Characterization of a rapid and reliable method for iodide biomonitoring in serum and urine based on ion chromatography–ICP-mass spectrometry

An appropriate and controlled supply of thyroid hormones is vital for proper body function. In turn, an appropriate synthesis of T3 and T4 in the thyroid gland is dependent on a sufficient and balanced iodide concentration in blood serum. Due to widespread iodine deficiency or some cases of iodine over exposure, iodide biomonitoring in serum is important and it is that biomonitoring approach being closest to the bioavailable I⁻ supply for the thyroid gland. Therefore, this paper describes a biomonitoring method for iodide determination in serum based on ion chromatography–inductively coupled plasma mass spectrometry (IC–ICP-MS). Since in literature only very few data are available on iodide in serum but many in urine the method is also extended to I⁻ monitoring in urine. The method was additionally designed to have short analysis time (8 min) for increased sample throughput, good precision in serial measurement (serum: 4.86%; urine: 1.4%), and day-to-day determination (serum: 5.7%; urine: 2.28%), high accuracy (serum: 105%; urine: 101%) and good recovery (serum: 102%; urine: 99%) even in matrix-rich samples at low I⁻ concentration. Also, investigations were performed to elucidate whether internal standardization during chromatography, sample preparation for protein-matrix removal or matrix-matched calibration are advantageous for analytical performance. Finally, limits of detection (3σ) of 0.12 μg/L or 0.05 μg/L (serum or urine) and limit of quantification (10σ) of 0.39 μg/L or 0.17 μg/L (serum or urine) were achieved.     

Application of capillary electrophoresis to the simultaneous screening and quantitation of benzodiazepines

Capillary electrophoresis (CE) is an attractive approach for the analysis of drugs in body fluids. We made a simultaneous analysis of nitrazepam, diazepam, estazolam, bromazepam, triazolam and flurazepam using CE with on-column detection at 200 nm. We obtained the best electropherograms under a condition of 5 mM phosphate-borate (pH 8.5) containing 50 mM SDS and 15% methanol. We examined the effect of the sample solvent matrix on the electropherograms obtained, indicating that increasing the methanol content in the sample solvent or the injection volume above a certain threshold limit decreased the resolution. We then focused on application of the CE to the analysis of the drugs in spiked serum, being appropriate for an analysis within 25 min. Linearity, the detection limit, accuracy and reproducibility were established using this method. The calibration curve was linear up to 1 mg/l of serum concentration. The lower limit of detection was 5 pg per injection and 0.025 mg/l of the serum concentration for all the compounds except for flurazepam, for which they were 40 pg/injection and 0.2 mg/l. The detection limits obtained allowed toxicological and pharmacological determinations for nitrazepam, diazepam, estazolam and bromazepam, but not for triazolam and flurazepam. Only toxic blood levels for the latter two benzodiazepines could be quantified by this method. We concluded that the CE could at least be applicable to simultaneous screening for toxic levels of benzodiazepines. We suggest that this technique may offer criminal toxicologists a rapid, simple and adaptable approach for the estimation of many other drugs in body fluids.     

High-sensitivity capillary electrophoresis determination of inorganic anions in serum and urine using on-line preconcentration by transient isotachophoresis

Concentrations of inorganic anions, both as individual species and biotransformation products, in physiological fluids are of strong concern in clinical studies. To date, analytical methodologies have either required different analytical procedures to determine these analytes in plasma and urine, or extensive sample preparation, or unconventional and often expensive detection schemes, or both. A simple and sensitive capillary electrophoresis (CE) method with direct UV detection was developed for the simultaneous determination of iodide, bromide and nitrate in human plasma and urine, with a special focus on reliable quantification of the trace serum iodide. With the latter objective, the method incorporates a transient isotachophoresis (tITP) procedure enabling an efficient on-line preconcentration of iodide (limit of detection, 1.4 microg l(-1)) as well as other moderately mobile analytes that fall into the tITP range. The analyses of both types of biofluids were performed using an acidic electrolyte system composed of 0.25 mol l(-1) sodium chloride and 7.5 mmol l(-1) cetyltrimethylammonium chloride at pH 2.2 and 0.5 mol l(-1) 2-(N-morpholino)ethanesulfonate (pH 6.0) as terminating electrolyte. Relative standard deviations (R.S.D.) below 3.0% and 9.2% were obtained for within-day and between-day precision, respectively. Resolution and quantification of oxalic acid was also feasible under optimized tITP-CE conditions. Sample preparation required only ultrafiltration (serum) and dilution (urine). A number of plasma and urine samples were evaluated with this assay and the iodide, bromide and nitrate concentrations were in the expected clinical concentration ranges.     

