A critical evaluation of a long pathlength cell for flow-based spectrophotometric measurements

Coupling of a flow cell based on a liquid core waveguide (LCW) to flow systems for spectrophotometric measurements was critically evaluated. Flow-based systems with and without chemical reactions were exploited to estimate the increase in analytical signal in comparison to those obtained with a conventional 1-cm cell under different experimental conditions. The Schlieren effect associated to intense concentration gradients in the sample zone was investigated with model solutions that do not absorb visible electromagnetic radiation. The effect of radiation scattering was lower than the expected by considering the increase in the optical path, being the magnitude of the perturbation up to 40% higher for the 100-cm LCW cell. Several alternatives for compensation of the Schlieren effect were experimentally investigated. The potentiality of the LCW for turbidimetric measurements and coupling to monosegmented flow analysis was also evaluated.     

Dilution Methods in Flow Injection Analysis. Evaluation of Different Approaches as Exemplified for the Determination of Nitrosyl in Concentrated Sulphuric Acid

Abstract

Instigated by developing a flow injection procedure for assay of nitrosyl in concentrated sulphuric acid, different approaches for reliable and robust on-line dilution in FIA were evaluated. These comprised the application of mixing tees in conjunction with mixing coils (including knotted reactors) of different internal diameter, zone sampling, the use of a mixing chamber, micro-sampling, and sample injection by means of pseudo-hydrodynamic injection. The individual approaches are described in detail, their advantages and disadvantages being emphasized in regard to their practical applicability. For each approach the criteria stipulated were that the procedure should allow a dilution factor of approximately 100, yet without excessive zone spreading, so that it, on one hand, could effectively eliminate the pronounced Schlieren effect encountered when mixing concentrated sulphuric acid with an aqueous diluent, and, on the other hand, would permit the sample material to be appropriately conditioned for the ensuing chemical derivatization procedure. It was found that this most reliably could be effected by a combination of pseudo-hydrodynamic injection comprising a mixing point and the use of mixing tees in conjunction with knotted reactors of relatively large internal diameter (1.5 mm). The optimized FI-manifold was used with the Griess method for the spectrophotometric assay of nitrosyl (nitrite) in standards prepared in the matrix of concentrated sulphuric acid (detection limit 0.16 mg/1 NO⁺-N (3[sgrave])) and in practical WSA-samples.     

A novel strategy to verification of adulteration in alcoholic beverages based on Schlieren effect measurements and chemometric techniques

A novel strategy to evaluation of adulteration in alcoholic beverages based on the measurement of the Schlieren effect using an automated FIA system with photometric detection is proposed. The assay is based on the Schlieren effect produced when beverage samples are injected in a single-line FIA system that uses water as carrier stream and a light-emitting diode-phototransistor photometer controlled by microcomputer as detector. The flow system presents limited mixing conditions which make possible to create gradients of refractive index (Schlieren effect) in the injected sample zone. These gradients are reproducible, characteristic of each alcoholic beverage and undergo specific modifications when adulterations with water or ethanol are imposed. Schlieren effect data of brandies, cachaças, rums, whiskies and vodkas were treated by SIMCA to elaborate class models applied in the evaluation of alcoholic beverages adulteration. Samples of the original matrix of each sort of beverages were adulterated in laboratory by adding water, methanol and ethanol in levels of 5% and 10% (v/v). These samples were used as test set to validate SIMCA class models. The verification of authenticity using Schlieren effect measurements presented good results making possible to identify 100% of the beverages samples adulterated in laboratory and 93% of the actual adulterated alcoholic beverages with confidence levels of 95%. As principal advantage, the automated system does not use reagents to carry out the analysis.     

Compensation of the Schlieren effect in flow-injection analysis by using dual-wavelength spectrophotometry

The Schlieren effect in flow-injection analysis is critically examined. Effects of sample constitution, injection volume, coil lengths, flow-rates, confluent stream addition and temperature are studied and practical implications in flow-injection design with and without the stopped-flow approach are discussed. For Schlieren compensation, a diode-array spectrophotometer is used and non-specific absorbance subtraction is exploited: the incident light passes through the flowing sample, the emergent light is dispersed, the intensities of two selected monochromatic beams are measured simultaneously by separate detectors and real-time subtraction of the wavelength-independent noise is achieved. The sensitivity and measurement precision improve after application of the subtraction algorithm. The potential, limitations and practical applications of the method are discussed.     

