Statistical evaluation of the performance of a new programmed-scan monochromator for multielement determinations by atomic emission

The reproducibility of a programmed-scan monochromator with stationary dispersion optics was evaluated by means of analysis of variance (ANOVA). The spectrometer used an optical multiplexer coupled with glass-fiber optic light-guides to a multiple entrance-slit spectrometer employing a photomultiplier as the detector. With this spectrometer, 15 emission intensity measurements at the lithium resonance line wavelength (670.7 nm) were collected for five rotations of the optiplexer mirror under four different emission situations: flame background emission at 670.7 nm, lithium emission from an acetylene-air flame in the absence of an ionization buffer, lithium emission from an acetylene-air flame in the presence of an ionization buffer, and tungsten lamp emission at 670.7 nm. For all four situations, the ANOVA results showed that instrumental changes which occurred during mirror rotation in the optiplexer were a significant source of signal variation compared with factors not associated with mirror rotation, i.e., photon shot noise, source fluctuation noise, and electronic drift. The actual magnitude of the signal variability introduced during mirror rotation, however, was found to be quite small, producing an average relative standard deviation of only 0.76% for the signal.     

A dual-wavelength light-emitting diode based detector for flow-injection analysis process analysers

In this paper, a small dual-wavelength light-emitting diode (LED) based detector for FIA process analysers is designed. The detector's optical parts include a flow cell, a dual-wavelength LED and a photodiode. Neither mirrors nor lenses are used. The optical paths for the different light beams are almost the same, distinguishing it from previously reported LED based detectors. The detector's electronic components, including a signal amplifier, an A/D and D/A converter, and an Intel 8031 single-chip microcomputer, are integrated on one small board. In order to obtain response signals of approximate intensity for the two colours, the D/A converter and a multiplexer are used to adjust the emission intensity of the two colours respectively. Under microcomputer control, light beams are rapidly electronically modulated. Therefore, dark current and intensity of the light beams are measured almost simultaneously; as a result, the effect of drift is negligible. While a solution of absorbance 0.875 was measured repeatedly, an RSD (relative standard deviation) of 0.24% could be reached. Furthermore, such a detector with a red/yellow LED has been coupled with the FIA technique for the determination of 10(-6)M levels of cobalt.     

Photometric detection in flow analysis systems using integrated PEDDs

A novel inexpensive optical-sensing technique has been developed for colorimetric flow analysis. This sensing system employs two LEDs whereby one is used as the light source and the other as a light detector. The LED used as light detector is reverse biased with a 5-V supply so that the photocurrent generated by the incident light discharges the capacitance. Direct digital output is provided by a simple timer circuit that measures the time taken for this discharge process from 5 V (logic 1) to 1.7 V (logic 0).

This sensing concept has been applied in flow analysis by constructing an optical flow cell with a pair of LEDs. Calibration of the integrated optical flow cell using a dye resulted in a linear response that obeys the Beer–Lambert law. The flow rate, dynamic range, sensitivity and limits of detection were investigated. The system was also used for pH determination in the range of pH 2.5–6.8 using bromocresol green (BCG). The pK_a of BCG was successfully determined by this technique.     

Optical analysis of dichroism measurements in polymer science

The polarization properties of an optical system, source–interferometer–polarizer–polymer film–detector, have been calculated. Using Mueller matrices, the intensity has been obtained as a function of polarizer angle. It is shown in some detail how polarization of the beam in both interferometer and detector optics distort the spectra. The contributions from the finite extinction ratio of the polarizer are also calculated and intensity variations caused by beam-wandering are discussed. It is shown that the commonly used procedure for correcting the spectra is wrong. Better methods for correcting the spectra are proposed. The influence of a uniaxial refractive index on the data is discussed, and experimental methods that can deal with refraction effects are presented. © 1993 John Wiley & Sons, Inc.     

Two-dimensional multiple entrance-slit vidicon spectrometer for simultaneous multielement analysis

A new type of wavelength dispersion system for use with a multichannel detector has been developed for simultaneous multielement analysis. The system employs a monochromator with fixed grating position, and incident angle varied by horizontal displacement of the entrance slits. The overlapping spectral windows which result can be arranged to produce a composite spectrum having minimal interference from emissions by other sample constituents. Entrance slits may also be displaced vertically to create a two-dimensional system in which spectra are stacked one above the other and scanned by use of a multi-raster scanning pattern. A number of optical and performance characteristics of the system are evaluated in both the one- and two-dimensional modes, and the system is applied to the determination of Ca, Na and K in blood serum and to the determination of the exchangeable cations Ca, Na, Li and K in clay. The advantages of this system for simultaneous multielement analysis are discussed.     

