Potentiometric detection of citrate in beverages using a graphite carbon electrode

The development, evaluation and application of a simple and low-cost graphite carbon electrode for the direct determination of citrate in food samples are described here. The electrode exhibits a linear response with a slope of −29.0 ± 1.0 mV decade⁻¹ in a concentration range of 0.07-7.0 mmol L⁻¹ in 0.1 mol L⁻¹ KCl/1.0 mmol L⁻¹ phosphate buffer solution with a limit of detection of 3.0 μmol L⁻¹. The electrode is easily constructed at a relatively low cost and has a fast time response (within 120 s) with no significant changes in its performance characteristics. The performance of the graphite sensor was tested to determine citrate in beverage samples (juices and an isotonic drink), and the results were validated against a reference procedure. The proposed method is quick, inexpensive, selective and sensitive, and is based entirely on conventional instrumentation.     

Azo calix[4]arene based neodymium(III)-selective PVC membrane sensor

We found that the PVC membrane, containing azo calix[4]arene is a suitable ionophore, exhibited a Nernstian response for neodymium (Nd³⁺) ions (with slope of 19.8 ± 0.2 mV decade⁻¹ for the triply charged ion) over a wide linear range of 4.0 × 10⁻⁸ to 1.0 × 10⁻¹ mol L⁻¹ with a detection limit 1.0 × 10⁻⁸ mol L⁻¹, a relatively fast response time, in the whole concentration range (<10 s), and a considerable life time at least for four months in the pH range of 4.0-8.0. Furthermore, the electrode revealed high selectivity with respect to all the common alkali, alkaline earth, transition and heavy metal ions, including the members of the lanthanide family other than Nd³⁺. Concerning its applications, it was effectively employed for the determination of neodymium ions in industrial waste water as well as in lake water.     

CdSe quantum dots capped PAMAM dendrimer nanocomposites for sensing nitroaromatic compounds

The detection of nitroaromatic compounds, best known as raw materials in explosives preparations, is important in many fields including environmental science, public security and forensics. CdSe quantum dots capped with PAMAM-G₄ dendrimer were synthetized in water and used for the detection of trace amounts of three nitroaromatic compounds: 4-methoxy-2-nitrophenol (MNP), 2-amine-5-chloro-1,3-dinitrobenzene (ACNB) and 3-methoxy-4-nitrobenzoic acid (MNB). To increase the apparent water solubility of these compounds α-cyclodextrin (α-CD) was used to promote the formation of inclusion complexes. The studied nitroaromatic compounds (plus α-CD) significantly quenched the fluorescence intensity of the nanocomposite with linear Stern-Volmer plots. The Stern-Volmer constants (standard deviation in parenthesis) were: MNB, K_SV = 65(5) × 10⁴ M⁻¹; ACNB, K_SV = 19(2) × 10⁴ M⁻¹; and, MNP, K_SV = 33(1) × 10² M⁻¹. These constants suggest the formation of a ground state complex between the nitroaromatric compounds and the sensor which confers a relatively high analytical sensitivity. The detection sensibilities are about 0.01 mg L⁻¹ for MNB and ACNB and about 0.1 mg L⁻¹ for MNP. No interferences or small interferences are observed for trinitrotoluene [K_SV = 10(2) × 10² × M⁻¹], 2,4-dinitrotoluene [K_SV = 20(3) × 10 M⁻¹], 2,6-dinitrotoluene [K_SV = 11(4) × 10 M⁻¹] and nitrobenzene [K_SV = 2(1) × 10³ × M⁻¹].     

Evaluation of oxygen pressurized microwave-assisted digestion of botanical materials using diluted nitric acid

