Analysis of short‐chain aliphatic amines in food and water samples using a near infrared cyanine 1‐(ε‐succinimydyl‐hexanoate)‐1′‐methyl‐3,3,3′,3′‐tetramethyl‐indocarbocyanine‐5,5′‐disulfonate potassium with CE–LIF detection

Precolumn derivatization of six short‐chain aliphatic amines by a near‐infrared dye, 1‐(ε‐succinimydyl‐hexanoate)‐1′‐methyl‐3,3,3′,3′‐tetramethyl‐indocarbocyanine‐5,5′‐ disulfonate potassium (MeCy5‐OSu), followed by MEKC–CE–LIF detection has been developed as a method for the determination of aliphatic amines in environmental water and food. Optimum derivatization was operated nicely in pH 9.0 borate buffer at 20°C for 30 min. Well separated peaks were observed with a pH 9.5 BGE containing 10 mmol L^?1 phosphoric acid, 20 mmol L^?1 SDS, and 7% methanol buffered with 1.0 mol L^?1 NaOH. The separation procedure was rapidly achieved within 11 min and the matrix interferences could be effectively eliminated. A linear calibration graph was obtained for 5–200 nmol L^?1 analytes with a correlation coefficient in the range 0.9933–0.9995 for amines. This method was successfully utilized to determine aliphatic amines in lake, sewage water, and red wine with recoveries ranging from 96.4 to 105% and the RSDs ranging from 0.9 to 2.9%. Near‐infrared, LIF‐detector‐compatible MeCy5‐OSu was proved suitable for the accurate, sensitive, and rapid separation and determination of aliphatic amines in water and food samples.     

Capillary electrophoresis‐laser‐induced fluorescence detection of rat brain catecholamines with microwave‐assisted derivatization

In this study, a rapid and sensitive method is described for the catecholamines detection in rat brain. CE with LIF detection for the determination of FITC derivatized catecholamines (dopamine, epinephrine, and norepinephrine) was demonstrated. Conventional water bath and microwave‐assisted derivatization methods were employed and a significant reduction in the derivatization time from 2 h for the conventional water bath at room temperature (ca. 25°C) to 2 min for the microwave‐assisted derivatization was achieved. Online sample concentration of field‐amplified sample stacking (FASS) method was employed to achieve higher sensitivities (the detection limits obtained in the normal injection mode ranged from 2.6 to 4.5 ng L^?1 and in the FASS mode ranged from 22 to 34 pg L^?1). Furthermore, this microwave‐assisted derivatization CE–LIF method successfully determined catecholamines in rat brain with as low as 100 ng L^?1 (FASS mode) to 10 μg L^?1 (normal injection mode). This CE–LIF method provided better detection ability when compared to the best reports on catecholamines analyses.     

Simultaneous Derivatization and Dispersive Liquid–Liquid Microextraction for Fatty Acid GC Determination in Water

Simultaneous derivatization and dispersive liquid–liquid microextraction technique for gas chromatographic determination of fatty acids in water samples is presented. One hundred microlitre of ethanol:pyridine (4:1) were added to 4 mL aqueous sample. Then a solution containing 0.960 mL of acetone (disperser solvent), 10 μL of carbon tetrachloride (extraction solvent) and 30 μL of ethyl chloroformate (derivatization reagent) were rapidly injected into the aqueous sample. After centrifugation, 1 μL sedimented phase with the analytes was analyzed by gas chromatography. The effects of extraction solvent type, derivatization, extraction, and disperser solvents volume, extraction time were investigated. The calibration graphs were linear up to 10 mg L^?1 for azelaic acid (R ² = 0.998) and up to 1 mg L^?1 for palmitic and stearic acids (R ² = 0.997). The detection limits were 14.5, 0.67 and 1.06 μg L^?1 for azelaic, palmitic, and stearic acids, respectively. Repeatabilities of the results were acceptable with relative standard deviations (RSD) up to 13%. A possibility to apply the proposed method for fatty acids determination in tap, lake, sea, and river water was demonstrated.     

