols, and snow cover on ground-level UV spectral irradiance. We present the results of simultaneous measurements of aerosol optical depth (AOD) made at various sites on two cloudless days in March 1999. The two days exhibited different aerosol conditions. Results derived from spectral measurements of UV irradiance are compared with data from filter radiometer measurements made at discrete wavelengths extending from the UV to the near IR. The different methods generated values for the AOD that were in good agreement. This result confirms that one can use either method to retrieve the AOD with an uncertainty of approximately 0.03-0.05. On 18 March, high turbidity was observed at low altitude (400-nm AOD approximately 0.5 at 700 m above sea level), and the AOD decreased regularly with altitude; on 24 March, the turbidity was much less (0.11 at 700 m above sea level). On both days very low AODs (0.05-0.09) were measured at 3000 m above sea level. The spectral dependence of the AOD is often parameterized by the angstrom relationship; the alpha parameter is generally difficult or impossible to retrieve from spectral measurements because of the relatively narrow wavelength range (320-400 nm), and only one of the spectro-radiometers used during the campaign permits this retrieval. In most cases, during this field campaign, alpha was found by filter sunphotometers to be 1.1-1.5. 相似文献
988.
An interferometric arrangement that automatically compensates for thermal expansion was used to examine the changes in the refractive index of liquid water at 632.8 nm as a function of temperature from 10 to -15 degrees C. By combining the results of this research with existing data, we calculated the absolute refractive index in the supercooled region with an accuracy ranging from 3 x 10(-6) to 1 x 10(-6). A direct observation of the refractive-index maximum of water is reported for the first time to our knowledge and found to occur between 0 and 0.1 degrees C. 相似文献
989.
On functionally graded balls and cones 总被引:1,自引:0,他引:1
P.A. Martin 《Journal of Engineering Mathematics》2002,42(2):133-142
The heat equation, for both steady and unsteady situations, is considered when the material parameters are spherically symmetric functions of position. Explicit separated solutions are derived when the material parameters are exponential functions; the radial part of these solutions is given in terms of confluent hypergeometric functions or Whittaker functions. In the steady case, explicit solutions are found when the conductivity k(r)= exp(–r
q), where and q are parameters with q>0. The behaviour near the tip of a spherically-graded cone is also investigated. 相似文献
990.
Work-related musculoskeletal disorders (WRMSDs) by definition are a subset of musculoskeletal disorders (MSDs) that arise out of occupational exposures. While traditional exposure assessment techniques have proved to be successful in identifying ergonomic exposures that are epidemiologically linked to these disorders, some are troubled by the lack of one-to-one correspondence between specific occupational exposure profiles and specific MSDs. In the absence of more sophisticated hypotheses that might explain the occurrence of WRMSDs in a variety of exposure patterns, the aetiologic relationships may (again) be called into question. Another unanswered question is whether specific types of WRMSDs have qualitatively different exposure-response relationships. A clearer understanding of the underlying pathomechanisms associated with specific WRMSDs could help future researchers better determine how and when various occupational exposure profiles become pathogenic. Such knowledge could also be used to design exposure assessment tools to capture exposure information more relevant to the risk of WRMSDs. The main goals of this paper are to summarize several recently described pathomechanisms, most of which have been discussed primarily in clinical and experimental literature that might not be widely read by occupational health scientists. Suggestions are made as to how future research could evaluate whether these phenomena are relevant to the effects of physical exposures and the underlying disease processes of common WRMSDs. 相似文献