Spectrophotometric determination of iron and boron in soil extracts using a multi-syringe flow injection system

In the last decade, significant advances in flow analysis have been reported, namely the extensive use of computer-controlled devices to enhance the autonomy and performance of analysers. In the present work, computer-controlled multi-syringe flow injection systems are proposed to perform the spectrophotometric determination of available iron and boron in soil extracts. The methodologies were based on the formation of ferroin complex (determination of iron) and azomethine-H reaction (determination of boron). Both determinations were performed in manifolds with similar configurations by changing the reagents present in the different syringes. In the determination of iron, elimination of Schlieren effect in the detection system was achieved through the binary sampling approach, where a three-way valve was actuated to intercalate small slugs of sample and reagent, promoting better mixing conditions for solutions with different values of refractive index. In the determination of boron, in-line sample blank measurement was attained by omitting the introduction of reagent through software control, without manifold reconfiguration. Linear calibration curves were established between 0.50 and 10.0 mg Fe l⁻¹ and between 0.20 and 4.0 mg B l⁻¹. No systematic difference was found when soil extracts were analysed by the proposed methodologies and compared to the respective reference procedures.     

Chemical Derivatization in Flow Analysis

Chemical derivatization for improving selectivity and/or sensitivity is a common practice in analytical chemistry. It is particularly attractive in flow analysis in view of its highly reproducible reagent addition(s) and controlled timing. Then, measurements without attaining the steady state, kinetic discrimination, exploitation of unstable reagents and/or products, as well as strategies compliant with Green Analytical Chemistry, have been efficiently exploited. Flow-based chemical derivatization has been accomplished by different approaches, most involving flow and manifold programming. Solid-phase reagents, novel strategies for sample insertion and reagent addition, as well as to increase sample residence time have been also exploited. However, the required alterations in flow rates and/or manifold geometry may lead to spurious signals (e.g., Schlieren effect) resulting in distorted peaks and a noisy/drifty baseline. These anomalies can be circumvented by a proper flow system design. In this review, these aspects are critically discussed mostly in relation to spectrophotometric and luminometric detection.     

Extractive spectrophotometric determination of micro and sub-micro amounts of fluoride

A simple and sensitive extractive spectrophotometric determination of fluoride with the cerium(III)-alizarin complexan chelate has been investigated. The fluoro chelate formed is extracted into n-pentanol containing triethylamine. It is possible to achieve under selected conditions a selective extraction of the cerium(III)alizarin complexan-fluoride chelate. The stability of the chelate, the effect of temperature and the low absorbance of the blank are discussed. It is found that it is necessary to add a pH 9 buffer before the extraction. Procedures are given for the determination of 0.1-1 mug of fluoride in a 4-ml sample and 5-25 mug of fluoride in a 90-ml sample.     

Evolution of the commutation concept associated with the development of flow analysis

Evolution of the commutation concept has lead to the proposal and development of different generations of flow analyzers. Since the inception of the air-segmented flow systems till the availability of modern flow injection, sequential-injection and other flow-based analytical systems, a noteworthy improvement of the commutating devices has been noted.

Multi-functional manifold is described as a polyvalent approach for methodology implementation in a flow analyzer. It permits the investigation of mixing conditions under different flow patterns (unsegmented, segmented, monosegmented) with optional exploitation of the stopped-flow approach. For this purpose, spectrophotometric or turbidimetric measurements eventually affected by Schlieren noise were considered. Potentialities and limitations of the manifold are discussed in relation with methods based on relatively fast or slow chemical reactions. As applications, phosphate and chloride determinations in plant digests and natural waters were selected.

The manifold is characterized by high versatility and may work in connection with different flow configurations. Development will certainly lead to simple, versatile and miniaturized analyzers, able to run samples in a personalized fashion. In addition, random reagent selection, full automation, expansion of the analytical application range and increasing potentialities of the already existing methodologies are devised.     

On-line digitalization of Schlieren pictures inside the analytical ultracentrifuge

A rationalization of the analytical ultracentrifuge (AUC) is reported that also improves the accuracy of measurement with sedimentation runs controlled by Schlieren optics. A digital video camera was inserted into the optic beam of the AUC which detects Schlieren pictures on-line by means of an attached computer and evaluates them by instantaneous data reduction. Thus the photographic production of Schlieren pictures and their time-consuming manual evaluation can be avoided. With the new technique, a reference cell, a dark current cell, a brightness distribution cell, and five sample cells are simultaneously measured within an eight-cell rotor. Either a triggerable laser or a flashlight serves as a light source. Every 25 s, a Schlieren picture can be recorded and then be evaluated on-line by means of image processing.This paper was presented at the VI. Symposium on Analytical Ultracentrifugation, Marburg, FRG, February 16–17, 1989.     

Modification of the methylene blue method for spectrophotometric selenium determination

The spectrophotometric method for Se(IV) determination based on its catalytic effect in the reduction of Methylene Blue (MB) by sulphide is modified. The variables that affect the decolorization of MB were taken into account: reagent concentrations, order of addition, mixing and standing times, pH, ionic strength, temperature, solution volume, wavelength, etc. The results of this study allowed a decrease of the determination limit and, by selection of the appropriate analytical conditions, choice of optimum linear range according to the selenium content in the sample. The lower limit range is 15-75 mug/1., with 3% relative standard deviation and no systematic errors. Procedures for overcoming several potential interferences were studied. The proposed method was applied to several environmental samples and the results were compared with those obtained by other standard methods.     