Determination of Active Ingredients of Hawthorn by Capillary Electrophoresis with Electrochemical Detection

A method based on capillary electrophoresis with electrochemical detection has been developed for the separa-tion and determination of epicatechin,kaempferol,chlorogenic acid,4-hydroxybenzoic acid,quercetin and proto-catechuic acid in hawthorn for the first time.The effects of working electrode potential,pH and concentration ofrunning buffer,separation voltage and injection time on CE-ED were investigated.Under the optimum conditions,the analytes could be separated in a 60 mmol·L~(-1) borate buffer(pH 8.7)within 21 min.A 300 μm diameter carbondisk electrode has a good response at 0.95 V(vs.SCE)for all analytes.The response was linear over three ordersof magnitude with detection limits(S/N=3)ranging from 3×10~(-8) to 2×10~(-7) g·mL~(-1) for the analytes.The methodhas been successfully applied to the analysis of real sample,with satisfactory results.     

Determination of Active Ingredients of Origanum Vulgare L. and Its Medicinal Preparations by Capillary Electrophoresis with Electrochemical Detection

Abstract

A method based on capillary electrophoresis with electrochemical detection (CE‐ED) has been developed for the first time for the separation and determination of isovanillic acid, vanillic acid, quercetin, rosmarinic acid, caffeic acid, and protocatechuic acid in Origanum vulgare L. and its medicinal preparations. The effects of working electrode potential, pH level, concentration of running buffer, separation voltage, and injection time on CE‐ED were investigated. Under the optimum conditions, the analytes could be separated in a 50 mmol L^?1 borate buffer (pH 8.7) within 21 min. A 300‐µm diameter carbon disk electrode has a good response at +0.95 V (vs. SCE) for all analytes. The response was linear over three orders of magnitude with detection limits (S/N=3) ranging from 4×10^?8 g mL^?1 to 2×10^?7 g mL^?1 for the analytes. The method has been successfully applied to the analysis of real sample, with satisfactory results.     

Speciation of methyltins by dispersive liquid–liquid microextraction and gas chromatography with mass spectrometry

Dispersive liquid–liquid microextraction in combination with an in situ derivatization is suggested for methyltin compound sampling and preconcentration from water solutions. The derivatization was carried out with sodium tetraethylborate at pH 3. The effects of extraction and disperser solvents type, volume, and extraction time on the extraction efficiency were investigated. 1,2‐Dichlorobenzene was used as an extraction solvent and ethanol was used as a disperser solvent. The calibration graphs for all the analytes were linear up to 2 μg (Sn) L^?1, correlation coefficients were 0.998–0.999, LODs were 0.13, 0.05, and 0.06 ng (Sn) L^?1 for trimethyltin, DMT, and monomethyltin, respectively. Repeatabilities of the results were acceptable with RSDs up to 12.1%. A possibility to apply the proposed method for methyltin compound determination in water samples was demonstrated.     

Tubular and Microcylindrical Platinum Electrodes for Amperometric Detection of Aminobiphenyls and Aminonaphthalenes in HPLC

Platinum electrodes in microcylindrical and tubular arrangements were compared as working electrodes for amperometric detection of 2‐aminobiphenyl, 4‐aminobiphenyl, 1‐aminonaphthalene, and 2‐aminonaphthalene in HPLC. Factors influencing separation efficiency are favourable for microcylindrical arrangement while tubular arrangement exhibits higher sensitivities and lower limits of detection. These are in the range of 0.0078–0.027 µmol L^?1 for tubular, and 0.11–0.42 µmol L^?1 for microcylindrical arrangement. Further, a new method with nanomolar detection limits was proposed for determination of tested compounds in urine using solid phase extraction for preliminary separation and preconcentration of the analytes.     