The feasibility of diluted nitric acid solutions for microwave-assisted decomposition of botanical samples in closed vessels was evaluated. Oxygen pressurized atmosphere was used to improve the digestion efficiency and Al, Ca, K, Fe, Mg and Na were determined in digests by inductively coupled plasma optical emission spectrometry (ICP OES). Efficiency of digestion was evaluated taking into account the residual carbon content (RCC) and residual acidity in digests. Samples were digested using nitric acid solutions (2, 3, 7, and 14 mol L⁻¹ HNO₃) and the effect of gas phase composition inside the reaction vessels by purging the vessel with Ar (inert atmosphere, 1 bar), air (20% of oxygen, 1 bar) and pure O₂ (100% of oxygen, 1 bar) was evaluated. The influence of oxygen pressure was studied using pressures of 5, 10, 15 and 20 bar. It was demonstrated that a diluted nitric acid solution as low as 3 mol L⁻¹ was suitable for an efficient digestion of sample masses up to 500 mg of botanical samples using 5 bar of oxygen pressure. The residual acidities in final digests were lower than 45% in relation to the initial amount of acid used for digestion (equivalent to 1.3 mol L⁻¹ HNO₃). The accuracy of the proposed procedure was evaluated using certified reference materials of olive leaves, apple leaves, peach leaves and pine needles. Using the optimized conditions for sample digestion, the results obtained were in agreement with certified values. The limit of quantification was improved up to a factor of 14.5 times for the analytes evaluated. In addition, the proposed procedure was in agreement with the recommendations of the green chemistry once it was possible to obtain relatively high digestion efficiency (RCC < 5%) using only diluted HNO₃, which is important to minimize the generation of laboratory residues.     

Silver nanoparticles fluorescence enhancement effect for determination of nucleic acids with kaempferol-Al(III)

Nucleic acids can greatly enhance fluorescence intensity of the kaempferol (Km)-Al(III) system in the presence of silver nanoparticles (AgNPs). Based on this, a novel method for the determination of nucleic acids is proposed. Under studied conditions, there are linear relationships between the extent of fluorescence enhancement and the concentration of nucleic acids in the range of 5.0 × 10⁻⁹ to 2.0 × 10⁻⁶ g mL⁻¹ for fish sperm DNA (fsDNA), 7.0 × 10⁻⁹ to 2.0 × 10⁻⁶ g mL⁻¹ for salmon sperm DNA (smDNA) and 2.0 × 10⁻⁸ to 3.0 × 10⁻⁶ g mL⁻¹ for yeast RNA (yRNA), and their detection limits are 2.5 × 10⁻⁹ g mL⁻¹, 3.2 × 10⁻⁹ g mL⁻¹ and 7.3 × 10⁻⁹ g mL⁻¹, respectively. Samples were satisfactorily determined. And the system of Km-Al(III)-AgNPs was used as a fluorescence staining reagent for sensitive DNA detection by DNA pattern of agarose gel electrophoresis analysis. The results indicate that the fluorescence enhancement should be attributed to the formation of Km-Al(III)-AgNPs-nucleic acids aggregations through electrostatic attraction and adsorption bridging action of Al(III) and the surface-enhanced fluorescence effect of AgNPs.     

Ultrasensitively sensing acephate using molecular imprinting techniques on a surface plasmon resonance sensor

An ultrathin molecularly imprinted polymer film was anchored on an Au surface for fabricating a surface plasmon resonance sensor sensitive to acephate by a surface-bound photo-radical initiator. The polymerization in the presence of acephate resulted in a molecular-imprinted matrix for the enhanced binding of acephate. Analysis of the SPR wavenumber changes in the presence of different concentrations of acephate gave a calibration curve that included the ultrasensitive detection of acephate by the imprinted sites in the composite, K_ass for the association of acephate to the imprinted sites, 7.7 × 10¹² M⁻¹. The imprinted ultrathin film revealed impressive selectivity. The selectivity efficiencies for acephate and other structurally related analogues were 1.0 and 0.11-0.37, respectively. Based on a signal to noise ratio of 3, the detection limits were 1.14 × 10⁻¹³ M for apple sample and 4.29 × 10⁻¹⁴ M for cole sample. The method showed good recoveries and precision for the apple and cole samples spiked with acephate solution. This suggests that a combination of SPR sensing with MIP film is a promising alternative method for the detection of organophosphate compounds.     