Design of a new cartridge for selective solid phase extraction using molecularly imprinted polymers: Selective extraction of theophylline from human serum samples

This paper describes design of a new cartridge for selective solid phase extraction (SPE) using molecularly imprinted polymers (MIPs). The apparatus which is termed solvent extraction-MISPE (SE-MISPE) cartridge, consisted of a modified conventional micro test tube and has been developed to perform simultaneous forward-extraction of analyte from aqueous sample solution to an organic phase and back-extraction to MIP solid phase. In order to evaluate the performance of the proposed method, extraction of theophylline (THP) from human serum sample was investigated. An appropriate amount of THP-imprinted polymer was placed in the bottom of the micro tube and an organic solvent pipetted onto it and left to swell the polymer completely. A polyethylene frit to secure MIP particles was positioned by two Teflon rings such that it was fixed below the level of the organic layer. Then, aqueous sample solution containing THP was layered over the organic phase and the lid was closed. After completion of extraction, the organic and aqueous phases were removed and the adsorbed analyte was desorbed using a polar organic solvent. In order to reach the highest recovery, the experimental parameters such as the type of organic solvent, pH and ionic strength of aqueous phase, organic to aqueous volume ratio, time of extraction, type and amount of desorbent solvent were optimized. Under the experimental conditions, a plot of HPLC peak areas vs. initial concentrations of THP in the concentration interval of 0.5–30 μg ml⁻¹ showed a good linearity (r = 0.9974). The limit of detection (LOD) and limit of quantification (LOQ) based on three and ten times of the noise of HPLC profile were 0.09 and 0.3 μg ml⁻¹, respectively. The relative standard deviation (RSD) of the proposed method for the extraction and determination of 5 μg THP from 200 μl standard sample solution for 3 replicate measurements was 3.5%. The results showed that by means of the proposed cartridge, THP could significantly separate from the other structurally related compounds such as theobromine (THB) and caffeine (CAF). The added THP could be quantitatively recovered (79–83%) from the serum samples by the proposed procedure, being thus a guarantee of the accuracy of the SE-MISPE procedure. In addition, the loss of capability of the SE-MISPE cartridge was not considerably observed after 10 times loading and elution cycles.     

Determination of trace cadmium in saliva samples using spray assisted droplet formation-liquid phase microextraction prior to the measurement by slotted quartz tube-flame atomic absorption spectrophotometry

BackgroundAn effective, green and rapid analytical strategy namely the simultaneous spray assisted droplet formation-liquid phase microextraction (S-SADF-LPME) method was developed for the determination of trace quantity of cadmium in saliva samples by using the slotted quartz tube-flame atomic absorption spectrophotometry (SQT-FAAS). By the developed method, external dispersive solvent usage for droplet formation was reduced to obtain a more environmental-friendly method.MethodsMethod consists of a simultaneous complexing and extraction step, which was based on spraying an extraction solvent containing a solid ligand into the aqueous sample solution, forming fine droplets without the use of dispersive solvent. The procedure was implemented using a customized, cost effective and portable spray apparatus to minimize the consumption of reagent, analysis time and operation steps. Thus, this methodology ensures better repeatability and accuracy while minimizing the relative errors caused by the experimental steps. Parameters including the buffer amount, extractant/ligand concentration, extraction solvent type, extraction/ligand solution volume, spraying number and vortex period were systemically optimized to lower the detection limit.ResultsUnder the optimal extraction conditions, 96.9-folds enhancement in the detection power of the traditional FAAS was achieved. The limit of detection and limit of quantification values of presented method were calculated to be 0.65 and 2.17 ng mL⁻¹, respectively. Accuracy and applicability of the optimized method was investigated by collecting saliva samples from smokers. Satisfactory percent recovery values wereachieved for cadmium with a low standard deviation in the acceptable range of 84.9–109.6 %.ConclusionThe developed dispersive solvent-free S-SADF-LPME technique presents a fast, simple, cost-effective and eco-friendly microextraction method based on the use of an easily accessible and functional spray apparatus.     

