A multicommuted stop-flow system employing LEDs-based photometer for the sequential determination of anionic and cationic surfactants in water

It has been developed an automatic stop-flow procedure for sequential photometric determination of anionic and cationic surfactants in a same sample of water. The flow system was based on multicommutation process that was designed employing two solenoid micro-pumps and six solenoid pinch valves, which under microcomputer control carry out fluid propelling and reagent solutions handling. A homemade photometer using a photodiode as detector and two light emitting diodes (LEDs) with emission at 470 nm (blue) and 650 nm (red) as radiation sources, which was tailored to allow the determination of anionic and cationic surfactants in waters. The procedure for anionic surfactant determination was based on the substitution reaction of methyl orange (MO) by the anionic surfactant sodium dodecylbenzene sulfonate (DBS) to form an ion-pair with the cetyl pyridine chloride (CPC). Features such as a linear response ranging from 0.35 to 10.5 mg L⁻¹ DBS (R = 0.999), a detection limit of 0.06 mg L⁻¹ DBS and a relative standard deviation of 0.6% (n = 11) were achieved. For cationic surfactant determination, the procedure was based on the ternary complex formation between cationic surfactant, Fe(III) and chromazurol S (CAS) using CPC as reference standard solution. A linear response range between 0.34 and 10.2 mg L⁻¹ CPC (R = 0.999), a detection limit of 0.05 mg L⁻¹ CPC and a relative standard deviation of 0.5% (n = 11) were obtained. In both cases, the sampling throughput was 60 determinations per hour. Reagents consumption of 7.8 μg MO, 8.2 μg CPC, 37.2 μg CAS and 21.6 μg Fe(III) per determination were achieved. Analyzing river water samples and applying t-test between the results found and those obtained using reference procedures for both surfactant types provide no significant differences at 95% confidence level.     

Determination of phenols in waters using micro-pumped multicommutation and spectrophotometric detection: an automated alternative to the standard procedure

An automated and greener spectrophotometric procedure has been developed for the determination of phenol in water at 700 nm. The method uses the reaction between phenol, sodium nitroprusside, and hydroxylamine hydrochloride in a buffered medium at pH 12.3. The flow manifold comprises four solenoid micro-pumps employed for sample and reagent introduction into the reaction coil and to transport the colored product formed to the detector. The linear dynamic range was 50–3,500 ng mL⁻¹ (R = 0.99997; n = 6) and the method provided a limit of detection (3σ) of 13 ng mL⁻¹. The sampling throughput was estimated to be 65 measurements per hour and the coefficient of variation was 0.5% (n = 10) for a 1.0 μg mL⁻¹ phenol concentration. Recoveries of 92–105% were obtained for phenol determination in spiked water samples at concentration levels from 50 to 5,000 ng mL⁻¹. The use of multicommutation reduced the reagent consumption 25-fold, the sample consumption 225-fold, and the waste generation 30-fold compared with the batch procedure. The proposed method is an environmentally friendly alternative to the official 4-aminoantipyrine method since it avoids the use of chloroform.     

Liquid-liquid extraction procedure exploiting multicommutation in flow system for the determination of molybdenum in plants

A liquid-liquid extraction flow analysis procedure for the spectrophotometric determination of molybdenum in plants at μg l⁻¹ level is described. The flow network comprised a set of solenoid valves assembled to implement the multicommutation approach under microcomputer control. Radiation source (LED, 475 nm), detector (photodiode) and separation chamber were nested together with the flow cell comprising a compact unit. The consumption of reagents (potassium thiocyanate and stannous chloride) and also extracting solvent (isoamyl alcohol) were optimized to 32 mg and 200 μl per determination, respectively. Accuracy was assessed by comparing results with those obtained with ICP-OES and no significant difference at 95% confidence level was observed. Other favorable characteristics such as a linear response ranging from 25 to 150 μg l⁻¹ molybdenum (r=0.999); detection limit of 4.6 μg l⁻¹ sample throughput of 25 determinations per hour and relative standard deviation of 2.5% (n=10) were also achieved.     