Effect of mixing on the formation of complexes of hyperbranched cationic polyelectrolytes and anionic surfactants

The effect of different mixing protocols on the charged nature and size distribution of the aqueous complexes of hyperbranched poly(ethylene imine) (PEI) and sodium dodecyl sulfate (SDS) was investigated by electrophoretic mobility and dynamic light scattering measurements at different pH values, polyelectrolyte concentrations, and ionic strengths. It was found that at large excess of the surfactant a colloidal dispersion of individual PEI/SDS nanoparticles forms via an extremely rapid mixing of the components by means of a stop-flow apparatus. However, the application of a less efficient mixing method under the same experimental conditions might result in large clusters of the individual PEI/SDS particles as well as in a more extended precipitation regime compared with the results of stop-flow mixing protocol. The study revealed that the larger the charge density and concentration of the PEI, the more pronounced the effect of mixing becomes. It can be concluded that an efficient way to avoid precipitation in the solutions of oppositely charged polyelectrolytes and surfactants might be provided by extending the range of kinetically stable colloidal dispersion of polyelectrolyte/surfactant nanoparticles via the application of appropriate mixing protocols.     

Collision induced mixing of two light beams in Na2 molecules

We have studied the signal of two wave mixing in Na₂ molecules under high buffer gas pressure (10–100 Torr of He). The laser light was resonant to the Na₂ (X(v=3,J=43)→B(v′=6,J′=43) transition. The mixing signal appeared under high absorption conditions (370°–640 °C) and was collision induced. In the mixing process the transmitted intensity of the weaker beam was amplified at the cost of the stronger beam intensity. The influence of the dynamics of the ground state pumping process (depopulation by light absorption and repopulation by collisional relaxation) on the mixing process was analyzed.     

Optofluidic micro-sensors for the determination of liquid concentrations

We present a novel optofluidic device for non-invasive and label-free determination of liquid concentrations. A microfluidic channel filled with the sample solution is hit by laser light in an angle close to the critical angle for total internal reflection. Due to the intentionally defined divergence of the incident beam, parts of the rays will experience total internal reflection while another part will be transmitted. Both reflected and transmitted light signals are recorded and the ratio of these signals is used for sample characterization. The stability compared to single signal analyses is significantly improved, resulting in a resolution of approximately 40 mmol L(-1). The typical working range of the device under investigation is between a few tens of mmol L(-1) and 5 mol L(-1) making it useful for applications in the food industry, for example to determine the amount of phosphates in liquid products.     

TiO2-, ZnO-, and CdS-photocatalyzed oxidation of ethylene-propylene thermoplastic elastomers

The ZnO-, TiO₂-, and CdS-photocatalyzed oxidations of an amorphous ethylene-propylene copolymer ( EP copolymer) containing 75% w/w of ethylene are described. In solid films exposed under polychromatic (λ > 300 nm) or monochromatic (λ = 365 nm) UV light, it is observed that the introduction of pigment (0.5–5% w/w) strongly modified the course of the photooxidation of a transparent sample. Ketonic and lactonic groups accumulate in the polymer matrix without being converted photochemically into acidic, ester, and vinyl groups. In the kinetic study it is pointed out that the variations of the rate of formation of carbonyl groups depend on the nature of the pigment. With highly photoactive pigments (ZnO and untreated TiO₂ RL11A), the rate is at first a decreasing function of the pigment percent, then an increasing function. With poorly photoactive pigments (treated TiO₂ RL90 and CdS), the rate of formation of carbonyl groups is a decreasing function of the pigment content. It is therefore emphasized that, at a low pigment content, the inner filter effect prevails over the photocatalytic influence with any pigment. It is also observed that the rate of formation of vinyl groups, photoproducts formed from the excited ketones, is a monotonously decreasing function of the pigment content. The complete inhibition of the ketone photochemistries is observed with ZnO in conditions in which the light is not absorbed by the pigment, suggesting that the carbonyl groups formed are adsorbed on the pigment.     

Use of an oxidation reaction for the quantitative determination of albendazole with Chloramine-T and acid dyes.

One titrimetric and two spectrophotometric procedures have been reported for the determination of albendazole and its tablets. Using titrimetry, the drug was titrated directly with Chloramine-T under acidic conditions using a Methyl Orange indicator. The spectrophotometric procedures involve treating the sample solution with a measured excess of Chloramine-T in an acid medium, followed by an estimation of unreacted Chloramine-T by reacting with a fixed amount of either Methyl Orange or Indigo Carmine dye solution and measuring the absorbance at 510 nm or 610 nm. The stoichiometric ratio, which forms the basis for the calculations in titrimetry as well as the range of the applicability, are reported. The Beer's law range and sensitivity values for spectrophotometric procedures are included. The methods were applied to the determination of albendazole in tablets with satisfactory results.     