Chemiluminescence detection of trace iodide with flow injection analysis of KMnO4‐carbon dots system

Ultra‐weak chemiluminescence (CL) from the reaction of iodide and KMnO₄ was strongly enhanced by carbon nanodots (CNDs) in an acidic medium. The CL intensity was directly proportional to the concentration of iodide in the solution. Therefore, a flow‐injection CL system with high sensitivity, selectivity and reproducibility is proposed for the determination of iodide. The proposed method exhibited advantages over a linear range of 3.0 × 10^?6–1.0 × 10^?4 mol/L and had a detection limit of 3.5 × 10^?7 mol/L. The method was successfully applied to the evaluation of iodide in food samples with recoveries of between 96 and 103%. The relative standard deviations were 2.1 and 4.1% for intra‐ and inter‐assay precision, respectively.     

Fabrication of nitrogen‐ and phosphorous‐doped carbon dots by the pyrolysis method for iodide and iron(III) sensing

A facile and novel strategy to synthesize nitrogen‐ and phosphorous‐doped carbon dots (NPCDs) by single step pyrolysis method is described here. Citric acid is used as carbon source and di‐ammonium hydrogen phosphate is used as both nitrogen and phosphorous sources, respectively. Through the extensive study on optical properties, morphology and chemical structures of the synthesized NPCDs, it is found that as‐synthesized NPCDs exhibited good excitation‐dependent luminescence property, spherical morphology and high stability. The obtained NPCDs are stable in aqueous medium and possess a quantum yield of 10.58%. In this work, a new assay method is developed to detect iodide ions using the synthesized NPCDs. Here, the inner filter effect is applied to detect the iodide ion and exhibited a wide linear response concentration range (10–60 μM) with a limit of detection (LOD) of 0.32 μM. Furthermore, the synthesized NPCDs are used for the selective detection of iron(III) (Fe³⁺) ions and cell imaging. Fe³⁺ ions sensing assay shows a detection range from 0.2 to 30 μM with a LOD of 72 nM. As an efficient photoluminescence sensor, the developed NPCDs have an excellent biocompatibility and low cytotoxicity, allowing Fe³⁺ ion detection in HeLa cells.     

Determination of valproic acid in human serum and pharmaceutical preparations by headspace liquid-phase microextraction gas chromatography-flame ionization detection without prior derivatization

An efficient and fast extraction technique for the enrichment of valproic acid from human blood serum samples using the headspace liquid phase microextraction (HS-LPME) combined with gas chromatography (GC) analysis has been developed. The extraction was conducted by suspending a 2 microL drop of organic solvent in a 1 mL serum sample; following 20 min of extraction, withdrawing organic solvent into a syringe and injection into a GC with a flame ionization detector (FID), without any further pre-treatment. Four organic solvents, 1-decanole, benzyl alcohol, 1-octanol and n-dodecane, were studied as extractants, and n-dodecane was found to be the most sensitive solvent for valproic acid. The results revealed that HS-LPME is suitable for the successful extraction of valproic acid from human blood serum samples. Parameters like extraction time, ionic strength, pH, organic solvent volume, and temperature of the sample were studied and optimized to obtain the best extraction results. An enrichment factor of 27-fold was achieved in 20 min. The procedure resulted in a relative standard deviation of <13.2% (n=7) and a linear calibration range from 2 to 20 microg mL(-1) (r>0.98), and the limit of detection was 0.8 microg mL(-1) in serum blank samples. Overall, LPME proved to be a fast, sensitive and simple tool for the preconcentration of valproic acid from real samples. The proposed method was also applied to the analysis of valproate in pharmaceutical preparations.     

Monitoring the enzymatic conversion of urea to ammonium by conventional or microchip capillary electrophoresis with contactless conductivity detection

Interleukin-6 (IL-6), an inflammatory cytokine, is one of the most important mediators of fever, the acute phase response, and inflammatory conditions. Described here is an integrated microfluidic immunosensor capable of detecting the concentration of IL-6 in human serum samples by use of an electrochemical method in a microfluidic biochip format. The detection of IL-6 was carried out using a sandwich immunoassay method based on the use of anti-IL-6 monoclonal antibodies, immobilized on a 3-aminopropyl-modified controlled-pore glass (APCPG) packet in a central channel (CC) of the microfluidic system. The IL-6 in the serum sample is allowed to react immunologically with the immobilized anti-IL-6 and biotin-labeled second antibodies specific to IL-6. After washing, the streptavidin–alkaline phosphatase conjugate is added. p-Aminophenyl phosphate is converted to p-aminophenol by alkaline phosphatase, and the electroactive product is quantified on a gold electrode at 0.10 V. For electrochemical detection and enzyme immunoassay, the LOD was 0.41 and 1.56 pg mL⁻¹, respectively. Reproducibility assays employed repetitive standards of IL-6, and the intra- and inter-assay coefficients of variation were below 6.5%. Compared with the traditional IL-6 sensing method, the integrated microfluidic immunosensor required smaller amounts of sample to perform faster detection.     

