A non-extraction sequential injection method for determination of loratadine using formation of its ion-association complex with bromocresol purple in acetonitrile.

The formation of an ion-association complex (IA) between sulfonephthalein dye and basic nitrogen-containing compound in an organic solvent medium has been for the first time used to develop an automated SIA method. In highly polar aprotic solvents, the tautomeric equilibrium for such dyes is strongly shifted towards the colorless lactonic form. The addition of a basic nitrogen-containing substance leads to the formation of IA with a highly colored quinonoid form, which is accompanied by an increase in the absorbance of the dye band at approximately 400 nm. Protonation of pyridine nitrogen in loratadine, structure and binding places of IA were shown using quantum-chemical calculations. The very simple, direct and non-extraction spectrophotometric SIA method with high throughput of 43 h-1 was developed based on the formation of IA between loratadine and bromocresol purple in the medium of acetonitrile used both as solvent and carrier. The calibration graph was linear in the concentration range from 1.0 to 20 mg L-1 with correlation coefficient of 0.9992. The developed method was successfully applied to the analysis of pharmaceutical formulations.

Extraction-less green spectrofluorimetric method for determination of mercury using an Astra Phloxine fluorophore: Comprehensive experimental and theoretical studies.

A new sensitive and selective extraction-less method for the spectrofluorimetric determination of Hg2+ has been developed using the polymethine dye Astra Phloxine (AP) with requirements for green analytical chemistry. The principle of this method for analytical use is the formation of an ion associate (IA) in the presence of mercury ions and AP, which causes a change in the electronic structure of the dye cation and its subsequent fluorescence quenching. The IA created during the process was sufficiently stable in aqueous solutions and did not require the use of surfactants or organic solvents, which are typically used for similar analytical systems. The system indicated high selectivity towards Hg2+ in the presence of at least 100-fold higher concentrations of Co2+, Fe2+, Mg2+, Ni2+, Zn2+, Ca2+, Ba2+, K+, Na+. The calibration curve was linear in the range from 0.003 to 0.1 mg L-1. Precision and accuracy were expressed as intra-day and inter-day analysis with RSD values of 2.9 - 4.8 % and recovery of 97.1 - 110.0 %. The proposed method was used for the determination of Hg2+ on the model and real water samples. Theoretical calculations were used to predict the IA structure and to explain the experimentally observed fluorescence spectra. A few theoretical methods were tested for predicting IA emission energies, and the CIS(D) method was found to be the most accurate.

Direct immersion single-drop microextraction combined with fluorescence detection using an optical probe. Application for highly sensitive determination of rhodamine 6G.

The use of an optical probe for fluorescence detection combined with direct immersion single-drop microextraction has been demonstrated as an innovative approach. The optical probe served both as a drop holder for extractant and as a measuring device which made it possible to eliminate the use of cuvettes. A laser and a light emitting diode (LED) were tested as possible light sources. Both of them showed comparable results. However, given the much smaller half-band width of the laser radiation, its use has proven to be preferable since background correction can be eliminated. Direct immersion single-drop microextraction of an ionic association complex of rhodamine 6G with picric acid with subsequent fluorescent detection (λex was 532 nm and 525 nm for laser and LED, respectively; λem was 560 nm for both laser and LED) was used a model system to evaluate the new approach. The extractant phase was a 55 µL amyl acetate microdrop fixed in the optical part of the probe. LOD, LOQ and linear calibration range were found as 0.14, 0.48 and 0.5-10 nmol L-1, and 0.15, 0.50 and 0.5-5 nmol L-1 for laser and LED light sources, respectively. The accuracy of the method was assessed by analyzing real water samples.

Headspace Microextraction. A Comprehensive Review on Method Application to the Analysis of Real Samples (from 2018 till Present).