Determination of fumaric and maleic acids with stacking analytes by transient moving chemical reaction boundary method in capillary electrophoresis

The paper presents an on-line transient moving chemical reaction boundary (MCRB) method for simply but efficiently stacking analytes in capillary electrophoresis (CE). The CE technique was developed for a rapid determination of fumaric and maleic acid. Based on the theory of MCRB, Effects of several important factors such as the pH and concentration of running buffer and the conditions of stacking analytes were investigated to acquire the optimum conditions. The optimized separations were carried out in a 20 mmol/L sulphate neutralized with ethylenediamine to pH 6.0 electrolytes using a capillary coated with poly (diallyldimethylammonium chloride) and direct UV detection at 214 nm. The optimized preconcentrations were carried out in 50 mmol/L borax (pH 9.0). The calibration curves were linear in the concentration range of 1.0 × 10⁻⁷–1.0 × 10⁻⁴ mol/L and 5.0 × 10⁻⁷–1.0 × 10⁻⁴ mol/L for fumaric and maleic acid with correlation coefficients higher than 0.9991. The detection limits were 5.34 × 10⁻⁸ mol/L for fumaric acid and 1.92 × 10⁻⁷ mol/L for maleic acid. This method was applied for determination of fumaric acid in apple juice and of fumaric and maleic acid in dl-malic, the recovery tests established for real samples were within the range 95–105%. This work provided a valid and simple approach to detect fumaric and maleic acid.     

Fesoterodine stress degradation behavior by liquid chromatography coupled to ultraviolet detection and electrospray ionization mass spectrometry

In the present study, a rapid validated stability-indicating LC method was established and comprehensive stress testing of fesoterodine was carried out according to ICH guidelines. Fesoterodine was subjected to stress conditions of acid and basic hydrolysis, oxidation, photolysis and thermal decomposition. The degradation products formed under stress conditions were investigated by LC-UV and LC-ESI-MS. Successful separation of the drug from its degradation products was achieved on a monolithic C₁₈ column (100 mm × 4.6 mm i.d.) maintained at 45 °C using acetonitrile-methanol-0.03 mol L⁻¹ ammonium acetate (pH 3.8) (30:15:55, v/v/v) as the mobile phase. The flow rate was 2.4 mL min⁻¹ and the detection wavelength was 208 nm. Validation parameters such as specificity, linearity, precision, accuracy, and robustness were evaluated. Chromatographic separation was obtained within 2.5 min and it was suitable for high-throughput analysis. Fragmentation patterns of degradation products formed under different stress conditions were studied and characterized through LC-ESI-MS fragmentation. Based on the results, a drug degradation pathway was proposed, and the validated LC method was successfully applied to the quantitative analysis of fesoterodine in tablet dosage forms, helping to improve quality control and to assure therapeutic efficacy.     

Simple spectrophotocolorimetric method for quantitative determination of gold in nanoparticles

A simple spectrophotocolorimetric method devoted to the measurement of gold content in nanoparticles (NPs) was developed. It includes two steps: (i) metal gold NPs (Au NPs) are oxidized into the AuCl₄⁻ anion using a 5 × 10⁻² M HCl-1.5 × 10⁻² M NaCl-7 × 10⁻⁴ M Br₂ solution, next (ii) AuCl₄⁻ concentration is measured using a spectrophotometric assay based on the reaction of AuCl₄⁻ with the cationic form of Rhodamine B to give a violet ion pair complex. This latter is extracted with diisopropyl ether and the absorbance of the organic complex is measured at 565 nm. The method is linear in the range 6-29 μM of AuCl₄⁻ with a limit of detection of 4.5 μM.The analytical method was optimized with respect of bromine excess to obtain complete Au NPs oxidation. The method was applied to two types of Au NPs currently under investigation: citrate-stabilized Au NPs and Au NPs capped with dihydrolipoic acid (Au@DHLA). Both the gold content of Au NPs and the concentration of NPs (using NP diameter measured by transmission electron microscopy) have been calculated.     

Indirect voltammetric detection of fluoride ions in toothpaste on a comb-shaped interdigitated microelectrode array

A novel technique based on dynamic electrochemistry for the detection of fluoride ions was developed. It is based on its strong complexation with ferric ion. Formed fluoroferric complex is cathodically inactive at the potential of the reduction of free ferric aquo ion. The voltammetric and amperometric response of platinum comb-shaped interdigitated microelectrode array is decreased after fluoride addition. This decrease serves for the quantification of fluoride ions added to the solution. The detection limit of 4.5 × 10⁻⁵ mol dm⁻³ was achieved when one of the segments of interdigitated microelectrode array (IDA) was used as an indicating electrode. The detection limit is about one order of magnitude lower than in the case of conventional platinum macroelectrode. In comparison with ISE electrodes this method is faster and also avoiding large error resulting from the antilogarithmization of ISE Nerstian response. The method was applied to the analysis of toothpaste.     