An improved flow system for phenols determination exploiting multicommutation and long pathlength spectrophotometry

A greener and sensitive procedure for spectrophotometric determination of phenols based on a multicommuted flow system with a 100 cm optical path flow cell is presented. The method exploited the oxidative coupling of phenolic compounds with 4-aminoantipyrine in alkaline medium containing potassium hexacyanoferrate(III). Sensitivity was 80-fold higher than that achieved with a 1 cm flow cell, making feasible the determination of phenols in the 10-100 μg l⁻¹ range with a detection limit estimated as 1 μg l⁻¹ phenol. The sampling rate and the coefficient of variation were estimated as 90 determinations per hour and 0.6% (n=10), respectively. The multicommutation approach allowed a 200-fold reduction of the reagent consumption in comparison with the reference batch method. Moreover, the chloroform extraction for analyte concentration is unnecessary in view of the increase in sensitivity. Recoveries within 93.3 and 106% were achieved for determination of phenol in natural and wastewater samples. Results agreed with the obtained by a reference method at the 95% confidence level.     

An improved procedure for flow-based turbidimetric sulphate determination based on a liquid core waveguide and pulsed flows

An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20–200 mg L⁻¹, described by the equation S = −0.0767 + 0.00438C (mg L⁻¹), r = 0.999. The detection limit was estimated as 3 mg L⁻¹ at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7–16 mg L⁻¹, described by the equation S = −0.865 + 0.132C (mg L⁻¹), r = 0.999. The detection limit was estimated as 150 μg L⁻¹ at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level.     

A green flow-based procedure for fluorimetric determination of acid-dissociable cyanide in natural waters exploiting multicommutation

A flow system designed with solenoid valves is proposed for determination of weak acid dissociable cyanide, based on the reaction with o-phthalaldehyde (OPA) and glycine yielding a highly fluorescent isoindole derivative. The proposed procedure minimizes the main drawbacks related to the reference batch procedure, based on reaction with barbituric acid and pyridine followed by spectrophotometric detection, i.e., use of toxic reagents, high reagent consumption and waste generation, low sampling rate, and poor sensitivity. Retention of the sample zone was exploited to increase the conversion rate of the analyte with minimized sample dispersion. Linear response (r = 0.999) was observed for cyanide concentrations in the range 1–200 μg L⁻¹, with a detection limit (99.7% confidence level) of 0.5 μg L⁻¹ (19 nmol L⁻¹). The sampling rate and coefficient of variation (n = 10) were estimated as 22 measurements per hour and 1.4%, respectively. The results of determination of weak acid dissociable cyanide in natural water samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. Additionally to the improvement in the analytical features in comparison with those of the flow system with continuous reagent addition (sensitivity and sampling rate 90 and 83% higher, respectively), the consumption of OPA was 230-fold lower.     

Chemiluminescence optosensing implemented with multicommutation: determination of salicylic acid

In this paper we have coupled, for the first time, chemiluminescent detection with multicommuted optosensing principles. This approach has been implemented with the use of a commercial flow cell of 1 mm optical path length filled with an appropriate anionic exchanger gel as chemiluminescence sensing phase. The cell was placed in front of the window of the photosensor module of a home-made luminometer developed in our laboratory and a flat mirror was stuck on the back of the cell. The suitability of using chemiluminescence as detection technique in multicommuted flow-through optosensors has been demonstrated: the determination of salicylic acid by simple oxidation with permanganate on the sensing solid phase was chosen as model reaction. The proposed system allows the determination of salicylic acid in pharmaceuticals, with a sample frequency as high as even 60 samples h⁻¹ and showing a detection limit of 0.30 μg mL⁻¹, the linear response range is 1–30 μg mL⁻¹ and the R.S.D. is 3.1%. Satisfactory results have been obtained when applying the sensor to pharmaceuticals. The accuracy of the proposed methodology has been tested by using a reference method.     

Photochemical-chemiluminometric determination of aldicarb in a fully automated multicommutation based flow-assembly

A sensitive and fully automated method for determination of aldicarb in technical formulations (Temik) and mineral waters is proposed. The automation of the flow-assembly is based on the multicommutation approach, which uses a set of solenoid valves acting as independent switchers. The operating cycle for obtaining a typical analytical transient signal can be easily programmed by means of a home-made software running in the Windows environment. The manifold is provided with a photoreactor consisting of a 150 cm long × 0.8 mm i.d. piece of PTFE tubing coiled around a 20 W low-pressure mercury lamp. The determination of aldicarb is performed on the basis of the iron(III) catalytic mineralization of the pesticide by UV irradiation (150 s), and the chemiluminescent (CL) behavior of the photodegradated pesticide in presence of potassium permanganate and quinine sulphate as sensitizer. UV irradiation of aldicarb turns the very week chemiluminescent pesticide into a strongly chemiluminescent photoproduct. The method is linear over the range 2.2-100.0 μg l⁻¹ of aldicarb; the limit of detection is 0.069 μg l⁻¹; the reproducibility (as the R.S.D. of 20 peaks of a 24 μg l⁻¹ solution) is 3.7% and the sample throughput is 17 h⁻¹.     