A double plasma gas chromatography injector and detector

A direct-current, chip-based plasma has been used for gas sample injection in gas chromatography. A second identical plasma chip has been used as the excitation source for an optical emission detector. The first plasma is normally continually sustained during operation, causing continuous ionisation/fragmentation of the sample, whilst the second plasma records the optical emission downstream. For injection, the first plasma is briefly interrupted, introducing a "plug" of unmodified sample into the system. Injection plug sizes of between 5 and 50 [micro sign]l have been reproducibly obtained, although significantly smaller volumes may be possible with the use of smaller cross-section columns, lower flow rates and/or shorter plasma interruption times.     

A windowless flow cell-based miniaturized fluorescence detector for capillary flow systems

A miniaturized fluorescence detector utilizing a three-dimensional windowless flow cell has been constructed and evaluated. The inlet and outlet liquid channels are collinear and are located in the same plane as the excitation paths, while the optical fiber used to collect the emission light is perpendicular to this plane. The straightforward arrangement of the flow path minimizes band dispersion and eliminates bubble formation or accumulation inside the cell. The use of high-brightness light-emitting diodes (LEDs) as the excitation source and a miniaturized metal package photomultiplier tube (PMT) results in a compact and sensitive fluorescence detector. The detection limit obtained from the system for fluorescein isothiocyanate (FITC) in flow injection mode is 2.6 nmol/L. The analysis of riboflavin and FITC by packed capillary liquid chromatography is demonstrated.      

Optical fiber light-emitting diode-induced fluorescence detection for capillary electrophoresis

A highly sensitive optical fiber light-emitting diode (LED)-induced fluorescence detector for CE has been constructed and evaluated. In this detector, a violet or blue LED was used as the excitation source and an optical fiber with 40 microm OD was used to transmit the excitation light. The upper end of the fiber was inserted into the separation capillary and was situated right at the detection window. Fluorescence emission was collected by a 40 x microscope objective, focused on a spatial filter, and passed through a cutoff filter before reaching the photomultiplier tube. Output signals were recorded and processed with a computer using in-house written software. The present CE/fluorescence detector deploys a simple and inexpensive optical system that requires only an LED as the light source. Its utility was successfully demonstrated by the separation and determination of amino acids (AAs) labeled with naphthalene-2,3-dicarboxaldehyde (NDA) and FITC. Low detection limits were obtained ranging from 17 to 23 nM for NDA-tagged AAs and 8 to 12 nM for FITC-labeled AAs (S/N=3). By virtue of such valuable features as low cost, convenience, and miniaturization, the presented detection scheme was proven to be attractive for sensitive fluorescence detection in CE.     

An improved configuration of a moving wire transport detector

An improved design of the transport detector is described that uses a pre-oxidized titanium ribbon as the transport medium. The titanium ribbon has a high loading capacity that permits a large proportion of the total column eluent to be taken into the sensing system. The solute is sensed by pyrolysis and the subsequent detection of pyrolysis products by a miniature argon detector. The pyrolyzer and sensor system is designed to ensure that all the pyrolysis products enter the detector with minimum dilution and band dispersion. As a result, the sensitivity of the detector (or minimum detectable concentration) has been reduced by approximately two orders of magnitude compared with the original design. The sensitivity of the system described to sucrose is 8 x 10(-8) g/mL, which is similar to the sensitivity of the fixed-wavelength UV detector to benzene (approximately 5 x 10(-8) g/mL). It would appear that the new design has potentially a sensitivity at least an order of magnitude lower than that reported here.     

Comparison of a gas chromatography-optical fibre (GC-OF) detector with a gas chromatography-flame ionization detector (GC-FID) for determination of alcoholic compounds in industrial atmospheres

An analytical methodology based on an optical fibre detector coupled to gas chromatograph has been developed for the speciation of some volatile alcoholic compounds. This methodology combines the separation capability of gas chromatography with an optical fibre detector made of an optical fibre sensitized with a thin polymeric film of poly[methyl(3,3,3-trifluoropropyl)siloxane] (PMTFPS). The response of the detector has been characterized at 650 nm for nine different alcohols (allyl alcohol, n-propyl alcohol, sec-butyl alcohol, isobutyl alcohol, n-butyl alcohol, isoamyl alcohol, methyl isobutyl carbinol, cyclohexanol and diacetone alcohol). An alternative method based on gas chromatography-flame ionization detector (GC-FID) was also used in order to evaluated the performance and compare the analytical results with the proposed method. The time of analysis, the analytical error and the analytical performance were similar for both methods. However, the analytical apparatus based on the GC-OF detector is much less expensive than the GC-FID and show high accuracy and suitability for actual monitoring on indoor atmospheres.     