Samarium (III) adsorption on bentonite modified with N-(2-hydroxyethyl) ethylenediamine

A new material has been synthesized using dry process to activate bentonite followed by N-(2-hydroxyethyl) ethylenediamine connecting chlorosilane coupling agent. The synthesized new material was characterized by elemental analysis, FT-IR and thermogravimetry which proved that bentonite was successfully modified. The most interesting trait of the new material was its selective adsorption for rare earth elements. A variety of conditions of the new material were investigated for adsorption. The optimal conditions were determined with respect to pH and shaking time. Samarium (Sm) was quantitatively adsorbed at pH 4 and shaking time of 2 min onto the new material. Under these conditions the maximum static adsorption capacity of Sm(III) was found to be 17.7 mg g⁻¹. The adsorbed Sm(III) ion were quantitatively eluted by 2.0 mL 0.1 mol L⁻¹ HCl and 5% CS (NH₂)₂ solution. According to IUPAC definition, the detection limit (3σ) of this method was 0.60 ng mL⁻¹. The relative standard deviation (RSD) under optimum conditions was less than 3% (n = 8). The new material also was applied for the preconcentration of trace Sm(III) in environmental samples with satisfactory results.     

Cytotoxic copper(II) complex of tripyridoquinoxaline with DNA hydrolase activity

A monomeric copper(II) complex, [Cu(tpq)₂(H₂O)₂](ClO₄)₂, (tpq = tripyridoquinoxaline), has been synthesized and characterized spectroscopically. This complex has been found to bind DNA intercalatively and the DNA binding constant, K_b, for this complex has been determined from absorption measurements and was found to be (5.7 ± 0.3) × 10³ M⁻¹. This complex successfully promotes hydrolytic cleavage of plasmid DNA, producing single and double DNA strand breaks in the absence of any added cofactor. The amount of conversion of the supercoiled form of plasmid to the nicked circular form depends on the concentration of the copper complex as well as the duration of the incubation of the complex with DNA. The rate of conversion of SC to NC has been determined to be 2.65 × 10⁻⁴ s⁻¹ at pH 7.2 in the presence of 80 μM of the complex. This complex has also been shown to be cytotoxic towards A549 lung adenocarcinoma cells. This complex has been shown to bring about apoptosis of the cancerous A549 cell line.     

Enantioseparation of phenylsuccinic acid by high speed counter-current chromatography using hydroxypropyl-β-cyclodextrin as chiral selector

High speed counter-current chromatography (HSCCC) was successfully applied to resolution of phenylsuccinic acid (PSA) with hydroxypropyl-β-cyclodextrin (HP-β-CD) as chiral selector (CS). The two-phase solvent system composed of n-hexane–methyl tert-butyl ether–0.1 mol L⁻¹ phosphate buffer solution with pH = 2.51 (0.5:1.5:2, v/v/v) was selected. Influence factors involved in the chiral separation were investigated, including the concentration of chiral selector, pH value of the aqueous phase, the separation temperature, and the thermodynamic parameters of inclusion complex were calculated. The complex formation constants were determined using analytical instrument. Two HSCCC elution modes were studied and peak resolution equation was discussed. Under optimum separation conditions, 712 mg of PSA racemate was separated using preparative apparatus. The purities of both of the fractions including (+)-PSA and (−)-PSA from the preparative CCC separation were over 98.5% determined by HPLC and enantiomeric excess of (+)-PSA and (−)-PSA reached 97.6% and 98.6%, respectively. Recovery for the target compounds from the CCC fractions reached 80–82% yielding 285 mg of (+)-PSA and 292 mg of (−)-PSA.     