Analytical strategy photodegradation/chemiluminescence/continuous-flow multicommutation methodology for the determination of the herbicide Propanil

The present paper is dealing with an analytical strategy based on coupling photodegradation, chemiluminescence and multicommutation continuous-flow methodology for the determination of the pesticide Propanil, a common herbicide. The pesticide solution is inserted as small segments sequentially alternated with segments of the solution for adjusting the suitable medium for the photodegradation. Both flow-rates (sample and medium) are adjusted to required time for photodegradation, 2.0 min; and then, the resulting solution is also sequentially inserted as segments alternated with segments of the oxidizing solutions system, 1.00 × 10⁻⁴ mol l⁻¹ potassium permanganate in 2.00 mol l⁻¹ sulphuric acid medium. The calibration range, from 10 μg l⁻¹ to 25 mg l⁻¹, resulted in a linear behaviour over the range 10 μg l⁻¹-5 mg l⁻¹ and fitting the linear equation: I = 780.30C + 95.28; correlation coefficient 0.9999. The limit of detection was 8 μg l⁻¹ and the sample throughput 20 h⁻¹. After testing the influence of a large series of potential interferents the method is applied to water samples obtained from different places and to one formulation. The method is valid for the determination of other pesticides from the same chemical family, namely: alachlor, flumetsulam, furalaxyl and ofurace. Calibration graphs, limits of detection, repeatability and determination in water samples are obtained for each reported pesticide.     

The potential of combining solid-phase optosensing and multicommutation principles for routine analyses of pharmaceuticals

In this work, we have explored the analytical potential of combining solid-phase optosensing and multicommutation principles, applied to the field of routine analyses of pharmaceuticals. This marriage benefits from the advantaging features of both concepts: the ability of multicommutation to provide increased repeatability, easier sample handling, reduced sample and reagent consumption as well as minor waste generation, combined with the enhancement of both sensitivity and selectivity obtained when a solid support is used to carry out the spectroscopic measurements directly on it. This approach has been evaluated by developing a method for the simultaneous analysis of two active principles (piroxicam and pyridoxine) in pharmaceutical formulations, using a non-polar sorbent as a solid support to attain the separation and subsequent preconcentration/detection of the targeted analytes. A multicommutated flow-through multisensor based on the direct intrinsic solid-phase UV absorbance measurements of the analytes on a packed C₁₈ silica gel bed was then thoroughly developed. The usefulness of this approach was assessed when it was applied to the determination of piroxicam and pyridoxine in different pharmaceutical formulations obtaining remarkable results.     

Monitoring of the smoking process by multicommutation Fourier transform infrared spectroscopy

Nicotine was selected as the target molecule for monitoring of the smoking process by multicommutation Fourier Transform Infrared spectroscopy (FTIR). The method involved the use of CHCl₃ for on-line extraction of nicotine from tobacco, cigarette filters and tobacco ash from NH₄OH alkalinized samples, and absorbance measurement of the characteristic band at 1316 cm⁻¹ in the stopped-flow mode, by obtaining the peak area in the range between 1334 and 1300 cm⁻¹. Under the best operational conditions, the procedure developed provided a detection limit of 0.05 mg mL⁻¹ nicotine, corresponding to 0.5 mg g⁻¹ in the solid sample, a relative standard deviation less than 2.5%, and a sampling frequency of 12 determinations h⁻¹. It can be concluded that nicotine migrates in the smoke mainstream towards the filter during the smoking process. The smoking of cigarettes and cigars is different. Nicotine is retained weakly by both tobacco and filter in the case of cigarettes, and strongly by the unburned tobacco in cigars. The incomplete smoking of cigars and cigarettes reduces nicotine intake and thus reduces the additive effect.     

