Stereoselective release behaviors of imprinted bead matrices

In this work, the stereoselective release behaviors of “low”-swelling molecularly imprinted polymer (MIP) bead matrices in pressed-coat tablet type were studied. Either R-propranolol selective MIP or S-propranolol selective MIP was combined with excipients and racemic propranolol and fabricated into the matrix. Subsequently, the release of different propranolol enantiomers from the matrices was examined. Also, the microscopic structure of the hydrated “low”-swelling MIP matrix was determined using a cryogenic scanning electron microscope in order to compare with that of the hydrated “high”-swelling MIP matrix. In vitro release profiles of the “low”-swelling matrices showed a difference in the release of enantiomers, in that the non-template isomer was released faster than the template isomer. However, in the last phase of dissolution this difference reduced and later reversed, resulting at last in the type of specificity being similar to that obtained previously with “high”-swelling MIP matrices.

n summary, MIP beads can be fashioned into matrices and incorporated into different formulations to regulate the resultant stereoselectivity. From the behaviors of stereoselective release observed in MIP matrices, we can conclude that the enantioselective-controlled delivery mechanism of MIPs via formulations depends on the relative affinity of the enantiomer for the template sites, as well as the nature of the polymer, such as hydrophobicity and swellability.     

Ion channel mimetic micropore and nanotube membrane sensors

This paper describes synthetic micropore and nanotube membranes that mimic the function of a ligand-gated ion channel; that is, these membranes can be switched from an "off" state (no or low ion current through the membrane) to an "on" state (higher ion current) in response to the presence of a chemical stimulus. Ion channel mimics based on both microporous alumina and Au nanotube membranes were investigated. The off state was obtained by making the membranes hydrophobic by chemisorbing either a C18 silane (alumina membrane) or a C18 thiol (Au nanotube membrane). Water and electrolyte are forbidden from entering these very hydrophobic pores/nanotubes. The transition to the on state was induced by the partitioning of a hydrophobic ionic species (e.g., a drug or a surfactant) into the membrane. The membrane switches to the on state because at a sufficiently high concentration of this ionic analyte species, the pores/nanotubes flood with water and electrolyte. A pH-responsive membrane was also prepared by attaching a hydrophobic alkyl carboxylic acid silane to the alumina membrane.     

Correction for particle-wall interactions in the separation of colloids by flow field-flow fractionation

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.     

In-channel electrochemical detection for microchip capillary electrophoresis using an electrically isolated potentiostat

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.     

Aspartame optical biosensor with bienzyme-immobilized eggshell membrane and oxygen-sensitive optode membrane

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.     

Measurements of chemical warfare agent degradation products using an electrophoresis microchip with contactless conductivity detector

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.     

4-Nitro-7-piperazino-2,1,3-benzoxadiazole as a reagent for monitoring of airborne isocyanates by liquid chromatography

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.     

Holographically recorded photopolymer diffractive optical element for holographic and electronic speckle-pattern interferometry

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.     

Retrieval of the ultraviolet aerosol optical depth during a spring campaign in the Bavarian Alps

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.     

Autocompensating interferometer for measuring the changes in refractive index of supercooled water as a function of temperature at 632.8 nm

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.