Anion separations for liquid chromatography using propylpyridinium silica as the stationary phase

This work describes the characterization and potential applications of a silica-based anion-exchange phase prepared by a two-step modification process that incorporates a propylpyridinium group. The effects of pH and eluent concentration on anion separation were examined using 150 mm × 3.9 mm HPLC columns packed with the new phase. The mobile phase pH values ranged from 3.8 to 6.6 using phthalic acid/Tris solutions. The best separation was achieved using 2.5 mmol L⁻¹ phthalate/2.4 mmol L⁻¹ Tris solution at pH 4.2 as mobile phase with non-suppressed conductivity detection. The new stationary phase was used for the separation of some inorganic and organic anions showing good resolution. The stability of the silica-based anion exchange phase was also evaluated.Analytical curves, for concentrations ranging from 0.25 to 10 mg L⁻¹ for the inorganic anions chloride, nitrite, bromide and nitrate, showed good linear correlations (r > 0.998). The method was tested with certified rainwater samples. The measured and certified values were in good agreement, indicating that the new phase holds significant promise for the analysis of these anions in environmental samples.     

Breath analysis by optical fiber sensor for the determination of exhaled organic compounds with a view to diagnostics

Breath analysis constitutes a promising tool in clinical and analytical fields due to its high potential for non-invasive diagnostics of metabolic disorders and monitoring of disease status. An optical fiber (OF) sensor has been developed for determination of volatile organic compounds (ethane, pentane, heptane, octane, decane, benzene, toluene and styrene) in human breath for clinical diagnosis.The analytical system developed showed a high performance for breath analysis, inferred for the analytical signal intensity and stability, linear range, and detection limits ranging from 0.8 pmol L⁻¹, for heptane, and to 9.5 pmol L⁻¹, for decane. The OF sensor also showed advantageous features of near real-time response and low instrumentation costs, besides showing an analytical performance equivalent to the breath analysis by gas chromatography-mass spectrometry (GC-MS), used as the reference method.     

A modified supported bilayer/diblock polymer--working towards a tunable coating for capillary electrophoresis

A surfactant bilayer/diblock polymer coating was previously developed for the separation of proteins. The coating consisted of a mixture of the cationic surfactant dioctadecyldimethylammonium bromide (DODAB) and the neutral polymer poly-oxyethylene (POE) 40 stearate (Journal of Chromatography A 1130 (2006) 265–271). Herein an improved method of generating DODAB/POE stearate coatings is demonstrated, which yields more predictable EOF, more stable coatings, greater average efficiencies and easier method development. In this sequential preparation method the DODAB is first flowed through the capillary, followed by a flow of the POE stearate (sequential method). A tunable EOF (−2.40 to −0.17 × 10⁻⁴ cm²/Vs) is achieved by varying the POE chain length (8, 40 and 100 oxyethylene units). Mixtures of POE 8 and POE 40 stearate enabled continuous variation in EOF from −2.44 to −0.42 × 10⁻⁴ cm²/Vs. Separations of basic proteins yielded efficiencies of 760 000–940 000 plates/m. Coatings formed using the sequential method were more stable over a larger number of runs (%RSD for migration times: 0.7–1.0% over 30 runs) than those formed using the original mixed method (%RSD: 2.4–4.6% over 14 runs). The ability to tune the EOF is important in maximizing the resolution of analytes with similar electrophoretic mobilities. Histone proteins are separated on a sequentially coated capillary with resolution of nine possible subtypes. Acidic proteins are separated on a sequentially coated capillary at pH 6.4.     

Capillary zone electrophoresis for U(VI) and short chain carboxylic acid sorption studies on silica and rutile

Capillary zone electrophoresis was used to study the uranyl and short chain carboxylic acid sorption on silica and rutile. The separation and the simultaneous determination (in a single run) of a number of short chain carboxylic acids (oxalic, formic, acetic and propionic) and U(VI) with direct UV detection is developed for the analysis of solutions after the sorption experiments. The reverse polarity mode is used (the injection is performed at the negative end). The matrix effect of Si(IV) (possible silica dissolution product) and perchlorate (added for constant ionic strength in sorption experiments) on the separation of U(VI) and organic acids is investigated. The influence of methanol addition in carrier electrolyte on the separation selectivity of given analytes is also studied. Under the chosen conditions (carbonate buffer (ionic strength of 0.1 M), pH 9.8, 0.15 mM of tetradecyltrimethylammonium bromide, 25% (v/v) of methanol) the calibration curves are plotted. They are linear in two ranges of concentration from ∼1 × 10⁻⁵ to ∼1 × 10⁻³ M for oxalate, acetate, propionate, U(VI) and ∼1 × 10⁻⁴ to ∼1 × 10⁻³ for formate. The accuracy of the procedure is checked by the “added-found” method in simulation solutions. The relative standard deviations of the concentrations found are within the range of 1-10% and the recovery is in the range of 90-115%. This method is applied for the analysis of aqueous samples issued from sorption experiments on silica and rutile. The obtained results indicate that the given organic acids decrease uranium sorption both on silica and rutile. These experiments demonstrate that short chain carboxylic acids can influence the mobility and the chemistry of U(VI) in the environment.     