This work describes current trends in the development of headspace microextraction methods. The main trends in the selection of detection techniques used in combination with microextraction and preferences in the selection of headspace liquid-phase microextraction (HS-LPME) or headspace solid-phase microextraction (HS-SPME) methods, depending on the analytes and their quantity, are also briefly presented. In the main part of the work, on the basis of current journal literature, headspace microextraction analytical methods used for the determination of various inorganic and organic analytes are classified and compared over the last five years. The work also reflects the current modifications of techniques and approaches proposed for these microextraction methods.

Trends in the development of headspace microextraction methods are discussed.Trends in choosing detector techniques after microextraction are also presented.Analytes determination with headspace microextraction is classified and compared.

Consecutive spectrophotometric determination of phosphate and silicate in a sequential injection lab-at-valve flow system.

A new highly sensitive and selective sequential injection lab-at-valve spectrophotometric method for the consecutive determination of silicate and phosphate is described. The proposed method is based on the formation of specific ion-association complexes (IAs) of 12-heteropolymolybdates of phosphorus and silicon (12-MSC) with Astra Phloxine. The addition of an external reaction chamber (RC) to the SIA manifold made it possible to significantly improve the conditions for the formation of the analytical form used. The formation of the IA took place in the RC; the solution is mixed by passing an air flow through it. The interfering effect on the determination of phosphate from silicate was completely eliminated by choosing an acidity at which the rate of 12-MSC formation is very low. The use of secondary acidification in the determination of silicate led to the complete exclusion of the influence of phosphate. The tolerable ratio of phosphate to silicate and vice versa is about 100-times, which allows the analysis of most real samples without the use of masking agents or complex separation steps. The determination ranges are 3.0-60 µg L-1 for phosphate as P(V) and 2.8-56 µg L-1 for silicate as Si(IV) at a throughput of 5 samples h-1. The detection limits are 5.0 and 3.8 µg L-1 for phosphate and silicate, respectively. Silicate and phosphate were determined in the tap water, river water, mineral water, main water of the Krivoy Rog (Ukraine) region, and the certified reference material of carbon steel.

A new approach for sulfite determination by headspace liquid-phase microextraction with an optical probe.

A new approach of headspace liquid-phase microextraction with an optical probe (HS-LPME-OP), which solves the problem of the extraction phase retention in the hole of the optical probe and provides the possibility of simpler, more precise and reliable online processing of the analytical signal, was used for sulfite determination. A 1 × 10-4 M 5,5'-dithiobis-(2-nitrobenzoic) acid (DTNB) solution was used as an acceptor phase. It was placed in a plastic vial fixed in the headspace above the analyte solution. An optical probe immersed in the acceptor phase was used to monitor the analytical signal. Sulfite determination is based on the release of sulfur dioxide from the sample after the addition of ortho-phosphoric acid, followed by its extraction with an aqueous solution of DTNB at pH 7.0. The absorbance was measured at 412 nm. The calibration graph was linear in the range from 32 to 320 µg L-1 with a detection limit of 14 µg L-1. The developed method is sensitive, highly selective and reproducible. It was successfully applied for the sulfite determination in juice, alcoholic beverages and jam.

Online determination of sulfide using an optical immersion probe combined with headspace liquid-phase microextraction.

A new design for headspace liquid phase microextraction in combination with an optical immersion probe (HS-LPME-OIP) was proposed and successfully tested for the determination of sulfide in wine and water samples. The developed method is based on the release of hydrogen sulfide from the aqueous phase after the addition of orthophosphoric acid and its extraction with an aqueous solution of 5,5'-dithiobis-(2-nitrobenzoic) acid (DTNB). The analytical signal was recorded using an optical probe immersed in a vial containing 200 µL of 0.1 mM DTNB solution. Using the optical immersion probe in combination with HS-LPME allowed to register the analytical signal online and significantly improve the reproducibility of sulfide determination compared to known microextraction approaches. In the proposed approach, the problems with drop stability, limitations in mixing rate or extraction time, too small volume of the acceptor phase and stability of the holding the acceptor phase in the hole of the optical probe were also satisfactorily solved. The calibration graph was linear in the range of 16-256 µg L-1 with a correlation coefficient of 0.9992. The limit of detection was 6 µg L-1.

