Flow-injection systems

Enzyme immunosensors are used in flow injection systems and Hquid chromatography to provide automated on-line analyses (71—73). These systems are capable of continuously executing the steps involved in the immunoassays, including the binding reactions, washing, and the enzyme reaction, in about 10 minutes. 

A flow-injection system with electrochemical hydride generation and atomic absorption detection for the determination of arsenic is described. This technique has been developed in order to avoid the use sodium tetrahydroborate, which is capable of introducing contamination. The sodium tetrahydroborate (NaBH ) - acid reduction technique has been widely used for hydride generation (HG) in atomic spectrometric analyses. However, this technique has certain disadvantages. The NaBH is capable of introducing contamination, is expensive and the aqueous solution is unstable and has to be prepared freshly each working day. In addition, the process is sensitive to interferences from coexisting ions. 

Saurina, J., Hemandez-Cassou, S., Tauler, R., Izquierdo-Ridorsa, A., Spectrophotometric determination of pKa values based on a pH gradient flow-injection system. Anal. Chim. Acta... 

C.A. Scolari and S.D. Brown, Multicomponent determination in flow-injection systems with square-wave voltammetric detection using the Kalman filter. Anal. Chim. Acta, 178 (1985) 239-246. 

Membrane separation coupled on-line to a flow-injection system was employed for the monitoring of propazine and terbutryn in natural water. A microporous hydro-phobic membrane was utilized in which the analytes were extracted from the aqueous medium into an organic solvent that was carried to the flow cell of a photodiode-array spectrophotometer. The LCDs were 4-5 qg so the technique could potentially be used for screening purposes. Samples with positive detection would require further analysis. 

Couto et al. [11] developed a flow injection system with potentiometric detection for determination of TC, OTC, and CTC in pharmaceutical products. A homogeneous crystalline CuS/Ag2S double membrane tubular electrode was used to monitor the Cu(II) decrease due to its complexation with OTC. The system allows OTC determination within a 49.1 1.9 x 103 ppm and a precision better than 0.4%. A flow injection method for the assay of OTC, TC, and CTC in pharmaceutical formulations was also developed by Wangfuengkanagul et al. [12] using electrochemical detection at anodized boron-doped diamond thin-film electrode. The detection limit was found to be 10 nM (signal-to-noise ratio = 3). 

Marquette C.A., Blum L.J., Electrochemiluminescence of luminol for 2,4-D optical immunosensing in a flow injection system, Sens. Actuators B 1998 51 100-106. 

S. Sawada, H. Torii, T. Osakai, and T. Kimoto, Pulse amperometric detection of lithium in artificial serum using a flow injection system with a liquid/liquid-type ion-selective electrode. Anal. Chem. 70, 4286-4290 (1998). 

The analytical performance of Prussian blue-modified electrodes in hydrogen peroxide detection were investigated in a flow-injection system equipped with a wall-jet cell. Nano-structured Prussian blue-modified electrodes demonstrate a significantly decreased background, which results in improved signal-to-noise ratio. 

Aschematic diagram of the flow injection system used by Anderson [126] is shown in Fig. 2.4. An Ismatec model MP13 peristaltic pump was used. Different flow rates were obtained by changing the pump tube diameter, as indicated in the legend to Fig. 2.4. The injection port was a rotary valve [131,170]. The sample volume could be varied between 10 and 1000 pi simply by changing the length of the sample loop. 

Olsen et al. [660] used a simple flow injection system, the FIAstar unit, to inject samples of seawater into a flame atomic absorption instrument, allowing the determination of cadmium, lead, copper, and zinc at the parts per million level at a rate of 180-250 samples per hour. Further, online flow injection analysis preconcentration methods were developed using a microcolumn of Chelex 100 resin, allowing the determination of lead at concentrations as low as 10 pg/1, and of cadmium and zinc at 1 pg/1. The sampling rate was between 30 and 60 samples per hour, and the readout was available within 60-100 seconds after sample injection. The sampling frequency depended on the preconcentration required. 