High-performance liquid chromatographic separation and electrochemical detection of cephalosporins

Pulsed amperometric detection (PAD) is useful for detection of cephalosporins following separation on a C₁₈ column using an acetate buffer solvent with a small percentage of organic modifier. Under these conditions, the indirect PAD mode worked better than direct PAD, with IPAD outperforming both. A gradient program was demonstrated that allowed separation and sensitive electrochemical detection of eleven different cephalosporins with widely differing side chain structures. The cephalosporins could be detected to sub-micromolar levels with this separation. Applications of the method for quantitation of pharmaceutical formulations and for monitoring cephalexin in porcine serum were demonstrated. To improve the detectability of cephalexin, an on-column concentration scheme using separate concentration and elution solvents was applied to porcine serum.     

Reduction of iodate in iodated salt to iodide during cooking with iodine as measured by an improved HPLC/ICP–MS method

Background: Iodate is a strong oxidant, and some animal studies indicate that iodate intake may cause adverse effects. A key focus of the safety assessment of potassium iodate as a salt additive is determining whether iodate is safely reduced to iodide in food. Objective: To study the reduction of iodate in table salt to iodide and molecular iodine during cooking. Materials and Methods: Fifteen food samples cooked with and without iodated salt were prepared in duplicate. The iodine in the cooked food was extracted with deionized water. The iodine species in the extracts were determined by using an improved high-performance liquid chromatography/inductively coupled plasma–mass spectrometry (HPLC/ICP–MS). The cooking temperature and the pH of the food were determined. Results: The conversion rate of iodate in iodated salt to iodide and molecular iodine was 96.4%±14.7% during cooking, with 86.8%±14.5% of the iodate converted to iodide ions and 9.6% ±6.2% converted to molecular iodine to lose. The limit of detection, limit of quantification, relative standard deviation and recovery rate of the method HPLC/ICP–MS were 0.70 μg/L for I⁻ (0.69 μg/L for IO₃⁻), 2.10 μg/L for I⁻ (2.06 μg/L for IO₃⁻), 2.6% and 101.6%±2.6%, respectively. Conclusion: Almost all iodate added to food was converted into iodide and molecular iodine during cooking. The improved HPLC/ICP–MS was reliable in the determination of iodine species in food extracts.     

Determination of temozolomide in serum and brain tumor with micellar electrokinetic capillary chromatography

Micellar electrokinetic capillary chromatographic (MEKC) with photodiode-array detection was applied to determine temozolomide (TMZ) in human serum and brain tumor. The limit of quantitation (LOQ) was 0.096 μg/mL using 325 nm as detection wavelength. The method made possible that the TMZ could be detected in in vivo serum samples without sample pretreatment. In order to detect TMZ at lower concentration, an extraction with ethyl acetate was applied to preconcentrate the analyte. Small amount of brain tumor tissues (less than 1g) were lyophilized and pretreated using extraction as a clean up and concentrating step. After removing the organic solvent a final sample volume of only 10 μL was analyzed. The obtained peak concentrations (8.2-10.1 μg/mL) and T(max) (44-65 min) of TMZ in serum were similar to the data reported by others, the in vivo TMZ concentrations found in brain tumor ranged between 0.061 and 0.117 μg/g.     

Quantification of indol-3-yl acetic acid in pea and maize seedlings by gas chromatography-mass spectrometry

A procedure is described for the identification and quantification of IAA in plant tissues by GC/MS analysis of the N-heptafluorobutyryl ethyl ester of IAA using [²H₅]IAA as an internal standard. The detection limit is ca 3 pmol IAA/tissue sample. By using this method, IAA levels of 30–90 pmol/g fr. wt were obtained for dark-grown Pisum sativum epicotyls and 71–199 pmol/g fr. wt for dark-grown Zea mays seedlings. When either methanol or ethanol was used as extraction solvent, some esterification of IAA during sample preparation was observed. No evidence for the natural occurrence of methyl or ethyl esters of IAA in Pisum sativum seedlings was found.     