Development of a New Kinetic Spectrophotometric Method for the Determination of Chromium with an Optical Probe.

The aim of this work is the development, optimization, and validation of a new spectrophotometric kinetic method for the determination of dissolved chromium species in water samples with the use of the polymethine dye Astra Phloxine FF. The progress of the chemical reaction was simple, effective, and precisely monitored from the start of the reaction using an optical probe. The method is based on the impact of Cr(VI) concentration on the rate of decrease in the Astra Phloxine FF concentration. The experimental data were evaluated using four experimental data analysis methods, namely with the initial rate method, the average rate method, the fixed time method, and the absorption peak volume change method. Under the optimal reaction conditions, the best results were achieved using the method of the average rate constant for evaluating the experimental data. Using this data evaluation method for the determination of Cr(VI), the LoD was found to be 1.87 µg L-1 and RSD ( n = 6; 0.2 mg L-1 Cr) 3.59%. The presented work was used for the determination of chromium in model samples-CRM material and tap and waste water-and with the calibration line method and the standard additions method.

Use of sequential injection analysis with lab-at-valve and an optical probe for simultaneous spectrophotometric determination of ascorbic acid and cysteine by mean centering of ratio kinetic profiles.

Two new, simple, relatively fast and robust methods for the simultaneous kinetic determination of binary mixtures of ascorbic acid (Asc) and cysteine (Cys) were developed using the mean centering of ratio kinetic profiles method. The methods are based on the difference in the reaction rates of Asc and Cys with 18-molybdodiphosphate at pH 5.1. An optical probe as well as the sequential injection analysis lab-at-valve (SIA-LAV) method were used to carry out simultaneous kinetic analysis. The benefits of the mean centering of ratio kinetic profiles method were shown in comparison with other spectrophotometric kinetic methods. Asc and Cys can be determined in the concentration ranges 20-200 and 8-90 µmol L-1 with the batch spectrophotometric method and 10-200 and 4-40 µmol L-1 with the SI-LAV method, respectively. The method was successfully used to determine Asc and Cys in dietary supplements.

Thin-Layer Chromatography: an Efficient Technique for the Optimization of Dispersive Liquid-Liquid Microextraction.

Thin-layer chromatography (TLC) is an often omitted analytical technique due to its lower sensitivity and separation capacity. Even in the era of high-performance liquid chromatography (HPLC), thin-layer chromatography still offers many advantages, such as simplicity, rapidity, and cost-effectiveness, which predict TLC to be the first-choice method for the laborious optimization process requiring analysis of numerous samples. In this work, a thin-layer chromatography method with chemical and densitometric detection was used to optimize a dispersive liquid-liquid microextraction (DLLME) process for the extraction and preconcentration of estradiol in human urine. The chromatographic system consisted of silica gel plates as the stationary phase and toluene-ethanol (9:1; v/v) mixture as the developing solvent. The plates were dyed with 10% phosphomolybdic acid reagent and sequentially evaluated densitometrically at λ = 430 nm. In the context of DLLME optimization, parameters including the type and volume of extraction and dispersive solvents, centrifugation, salt addition and extraction time, were studied. The proposed DLLME-TLC method was successfully applied to the determination of estradiol in real human urine samples.

Structural and spectrophotometric characterization of 2-[4-(dimethylamino)styryl]-1-ethylquinolinium iodide as a reagent for sequential injection determination of tungsten.