A flow injection procedure based on solenoid micro-pumps for spectrophotometric determination of free glycerol in biodiesel

A flow system designed with solenoid micro-pumps is proposed for fast and greener spectrophotometric determination of free glycerol in biodiesel. Glycerol was extracted from samples without using organic solvents. The determination involves glycerol oxidation by periodate, yielding formaldehyde followed by formation of the colored (3,5-diacetil-1,4-dihidrolutidine) product upon reaction with acetylacetone. The coefficient of variation, sampling rate and detection limit were estimated as 1.5% (20.0 mg L⁻¹ glycerol, n = 10), 34 h⁻¹, and 1.0 mg L⁻¹ (99.7% confidence level), respectively. A linear response was observed from 5 to 50 mg L⁻¹, with reagent consumption estimated as 345 μg of KIO₄ and 15 mg of acetylacetone per determination. The procedure was successfully applied to the analysis of biodiesel samples and the results agreed with the batch reference method at the 95% confidence level.     

An environmentally friendly flow system for high-sensitivity spectrophotometric determination of free chlorine in natural waters

A green and highly sensitive analytical procedure was developed for the determination of free chlorine in natural waters, based on the reaction with N,N-diethyl-p-phenylenediamine (DPD). The flow system was designed with solenoid micro-pumps in order to improve mixing conditions by pulsed flows and to minimize reagent consumption as well as waste generation. A 100-cm optical path flow cell based on a liquid core waveguide was employed to increase sensitivity. A linear response was observed within the range 10.0 to 100.0 µg L^− 1, with the detection limit, coefficient of variation and sampling rate estimated as 6.8 µg L^− 1 (99.7% confidence level), 0.9% (n = 20) and 60 determinations per hour, respectively. The consumption of the most toxic reagent (DPD) was reduced 20,000-fold and 30-fold in comparison to the batch method and flow injection with continuous reagent addition, respectively. The results for natural and tap water samples agreed with those obtained by the reference batch spectrophotometric procedure at the 95% confidence level.     

A downsized flow set up based on multicommutation for the sequential photometric determination of iron(II)/iron(III) and nitrite/nitrate in surface water

In this work, a downsized flow set up designed based on multicommutation concept for photometric determination of iron(II)/iron(III) and nitrite/nitrate is surface water is described. The flow system network comprised a set of three-way solenoid valves, reaction coil and a double-channel flow cell, which were nested in order to obtain a compact and small-size instrument. To accomplish the downsizing requirement light source (LED) and radiation detection (phototransistor) were coupled to the flow cell. In order to demonstrated the effectiveness of the system, the photometer methods based on Griess reaction and 1-10-phenantroline for nitrite and iron(II) determination, respectively, were selected. Under computer control the set up provided facilities to handle four reagent solutions employing a single pumping channel, thus permitting also the determination of nitrate and iron(III) after its reduction to nitrite and to iron(II), respectively. The overall system performance was demonstrated working several days running standard solution, no significant variation of base line, linear response range and slop (less than 1%) were observed. The usefulness of the downsized system was ascertained by analyzing a set of surface water. Aiming to access the accuracy sample were also analyzed employing reference procedures and no significant difference at 95% confidence level were observed for the four analytes. Other profitable features such as analytical throughput of 40 determination per hour; relative standard deviation of 1%; linear response range between 50 and 300 μg l⁻¹ for nitrite and nitrate, 0.5-6.0 mg l⁻¹ iron(II) and iron(III); low reagent consumption 75 μg for nitrate/nitrite and 0.6 mg for iron(II)/iron(III) per determination; and 2.4 ml waste generation per determination were also achieved.     

Flow-injection turbidimetric determination of homatropine methylbromide in pharmaceutical formulations using silicotungstic acid as precipitant reagent

A flow-injection turbidimetric procedure exploiting merging zones is proposed for determining homatropine methylbromide (HMB) in pharmaceutical preparations. The determination is based on the precipitation reaction of homatropine methylbromide with silicotungstic acid in acidic medium to form a precipitate, which was measured at 410 nm. The analytical curve was linear in the HMB concentration range from 8.1 × 10⁻⁵ to 2.2 × 10⁻⁴ mol l⁻¹, with a detection limit of 5.0 × 10⁻⁶ mol l⁻¹. The recoveries ranged from 96 to 103%, the sampling frequency was 70 determinations per hour and relative standard deviations were less than 1.5% (n = 10). The results obtained for commercial formulations using the FIA procedure were in good agreement with those obtained by using a comparative method.     