Radiometric detection in flow-injection analysis (Radiometric Flow-Injection Analysis)

A single line system with a detector of radioactivity was used for the determination of⁶⁰Co. In the determination, no additional chemistry is involved and limited dispersion is desirable. For this application, the FIA system is used only as a transport system for the sample up to the detector.     

Design and optimization of on-chip capillary electrophoresis

We present a systematic, experimentally validated method of designing electrokinetic injections for on-chip capillary electrophoresis applications. This method can be used to predict point-wise and charge-coupled device (CCD)-imaged electropherograms using estimates of species mobilities, diffusivities and initial sample plug parameters. A simple Taylor dispersion model is used to characterize electrophoretic separations in terms of resolution and signal-to-noise ratio (SNR). Detection convolutions using Gaussian and Boxcar detector response functions are used to relate optimal conditions for resolution and signal as a function of relevant system parameters including electroosmotic mobility, sample injection length, detector length scale, and the length-to-detector. Analytical solutions show a tradeoff between signal-to-noise ratio and resolution with respect to dimensionless injection width and length to the detector. In contrast, there is no tradeoff with respect to the Peclet number as increases in Peclet number favor both SNR and separation solution (R). We validate our model with quantitative epifluorescence visualizations of electrophoretic separation experiments in a simple cross channel microchip. For the pure advection regime of dispersion, we use numerical simulations of the transient convective diffusion processes associated with electrokinetics together with an optimization algorithm to design a voltage control scheme which produces an injection plug that has minimal advective dispersion. We also validate this optimal injection scheme using fluorescence visualizations. These validations show that optimized voltage scheme produces injections with a standard deviation less than one-fifth of the width of the microchannel.     

Application of the photoionization detector for the determination of ethanol in aqueous solutions and human breath

A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3delta-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results.     

Novel integrated paired emitter-detector diode (PEDD) as a miniaturized photometric detector in HPLC

A novel low power, low cost, highly sensitive, miniaturized light emitting diode (LED) based flow detector has been used as optical detector for the detection of sample components in high performance liquid chromatography (HPLC). This colorimetric detector employs two LEDs, one operating in normal mode as a light source and the other is reverse biased to work as a light detector. Instead of measuring the photocurrent directly, a simple timer circuit is used to measure the time taken for the photocurrent generated by the emitter LED (lambda(max) 500 nm) to discharge the detector LED (lambda(max) 621 nm) from 5 V (logic 1) to 1.7 V (logic 0) to give digital output directly without using an A/D converter. Employing a post-column reagent method, a Nucleosil 100-7 column (functionalized with iminodiacetic acid (IDA) groups) was used to separate a mixture of transition metal complexes, manganese(II) and cobalt(II) in 4-(2-pyridylazo)-resorcinol (PAR). All optical measurements were taken by using both the in-built HPLC variable wavelength detector and the proposed paired-emitter-detector-diode (PEDD) optical detector configured in-line for data comparison. The concentration range investigated using the PEDD was found to give a linear response to the Mn(II) and Co(II) PAR complexes. The effects of flow rate and emitter LED light source intensity were investigated. Under optimised conditions the PEDD detector offered a linear range of 0.9-100 microM and LOD of 0.09 microM for Mn-PAR complex. A linear range of 0.2-100 microM and LOD of 0.09 microM for Co-PAR complex was achieved.     

Dispersion Stability Evaluated by Experimental Design

The stability of paraffin and hydrocarbon oil dispersions stabilized by nonionic surfactants has been systematically evaluated. Using experimental design, the influence of the following parameters on dispersion stability was studied: surfactant concentration, shear rate, shear time and temperature of homogenisation. The experiments were evaluated with respect to particle size and particle migration velocity by a scanning optical analysis technique. This scanning technique monitors physical variations in a dispersion as a function of time and the technique is well suited for evaluation of dispersion stability. It was found that the only factor examined affecting particle migration velocity in a significant way was the surfactant concentration. A pronounced maximum in creaming rate was obtained at around 10 wt% surfactant both for the paraffin dispersions (suspensions at room temperature) and for the hydrocarbon oil emulsions. This surfactant-induced instability is explained as depletion flocculation caused by elongated surfactant micelles or by small oil-containing aggregates formed as microemulsion droplets during the emulsification process.     