Structure, spectrophotometric and protolytic properties of the styryl dye 2-[4-(dimethylamino)styryl]-1-ethylquinolinium iodide (R) as well as its complex with tungsten were studied. The selective protonation of dimethylamino group was confirmed by density functional theory investigation through the computation of Fukui function, NPA partial atomic charges, and NICS(0) aromaticity indexes. The TD-DFT study explains the experimental change of color by excluding the dimethylamino group from HOMO orbital upon protonation. The acid dissociation constant, the optimum wavelength and the molar absorptivity of R were found to be: 3.02, 501nm and 4.0×104Lmol-1cm-1, respectively. The protolytic properties of the reagent were found to change significantly in the presence of tungsten(VI). Analysis of bond critical points between the anions and Quinaldine Red cation gives the selectivity raw HWO4->MoO4->H2VO4->ReO4->ClO4-, that perfectly match with the experimental data. Based on this observation, a non-extractive sequential-injection spectrophotometric method for the determination of tungsten was developed. The absorbance of the colored extracts obeys Beer's law up to 55.2mgL-1 of W at 520nm wavelength. The limit of detection calculated from a blank test (n=10) based on 3s was 0.96mgL-1. The developed method was applied for the determination of tungsten in model samples.

Vortex-assisted liquid-liquid microextraction and indirect spectrophotometric determination of chromium(vi).

A novel, simple, sensitive and selective method for the indirect spectrophotometric determination of chromium(vi) was developed on the basis of vortex-assisted liquid-liquid microextraction (VALLME) of an ion association pair formed between the triiodide anion (I3 -) and cationic dye Astrazone Brilliant Red 4G (ABR). The indirect spectrophotometric determination of chromium(vi) was based on the redox-reaction of Cr(vi) with iodide and formed I3 -. The triiodide anion was determined spectrophotometrically at 530 nm following VALLME of an ion association pair with ABR. The calibration plot was linear in the range 0.050-4.2 µg L-1 (R 2 = 0.998), and limit of detection (LOD) was 0.015 µg L-1 for Cr(vi). The suggested procedure was successfully applied for the determination Cr(vi) in water samples (RSD 3.3-5.7%, recovery 97.7-102.8% when determining ultratrace levels Cr(vi) at 0.55-5.77 µg L-1), the accuracy of the method was assessed through a comparison with reference methods and certified reference materials.

Simultaneous determination of rutin and ascorbic acid in a sequential injection lab-at-valve system.

A green, simple, accurate and highly sensitive sequential injection lab-at-valve procedure has been developed for the simultaneous determination of ascorbic acid (Asc) and rutin using 18-molybdo-2-phosphate Wells-Dawson heteropoly anion (18-MPA). The method is based on the dependence of the reaction rate between 18-MPA and reducing agents on the solution pH. Only Asc is capable of interacting with 18-MPA at pH 4.7, while at pH 7.4 the reaction with both Asc and rutin proceeds simultaneously. In order to improve the precision and sensitivity of the analysis, to minimize reagent consumption and to remove the Schlieren effect, the manifold for the sequential injection analysis was supplemented with external reaction chamber, and the reaction mixture was segmented. By the reduction of 18-MPA with reducing agents one- and two-electron heteropoly blues are formed. The fraction of one-electron heteropoly blue increases at low concentrations of the reducer. Measurement of the absorbance at a wavelength corresponding to the isobestic point allows strictly linear calibration graphs to be obtained. The calibration curves were linear in the concentration ranges of 0.3-24mgL-1 and 0.2-14mgL-1 with detection limits of 0.13mgL-1 and 0.09mgL-1 for rutin and Asc, respectively. The determination of rutin was possible in the presence of up to a 20-fold molar excess of Asc. The method was applied to the determination of Asc and rutin in ascorutin tablets with acceptable accuracy and precision (1-2%).

Speciation of platinum by GFAAS using various possibilities of analytical signal enhancement.