Online preconcentration in capillary electrophoresis with contactless conductivity detection for sensitive determination of sorbic and benzoic acids in soy sauce

A sensitive method of online preconcentration followed by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C⁴D) is evaluated as a novel approach for the determination of benzoic acid and sorbic acid in soy sauce. The online preconcentration technique, namely field-enhanced sample injection, coupled with CE-C⁴D were successfully developed and optimized. In order to reduce the complex matrix interference resulting from the constituents of soy sauce, a suitable sample clean-up procedure was also investigated for real sample pretreatment. Under optimized conditions, sorbic acid and benzoic acid were well separated within 10 min, and the detection limits were 0.05 μM (5.6 μg L⁻¹) and 0.08 μM (9.8 μg L⁻¹), respectively. The accuracy was tested by spiking 10.0 mg L⁻¹ and 100.0 mg L⁻¹ of standards in the soy sauce samples, and the recoveries were 95-99%, respectively. Results of this study show a great potential for the proposed method as a tool for the fast screening of benzoic acid and sorbic acid in a complex matrix.     

Application of renewable silver amalgam annular band electrode to voltammetric determination of vitamins C, B1 and B2

In this work, the design and results of applying silver liquid amalgam film-modified silver solid amalgam annular band electrode (AgLAF-AgSAE), refreshed before each measurement, to voltammetric determination of vitamins C (VC), B₁ (VB1) and B₂ (VB2) are presented. The method is based on adsorptive accumulation of analytes at the AgLAF-AgSAE in a phosphate buffer (VB1), phosphate buffer with Triton X-100 (VB2) and an alkaline borate buffer with Triton X-100 (VC). The analytical parameters and procedure of electrode activation were optimized. The calibration graphs obtained for vitamins C, B₁ and B₂ are linear, respectively, for concentration range 0.05-12, 0.01-0.1 and 0.05-3 mg L⁻¹. The detection limits were calculated and equaled 0.02, 0.003 and 0.009 mg L⁻¹, while repeatability of the peak current was 2%, 1% and 3%, respectively. These results are comparable with results obtained for polarographic determination of the same vitamins using mercury electrodes. Finally, the AgLAF-AgSAE was applied to the determination of vitamins in pharmaceutical samples and fruit juices with satisfactory results.     

Development of a stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry method for determining synthetic musks in water samples

This study presents the development of an analytical method for determining 9 synthetic musks in water matrices. The developed method is based on stir bar sorptive extraction (SBSE), coated with polydimethylsiloxane, and coupled with a thermal desorption–gas chromatography–mass spectrometry system (TD–GC–MS). SBSE can efficiently trap and desorb the analytes providing low limits of detection (between 0.02 ng L⁻¹ and 0.3 ng L⁻¹). Method validation showed good linearity, repeatability and reproducibility for all compounds. Furthermore, the limited manipulation of the sample required in this method implies a significant decrease of the risk of external contamination of the samples. The performance of the method in real samples was evaluated by analysing biological wastewater treatment plant (WWTP) influent and effluent samples, reverse osmosis treatment plant effluents and river waters. The most abundant musk was galaxolide with values up to 2069 ng L⁻¹ and 1432 ng L⁻¹ in the influent and effluent of urban WWTP samples, respectively. Cashmeran, Pantolide and Tonalide were also detected in all the matrices with values up to 94 ng L⁻¹, 26 ng L⁻¹ and 88 ng L⁻¹, respectively. Although in Europe the use of nitromusks in cosmetics is prohibited, musk xylene and musk ketone were detected both in the WWTP and in the river samples. As far as we know, this is the first time than a SBSE method coupled with TD is applied for the determination of synthetic musks in water samples.