Novel luminescent liquid crystalline polyazomethines. Synthesis and study of thermotropic and photoluminescent properties

Novel semiflexible polyazomethines containing chromophoric units into azomethine mesogenic core have been synthesised by condensation of a flexible dialdehyde with mesogenic diamines containing fluorene, antraquinone, pyrimidine, azobenzene and benzophenone. The thermotropic behaviour of the resulting polyazomethines was assessed by differential scanning calorimetry, polarised light microscopy and investigations of the miscibility relations. While the pure polyazomethines showed a birefringent viscous texture difficult to be ascribed, by mixing with a liquid crystal dimer, clear Schlieren or marbled textures were observed, indicating a nematic mesophase. The polymers exhibited violet, blue or yellow light emission.     

Formation of intra- and interparticle polyelectrolyte complexes between cationic nanogel and strong polyanion

Polyelectrolyte complex formation of a strong polyanion, potassium poly(vinyl alcohol) sulfate (KPVS), with positively charged nanogels was studied at 25 degrees C in aqueous solutions with different KCl concentrations (C(s)) as a function of the polyion-nanogel mixing ratio based on moles of anions versus cations. Used as the gel sample was a polyampholytic nanogel consisting of lightly cross-linked terpolymer chains of N-isopropylacrylamide, acrylic acid, and 1-vinylimidazole; thus, the complexation was performed at pH 3 at which the imidazole groups are fully protonated to generate positive charges. Turbidimetric titration was employed to vary the mixing ratio. Also employed for studies of the resulting complexes at different stages of the titration were dynamic light scattering (DLS) and static light scattering (SLS) techniques. It was found from the titration as well as DLS and SLS that there is a critical mixing ratio (cmr) at which both the size and molar mass of the complexed gel particles abruptly increase. The value of the cmr at C(s) = 0 or 0.01 M (mol/L) was observed at approximately 1:1 mixing ratio of anions versus cations but at lower mixing ratios than the 1:1 ratio under conditions of C(s) = 0.05 and 0.1 M. At the mixing ratios less than the cmr, the molar mass of the complex agrees with that of one gel particle with the calculated amount of the bound KPVS ions, indicating the formation of an "intraparticle" KPVS-nanogel complex, by the aggregation of which an "interparticle" complex is formed at the cmr. During the process of the intraparticle complex formation, both the hydrodynamic radius by DLS and the radius gyration by SLS decreased with increasing mixing ratio, demonstrating the gel collapse due to the complexation. At C(s) = 0 or 0.01 M and under conditions where the amount of KPVS bindings was less than half of the nanogel cations, however, the decrease of the hydrodynamic radius was very small, while the radius gyration fell monotonically. These results were discussed in connection with a collapse of dangling chains attached to the nanogel surface by the binding of KPVS.     

3D mapping of the output laser beam from a PDLC sample

Self-transparency due to thermal non-linearities is presented as a basic switching effect in a thick polymer dispersed liquid crystal sample. For the first time a detailed 3D mapping of the output laser beam as a function of the x-y coordinates is presented: changes of the transmitted beam profile are recorded vs. both incident power and time. It is discussed how light intensity and temperature can be used as control parameters for the non-linear part of the refractive index. The experimental results confirm the existence of a threshold value of the incident light intensity at which the device switches from the scattering state to the transmissive state.     

A precise uranium assay using solvent extraction and spectrophotometry

The uranium spectrophotometric measurement using the uranylnitrate-quaternaryamine solvent extraction method is investigated to identify factors that affect precision and accuracy of the uranium determination. The inherent spectrophotometric precision was measured with neutral density filters in the sample light path and was found to be <0.1% relative standard deviation (RSD). Under selected experimental conditions, temperature instability has a –0.02% effect on the extraction, and a –0.4% effect on the absorbance of the uranium extract in 2-nitropropane (2-NP) or methyl isobutyl ketone (MIBK) solvents. Under optimum conditions at the 10 mg uranium level, RSDs of 0.1% resulted.     

3D mapping of the output laser beam from a PDLC sample

Self-transparency due to thermal non-linearities is presented as a basic switching effect in a thick polymer dispersed liquid crystal sample. For the first time a detailed 3D mapping of the output laser beam as a function of the x-y coordinates is presented: changes of the transmitted beam profile are recorded vs. both incident power and time. It is discussed how light intensity and temperature can be used as control parameters for the non-linear part of the refractive index. The experimental results confirm the existence of a threshold value of the incident light intensity at which the device switches from the scattering state to the transmissive state.