A novel method for determination of platinum species by application of graphite furnace atomic absorption spectrometry (GFAAS) was developed. The principle of determination is the formation of platinum ion associates (IA) with SCN- and polymethine basic agent 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3-dihydroindol-2-yliden)-propyl-1,3-dienyl]-3H-indolium chloride (TTDI), which can then be extracted by various organic solvents. Different options for analytical signal intensification (ultrasonic and microwave energy) were examined. The conditions found for ion associate formation and extraction have enabled the proposing of a new Pt(II) and Pt(IV) speciation process. These species can be reliably determined simultaneously at concentration ratios from 1:5 to 5:1. Moreover, the ion associates of platinum with TTDI can be extracted with toluene up to a volume ratio of aqueous and organic phases of Vaq:Vorg = 50:1. This fact for Pt determination using GFAAS means decreasing the limit of detection (LOD) from 7.1µgL-1 to 0.3µgL-1. The method was applied for Pt determination in a model and in spiked water samples.

A non-extractive sequential injection method for determination of molybdenum.

A non-extractive sequential injection spectrophotometric method for the determination of molybdenum has been developed. The method is based on the reaction between the thiocyanate complex of molybdenum and the polymethine dye (2-[2-(4-dipropylamino-phenyl)-vinyl]-1,3,3-trimethyl-3H-indolium chloride) in a hydrochloric acid medium. The calibration plot in the SIA system was linear from 0.080mgL(-1) to 1.92mgL(-1) of Mo; LOD was 0.021mgL(-1). The method was applied for the determination of molybdenum in spiked drinking water and mineral water.

Highly sensitive sequential injection determination of p-aminophenol in paracetamol formulations with 18-molybdodiphosphate heteropoly anion based on elimination of Schlieren effect.

A highly sensitive, precise and automated method using sequential injection analysis to assay quantitatively low levels of the p-aminophenol (PAP) in paracetamol formulations has been developed. A solution containing PAP and paracetamol is injected into an acetate buffer carrier stream and merged on-line with 18-molybdodiphosphate heteropoly complex reagent to form a specific blue derivative that is subsequently detected spectrophotometrically at 820nm. The procedure has been optimized mainly with respect to measurement sensitivity. It is based on the leveling off of the refraction indices of the liquids mixed in the flow system by the careful matching of the refractive index of the reagent solution with that of the carrier and sample solutions. Amount as low as 0.5µmolL(-1) of PAP, which corresponds to the 0.001% of PAP in paracetamol tablets, can be reliably determined using the proposed method, which is clearly below the specification limits recommended for PAP determination in paracetamol drug and tablet formulations (50ppm or 0.005% (w/w)). The developed method was successfully applied to the analysis of paracetamol formulations spiked with PAP and determination of PAP content in Rapidol tablets past their expiration date both by proposed SIA and reference HPLC methods.

Sequential injection determination of orthophosphate as ion associate of 12-molybdophosphate with Astra Phloxine.

A simple and fast reaction between 12-molybdophosphate heteropoly anion and the polymethine dye Astra Phloxine was used for the development of a new SIA method for the determination of orthophosphate. The suggested method has higher sensitivity and a broader calibration range than existing SIA methods. It can be used to detect phosphate in the range from 0.2 to 10 µmol L(-1) with a detection limit of 0.1 µmol L(-1) and an acceptable throughput of 20 samples h(-1). The comparably low molybdate (5.6 mmol L(-1)) and dye (0.1 mmol L(-1)) concentrations led to an improvement in the stability of the base line. Inter-day reproducibility was better than 5%, while the intra-day RSD was in the range 0.8-3.5%. The method was used for the analysis of natural water samples and phosphorus-containing chemicals having a low content of orthophosphate.

11-Molybdobismuthophosphate--a new reagent for the determination of ascorbic acid in batch and sequential injection systems.