Comparison of silver, gold and modified platinum electrodes for the electrochemical detection of iodide in urine samples following ion chromatography

The electrochemical (EC) detection of iodide at gold, silver and platinum electrodes under similar experimental conditions was evaluated. To achieve optimal amperometric detection, the electrode sensitivity, selectivity, and stability was compared. Isocratic separation of iodide was attained by ion chromatography (IC) using an anion-exchange column with nitrate as an eluent ion (25 mM HNO(3) + 50 mM NaNO(3)). Although the Ag electrode showed the highest selectivity due to the relatively low applied potential (+0.10 V versus Ag|AgCl), it requires continuous surface polishing upon injection of standard solutions or real samples; in addition, the chromatographic peak of iodide exhibited a pronounced dip-tailing. The limit of detection (LoD) of iodide was estimated to be 3.5 microg/L (S/N=3) with an injection volume of 50 microL. Likewise, pulsed electrochemical detection at the silver electrode did not demonstrate the expected results in terms of peak shape and low detection limit. Using the same chromatographic conditions, iodide detection at the Au electrode (E(app)= +0.80 V versus Ag|AgCl) exhibited a regular peak shape accompanied by a sensitivity comparable to the silver one. Yet, upon continuous injections the signal intensity displayed a progressive lowering up to ca. 40% in 6h. Best results in terms of signal stability, peak shape and analytical response were obtained with a modified platinum electrode which allowed to achieve a LoD of 0.5 microg/L (S/N=3). The present IC-EC detection method using a modified Pt electrode (E(app)= +0.85 V versus Ag|AgCl) was successfully applied to determine low contents of iodide in human urine with solid phase extraction as pretreatment. Such a developed method correlated very well with the reference colorimetric method in urine (r=0.95273), and it is specifically suggested when the iodide content is relatively low, i.e., <20 microg/L.     

Microextraction in packed sorbent for analysis of antidepressants in human plasma by liquid chromatography and spectrophotometric detection

A sensitive and reproducible method by microextraction packed sorbent and liquid chromatography with UV detection (MEPS/LC–UV) is described for the determination of new generation antidepressants (sertraline, mirtazapine, fluoxetine, citalopram and paroxetine) in human plasma samples. The MEPS variables, such as sample volume, pH, number of extraction cycles (draw–eject), and desorption conditions (solvent and solvent volume of elution) influenced the MEPS/LC efficiency significantly. Important factors in the optimization of MEPS efficiency, as well as washing steps and carryover effect are discussed. The analyses were carried out using small sample volumes (400 μL), and in a short time period (3 min for the entire sample preparation step). The MEPS/LC–UV method was shown to be linear at concentrations ranging from the limit of quantification (LOQ) to 1000 ng mL⁻¹. The LOQ values ranged from 10 to 25 ng mL⁻¹. The inter-day precision of the method presented coefficient of the variation ranging from 1.3% to 8.7%. On the basis of analytical validation, it is shown that the MEPS/LC–UV methodology is adequate for antidepressant analysis, from therapeutic to toxic levels. In order to evaluate the proposed method for clinical use, the MEPS/LC–UV method was applied to analysis of plasma samples from elderly depressed patients.     

Determination of very-long-chain fatty acids in serum by gas chromatography–nitrogen–phosphorus detection following cyanomethylation

A sensitive method for very-long-chain fatty acid analysis was developed by gas chromatography–nitrogen–phosphorus detection by using cyanomethyl derivatization. Bromoacetonitrile as alkylating reagent was used to improve nitrogen phosphorus detection detectability of compounds containing non-nitrogen. The carboxyl group of very-long-chain fatty acid was alkylated to cyanomethyl esters. Reaction conditions were 40 min at 60°C under potassium carbonate base. Heptacosanoic acid was used as an internal standard and hexane was used as a solvent of extraction. The extraction yield was 82.8% or more, relative standard deviation of the precision test was 8.3 % or more and the result of linearity test showed a good correlation coefficient of r²=0.999 in the range of 0.1–50 μg/ml. The quantification limits were 10 ng/ml when 0.5 ml of serum was used. The present method proved simple, rapid, inexpensive and resistant to contaminants. When it was applied to serum samples taken from patients with X-linked adrenoleukodystrophy which is a hereditary X-linked disorder characterized by progressive demyelination and adrenal insufficiency during childhood, relative increase of the concentration of hexacosanoic acid and the concentration ratios of hexacosanoic, lignoceric to behenic acid was observed in comparison with control samples.     