Fang et al. [661] have described a flow injection system with online ion exchange preconcentration on dual columns for the determination of trace amounts of heavy metal at pg/1 and sub-pg/1 levels by flame atomic absorption spectrometry (Fig. 5.17). The degree of preconcentration ranges from a factor of 50 to 105 for different elements, at a sampling frequency of 60 samples per hour. The detection limits for copper, zinc, lead, and cadmium are 0.07, 0.03, 0.5, and 0.05 pg/1, respectively. Relative standard deviations are 1.2-3.2% at pg/1 levels. The behaviour of the various chelating exchangers used was studied with respect to their preconcentration characteristics, with special emphasis on interferences encountered in the analysis of seawater. 

Several authors observed CL emission based on reduction reactions. Lu et al. [59] developed a method by applying a Jones reductor for producing unstable reductants. A column (100 X 3 mm i.d.) filled with Zn-Hg particles was inserted into the flow stream of a flow injection system. CL was measured using a homemade CL analyzer. Although the Jones reductor was more effective for the species studied in 0.5-5 mol/L H2S04 solution, the authors found that a lower acid concentration improved the CL emission. Hie optimal pH was 6.5 for V(II), 2.5 for Mo(III), 3.5 for U(III), 3.0 for W(III), 3.0 for Cr(II), 2.5 for Ti(III), and 2.5 for Fe(II). The methods allowed determination of the above-mentioned species at pg/mL to ng/mL levels. It was assumed that the CL reactions were related to the production of superoxide radicals by dissolved oxygen in the solutions. The proposed methods could be successfully applied to the determination of V [60], Mo [61], and U [62] in water or steel samples. 

Finally, Yamada and Suzuki made a comparative study of the use of DDAB, HTAB, STAC, and CEDAB to improve the sensitivity and selectivity of the determination of ultratraces of Cu(II) by means of the CL reaction of 1,10-phenanthroline with hydrogen peroxide and sodium hydroxide, used as detection in a flow injection system [46]. Of the four cited surfactants it was found that CEDAB causes the greatest enhancement of the chemiluminescent signal (Fig. 12) (an enhancement factor of 140 with respect to the absence of surfactant). 

A BASIC FLOW INJECTION SYSTEM FOR CHEMILUMINESCENCE MEASUREMENTS... 

The instrumentation used for FIA with CL detection is usually simple and is composed of the components depicted in Figure 2. These components are readily assembled to form the analytical manifold, although there are also commercially available flow injection systems with CL detection. Spectrophotometric or fluo-rimetric flow injection systems can often be used for CL measurements after some modifications. 

A sensor array where different haptens are immobilized at well-defined areas on a plain glass surface has been developed [66], Using an automated flow injection system it was possible to incubate all areas on the chip with analytes, specific antibodies, secondary HRP-labeled antibodies, and CL substrate. Measurement of the light output via imaging performed with a CCD device allowed determination of the analytes present in the sample on the basis of the spatial localization of the CL signal. 

As described for stopped flow experiments above, all commercially available SPR systems work under (pseudo) first-order conditions as well. This is realized either by a large excess of free ligand (in the large volume of the cuvette) compared with a nanoliter volume of the sensor layer [156] or by continuous replacement of free ligand in a flow injection system (e.g.,BIAcore [157]). 

In the method for extractable phosphorus [62, 64-66] the phosphorus is extracted from the soil at 20 1°C with sodium bicarbonate solution at pH8.5. After filtration and release of carbon dioxide the extracts are introduced into a flow-injection system for the determination of phosphate. Phosphate is determined by reaction with vanadomolybdate and the yellow colour evaluated at 410nm. Between 20 and lOOOmg kg-1 phosphorus in soil has been determined using this method. 

Zhu Z, Fang Z. 1987. Spectrophotometric determination of total cyanide in waste waters in a flow-injection system with gas-diffusion separation and pre-concentration. Anal Chim Acta 198 25-36. 

L. Arce, A. Rios and M. Valcarcel, Determination of anti-carcinogenic polyphenols present in green tea using capillary electrophoresis coupled to a flow injection system. J. Chromatogr.A 823 (1998) 113-120. 

The system described above has been designed to increase laboratory productivity. It is claimed to have 30-70% lower reagent consumption titan macroflow or flow injection systems. It also provides reagent change-over facihties, wash-out and shut-down sequencing, when the option is fitted. 

Fig. 2.19 Schematic diagram of a simple flow-injection system.

Fig. 2.20 Schematic diagram of simple flow-injection system designed by Malcolme-Lawes [41].

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