The guanidinium salt of the new heteropolymolybdate 11-molybdobismuthophosphate Gua(6)PBiMo(11)O(40) (11-MBP) was synthesized, characterized and used as a reagent for batch spectrophotometric (SP) and sequential injection determination of ascorbic acid (AsA). When compared to other Keggin's heteropolyanions, the reduction of 11-MBP with AsA is both fast and maximal within a pH range of 1.6-2.0. The stoichiometry of the reaction was determined using molar ratio and continuous variation methods and was shown to be 1:1. The molar absorptivity of the reduced form of 11-MBP was 6.0 x 10(3)L mol(-1)cm(-1) at 720 nm. The reaction is also specific for AsA. Only cysteine, hydroquinone and hydroxyacids were found to interfere with the reaction, while no interference was observed with the common reducing agents, including reducing sugars, catecholamines, nitrite, sulfite and iron(II) ions. Batch SP and sequential injection analysis (SIA) systems were developed for the determination of AsA, with calibration ranges of the SP methods at 2x10(-6)-8 x 10(-5)M for a 10mm cell and 5 x 10(-7)-3 x 10(-5)M for a 50mm cell and a limit of detection at 3 x 10(-7)M. The linear range of the SIA method was 6 x 10(-6)-5 x 10(-4)M, with a detection limit of 2 x 10(-6)M and a sample throughput of 15 h(-1). The proposed methods were successfully used for the determination of AsA in both pharmaceuticals and fruit juices, and the results were consistent with those provided by the 2,6-dichlorophenolindophenol method.

Spectrophotometric determination of [2-(2,6-dichloro-phenylamino)-phenyl]-acetic acid in pure form and in pharmaceuticals.

A new sensitive and selective spectrophotometric method has been developed for the determination of [2-(2,6-dichloro-phenylamino)-phenyl]-acetic acid in pharmaceuticals in the presence of nicotinic acid. The method is based on the reaction of [2-(2,6-dichloro-phenylamino)-phenyl]-acetic acid with 1,3,3-trimethyl-5-phenyl-2-[3-(1,3,3-trimethyl-1,3-dihydro-indol-2-ylidene)-propenyl]-3H-indolium chloride (PIC) followed by the extraction of the formed ion associate into toluene and spectrophotometric detection at 581 nm. Appropriate experimental conditions were found to be pH 7.8-9.8 and 3.6x10(-4) mol L(-1) of PIC. The molar absorptivity is 5.0x10(-4) L mol(-1) cm(-1). The absorbance obeys Beer's law in the range 0.61-12.60 microg mL(-1) of [2-(2,6-dichloro-phenylamino)-phenyl]-acetic acid, and the detection limit calculated from a blank test was 0.20 microg mL(-1).

An investigation of the reaction of copper ions with dimethylindodicarbocyanine dye: an application for the determination of Cu(I), Cu(II) and Cu(III).

In this work, the reactions of various copper ions with 1,3,3-trimethyl-2-[5-(1,3,3-trimethyl-1,3-dihydro-indol-2-ylidene)-penta-1,3-dienyl]-3H-indolium--more commonly known as dimethylindodicarbocyanine polymethyne dye (DIDC)--as well as the application of the results obtained for the development of a spectrophotometric method for the determination of Cu(I), Cu(II) and Cu(III) are described. Cu(I) and Cu(II) in the presence of chloride ions and DIDC reagent are extractable by a variety of organic solvents. It is important to emphasize that Cu(I) was extracted under considerably different experimental conditions than Cu(II). The optimum conditions for the extraction of the Cu ion associates with DIDC by amyl acetate and the determination of Cu(I) and Cu(II) were found to be: pH 3-5 and pH 3-6 and chloride concentrations of 0.5-0.8 mol L(-1) and 3-6 mol L(-1) for Cu(I) and Cu(II), respectively. The molar absorptivities for Cu(I) and Cu(II) are 1.8x10(5) L mol(-1) cm(-1) and 1.2x10(5) L mol(-1) cm(-1), respectively. A reaction mechanism is suggested. Cu(III) does not extract in the presence of chloride ions. However, Cu(III) is a strong oxidative agent which can cause the decolourisation of the DIDC reagent. The optimum conditions for Cu(III) determination were found to be: 2x10(-5) mol L(-1) DIDC; pH 8; water:acetone 4:1 medium. The developed procedures were tested for the determination of Cu(I), Cu(II) and Cu(III) in semiconductor samples.