Detection limit of negative staining electron microscopy for the diagnosis of bioterrorism‐related micro‐organisms

Aims: To determine the detection limit of diagnostic negative staining electron microscopy for the diagnosis of pathogens that could be used for bioterrorism. Methods and Results: Suspensions of vaccinia poxvirus and endospores of Bacillus subtilis were used at defined concentrations as a model for poxviruses and spores of anthrax (Bacillus anthracis), both of which are pathogens that could be used for bioterrorist attacks. Negative staining electron microscopy was performed directly or after sedimentation of these suspensions on to the sample supports using airfuge ultracentrifugation. For both virus and spores, the detection limit using direct adsorption of a 10‐μl sample volume onto the sample support was 10⁶ particles per ml. Using airfuge ultracentrifugation with a sample volume of 80 μl, the detection limit could be reduced to 10⁵ particles per ml for spores and to 5 × 10⁴ particles per ml for poxviruses. The influence on particle detection of incubation time, washing and adsorption procedures was investigated. Conclusions: The reproducibility and sensitivity of the method were acceptable, particularly considering the small sample volume and low particle number applied onto the sample support. Significance and Impact of the Study: Diagnostic negative staining electron microscopy is used for the diagnosis of pathogens in emergency situations because it allows a rapid examination of all particulate matter down to the nanometre scale. This study provides precise detection limit for the method, an important factor for the validation and improvement of the technique.     

A novel 4-(tetrahydro-2-furanmethoxy)-N-octadecyl-1,8-naphthalimide based blue emitting probe: Solvent effect on the photophysical properties and protein detection

A novel 4-(tetrahydro-2-mranmethoxy)-N-octadecyl-1,8-naphthalimide (4-TNI) blue emitting fluorophore was synthesized for solvent polarity probing and protein detection. The effect of various solvents on absorption and fluorescence spectra of 4-TNI was investigated. By comparison with other derivatives with heterocyclic electron-donating groups, 4-TNI had the advantage of higher fluorescence quantum yield. The bathochromic shift observed in absorption and fluorescence spectra of 4-TNI with increasing solvent polarity indicates that the transitions involved are ?? ?? ??*. The normalized transition energy value E _T ^N showed some scattering when plotted versus ????. According to the quantum mechanics second order perturbation method, the ground and excited state dipole moments of 4-TNI were calculated as 3.91 and 7.12 D, respectively. Density functional calculations were also used to obtain the ground and excited state dipole moments. The result was consistent with the experimental values. Binding of TNI with human serum albumin (HSA) was studied. Fluorescence data revealed that quenching of HSA fluorescence by 4-TNI was due to the formation of a 4-TNI-HSA complex. Hydrogen bonds and hydrophobic interactions are the driving force of complex formation. 4-TNI fluorescence was found to be very sensitive to quenching by HSA. Therefore, a new spectrofluorimetric method for detection of HSA in Tris-HCl buffer solution (pH 7.4) was developed. The linear range of the calibration curve was 0.1?C14.2 × 10^?6 M for HSA, with a detection limit (3??) of 1.37 × 10^?10 M. The method was applied to determination of total protein in clinical samples of human serum and the results were in good agreement with the data obtained by using Coomassie Brilliant Blue G-250 colorimetry.     

The determination of bifunctional compounds : IX. A selective reaction for the determination of guaifenesin in plasma by gas chromatography

Guaifenesin after extraction from plasma with an organic solvent can be selectively derivatized with 2,4-dichlorobenzeneboronic acid and determined by gas chromatography with electron-capture detection. The detection limit for guaifenesin was 15 ng ml⁻¹ for a 2.0-ml plasma sample. The mass spectra of the boronate derivatives of guaifenesin and mephenesin, used as internal standard, show good molecular ions with characteristic modes of fragmentation useful for their identification.     

Flow‐injection method for the determination of iodide/iodine using Ru(bpy)33+–NADH chemiluminescence detection

A two‐channel flow‐injection (FI) method is reported for the determination of iodide and iodine by its enhancement effect on the Ru(bpy)₃³⁺–NADH chemiluminescence (CL) system. The limit of detection (3 s of blank) was 1.0 × 10^–9 mol/L iodide/iodine, with a sample throughput of 60/h. The calibration graphs over the range 1.0–50 × 10^–8 mol/L gave correlation coefficients of 0.9994 and 0.999 (n = 5) with relative standard deviations (RSD; n = 4) of 1.0–2.5%, respectively. The effects of interfering cations, anions and some organic compounds were also studied. The method was applied to iodized salts and pharmaceutical samples and the results obtained were in good agreement with the value quoted. The CL method developed was compared with spectrophotometric method. Copyright © 2008 John Wiley & Sons, Ltd.