高热稳定性氟化聚醚砜的合成及其在阵列波导光栅复用器中的应用

用合成的3-三氟甲基苯侧基聚醚砜(3F-PES)作为波导芯层材料制作了新型硅基聚合物阵列波导光栅(AWG)复用器.采用DSC,TGA和AFM等方法对3F-PES的光学性质和热稳定性进行了表征.DSC和TGA结果显示,3F-PES的玻璃化转变温度为170℃,在空气中5%的热失重温度为542℃,表明具有非常好的热稳定性.3F-PES溶液在旋涂时具有很好的成膜性,AFM照片显示,粗糙度起伏为0.35nm.近红外吸收谱表明,3F-PES在光通讯波段有较小的吸收,适合用来制作低损耗的光波导器件.用3F-PES作为波导芯层材料制作的八通道硅基聚合物阵列波导光栅(AWG)复用器的通道间隔为1.603nm,中心波长为1550.15nm.     

High-performance liquid chromatography applications of optical rotation detection with compensation for scattering and absorbance at the laser wavelength.

Use of instrumentation developed to enable simultaneous monitoring of optical rotation (OR) and transmittance allows OR measurements to be made in the presence of high levels of absorbance, scattering or other effects that change the intensity of the plane-polarised light at the photodiode detector. This extends the application of OR detection to areas where it was previously difficult. Examples of the application of high-performance liquid chromatography (HPLC) with the improved OR detector include (i) the analytical scale separation of fructose and sucrose and (ii) the semi-preparative separation of enantiomers of warfarin and Tr?gers base. A signal-to-noise improvement of up to 150% is found when comparing signals with and without correction for transmittance changes. The improved OR detector has been used in series with a UV detector and the system shown to be suitable for on-line measurement of peak purity in separations using a chiral column under overload conditions.     

An optical rotatory detector for high-performance liquid chromatography using polarization modulation.

A sensitive and variable-wavelength optical rotatory (OR) detector for high-performance liquid chromatography is presented. This design is entirely different from that of conventional OR detectors consisting of a crossed polarizer pair. By placing a polarizing prism and a retardation plate into a commercial circular dichroism (CD) detector, the OR signal was obtained. The Mueller matrix approach was used to prove the principle of the OR signal appearance. Sugars and 4-androstene-3,17-dione were chosen as test compounds. The limit of detection was below 0.5 microg of injected sucrose at 260 nm, which was superior to that obtained with a conventional OR detector. For 4-androstene-3,17-dione, which is CD active, and shows a large anomalous OR dispersion curve, our detector gave a large OR signal with approximately half the intensity of the CD signal at 340 nm.     

发光二极管诱导荧光用于毛细管电泳检测

利用发光二极管作为激发光源，组装了用于毛细管电泳的荧光检测器。光纤用于传输荧光信号；光纤端面修饰成球形使耦合效率比平面端光纤提高了50．8％；光阑、光纤及毛细管检测池之间的光学校准简单、便捷。荧光素染料用于评价该体系性能，得到了fmol的质量检出限。     

电化学调制时间分辨紫外可见光谱技术及其在电显色研究中的应用

A new electrochemically modulated time resolved uv/vis spectroscopic(EMTRUV/VS) technique based on optical multienannel analyzer (OMA) has been presented. EM-TRUV/VS measurement apparatus consists of five units: an optical signal detection unit which includes a detector, a polychromator, a detector module; an optics unit; a spe-ctroelectrochemical cell unit, which includes optical transparent electrode (OTE); an electrochemical control unit. The limit of time resolution can reach the order of ms by continuously scanning mode and the order of μs by gate mode which is suitable to reversible system with respect to a potential change, respectively. A high S/N ratio can be obtained by subtractive spectrum method. The electrochromism of a poly-o-phenylenediamine (POPD)-coated Au OTE in aqueous 1 mol·L~(-1) H_2SO_4 solution was studied by EMTRUV/VS technique. The optical absorption (λ_(max)=550 nm) of oxidized POPE is ascribed to n→π* transition. The time resolved spectra acquired suggest that the oxidation reaction of PDPD occurs during the first 500 μs and that the electrochromism is controled by H~+ transport.