共振光散射比浊法测定钾

近年来共振光散射技术已成功用于生化、环境、食品等分析领域[1 5]。本文基于四苯硼钠与钾作用产生难溶盐,使用表面活性剂使悬浊液保持稳定,共振光散射比浊法试验发现在pH=8 78的缓冲溶液、2mL浓度为5×10-3mol/L的四苯硼钠溶液,8mL乙二醇作为分散剂的条件下,该体系空白溶液的RLS较弱,当加入一定量的钾离子后体系RLS强度明显增强,且体系在0 0～4 6×10-4mol/L范围内线性关系良好,回归方程为:I=3 828cK+-0 071　R=0 9969检测限以3δ计算为0 124×10-6mol/L。该法用于尿液中钾含量的测定简便快捷,回收率92 6～103 5%之间,相对误差0 …     

A clean method for flow injection spectrophotometric determination of cyclamate in table sweeteners

A flow system based on the multicommutation is proposed for fast and clean determination of cyclamate. The procedure exploits the reaction of cyclamate with nitrite in acidic medium and the spectrophotometric determination of the excess of nitrite by iodometry. The flow system was designed with a set of solenoid micro-pumps to minimize reagent consumption and waste generation. The detection limit was estimated as 30 μmol L⁻¹ (99.7% confidence level) with linear response ranging up to 3.0 mmol L⁻¹. The coefficient of variation was estimated as 1.7% for a solution containing 2.0 mmol L⁻¹ cyclamate (n = 20). About 60 samples can be analyzed per hour, consuming only 3 mg KI and 1.3 μg NaNO₂, and generating 2.0 mL of effluent per determination, thus providing an environmentally friendly alternative to previously proposed procedures. Common artificial and natural sweeteners did not interfere when present in concentrations 10-times higher than cyclamate. The procedure was successfully applied for determination of cyclamate in artificial table sweeteners with results in agreement with the reference method at the 95% confidence level.     

A comparative study of LED-induced fluorescence and laser-induced fluorescence in SDS-CGE: application to the analysis of antibodies

LEDs present an alternative to lasers in LIF detection with CE, resulting in LED-induced fluorescence (LEDIF). LEDs are much less expensive, consume less energy and are more stable. In addition, LED light sources allow a greater range of wavelengths to better match the maximum wavelength for the fluorescence of the dye. Antibodies were largely studied in SDS capillary gel electrophoresis (SDS-CGE) and LIF detection with different dyes to label the proteins. In this work, our goal is to show that LEDs can advantageously replace lasers. We used 5-carboxytetramethylrhodamine succinimidyl ester (5-TAMRA.SE), 3-(2-furoyl)-quinoline-2 carboxaldehyde (FQ), and naphthalene-2,3-dialdehyde (NDA) to label IgG and we compared the LIF sensitivity with that obtained from LEDIF. We measured that the LOD values of LEDIF are identical to that obtained with the wavelength equivalent laser, and for 5-TAMRA.SE analysis, LOD values are about six times better than when the classical 488 nm laser was used.     

Turbidimetric determination of sulphate in waters employing flow injection and lead sulphate formation

An analytical flow-injection procedure based on PbSO₄ colloidal formation is proposed as a turbidimetric determination of sulphate in natural waters. Ethanol-water was used as a medium in order to improve the sensibility of the method. Both chemical and flow variables as well as interfering species were studied. A detection limit of 0.3 μg SO²⁻₄ ml⁻¹ was found, and the analytical range (according to Beer's law) was 2–20 μg SO²⁻₄ ml⁻¹. The precision was better than 3% R.S.D. and the sample throughput was ca. 35 h⁻¹. The method, when compared with a standard methodology, gave good results when applied to water analysis.     

A concept of dual optical detection using three light emitting diodes

In this paper a concept of very simple measurement system dedicated for simultaneous photometric and fluorometric detection is presented. Only three ordinary unmodified light emitting diodes (LEDs) can be applied in this analytical device: one of them is used in the conventional way as a source of nearly monochromatic light inducing fluorescence, whereas two others are applied as photometric and fluorometric detectors of light. In this study quinine is chosen as a model analyte. The reported device enables simultaneous detection of this analyte in the micromolar range of concentration. The practical utility of prototype dual detector for complex sample analysis is illustrated by its application for determination of quinine in tonic water samples.