Simultaneous screening of homotaurine and taurine in marine macro-algae using liquid chromatography–fluorescence detection

Simultaneous analysis of homotaurine and its homologous, taurine, is a highly challenging issue, especially in matrices they exist simultaneously. A simple precolumn derivatization procedure combined with high-performance liquid chromatography–fluorescence detection was developed for simultaneous determination of homotaurine and taurine in marine macro-algae. The analytes were derivated with o-phthalaldehyde at an ambient temperature and alkaline medium. Calibration curves were linear in the ranges of 50–2500 µg L^?1 for homotaurine and 100–2500 µg L^?1 for taurine with the coefficients of determination higher than 0.998. Limits of detection of homotaurine and taurine were 15 and 30 µg L^?1, respectively. Intraday (n = 6) and inter-day (n = 4) precisions of the method were satisfactory with relative standard deviations less than 6.0%. Good recoveries (>94%) were acquired by the method for extraction of homotaurine and taurine from algae matrices. Liquid chromatography–mass spectrometry was also used to confirm detection of the analytes in algae samples. The data suggest that the method was successfully applied to simultaneous determination of homotaurine and taurine in algae samples.     

Rapid analysis of neurotransmitters in rat brain using ultra‐fast liquid chromatography and tandem mass spectrometry: application to a comparative study in normal and insomnic rats

Neurotransmitters and their metabolites in central nervous system were known to play a significant role in sedation and hypnosis. A rapid and sensitive UFLC‐MS/MS method for simultaneous determination of serotonin, 5‐hydroxyindole acetic acid (5‐HIAA), tryptophan (Try), dopamine (DA), norepinephrine (NE), γ‐aminobutyric acid (GABA), glutamic acid (Glu) and acetylcholine (Ach) in rat brain without derivatization, ion‐pairing reagent or pre‐concentration was developed. Analytes and IS were separated on a Inertsil ODS‐EP column (150 mm × 4.6 mm, 5 µm particles) and analyzed in a single chromatographic run in less than 9.0 min, using gradient elution with the mobile phase consisting of methanol and 0.01% acetic acid in water at a flow rate of 1.2 ml min^?1. The detection of the analytes was performed on 4000Q UFLC‐MS/MS system with turbo ion spray source in positive ion and multiple reaction monitoring mode. The developed method provided excellent linear calibration curves for the assay of analytes (R² ≥ 0.9915). Limits of quantification were in the range of 1.0 ng ml^?1 to 1.0 µg ml^?1 for the analytes in rat brain. Intra‐ and inter‐day precision and accuracy of analytes were well within acceptance criteria (15%). Mean extraction recoveries of analytes and IS from rat brain were all more than 80.0%. Furthermore, the validated method was successfully applied to comparing profiles of analytes in normal and insomnic rat brains. Results indicated that there were statistically significant differences for serotonin, 5‐HIAA, DA, NE, Glu and Ach, but no significant difference for Try and GABA between two groups. Copyright © 2013 John Wiley & Sons, Ltd.     

A Novel Voltammetric Method for the Determination of Maleic Acid Using Silver Amalgam Paste Electrode

An efficient voltammetric method was developed for the determination of maleic acid at a silver amalgam paste electrode (AgA‐PE) in Britton–Robinson buffer pH 2.0. The experimental parameters, such as pH of Britton–Robinson buffer, type of the supporting electrolyte and activation of the electrode surface were optimized. Under the optimal conditions, a linear response was observed over the 2×10^?6–1×10^?4 mol L^?1 maleic acid concentration range, determination limit being 5×10^?7 mol L^?1. A highly stable response, with a relative standard deviation (RSD) of 1.6% for 45 repetitive measurements of 1×10^?4 mol L^?1 maleic acid showed that there was no apparent surface passivation indicating the suitability of the method. The method was successfully applied for direct determination of maleic acid in drinking and river water.     

Preparation,Structure, and Optical Properties of the 1D Chain Red Luminescent Europium Coordination Polymer: {[Eu2L6(DMF)­(H2O)]·2DMF·H2O}n (L = C9H6ClO2–)

The 1D chain red luminescent europium coordination polymer: {[Eu₂L₆(DMF)(H₂O)] · 2DMF · H₂O}_n ( I ) (L = 4‐chloro‐cinnamic acid anion, C₉H₆ClO₂^–, DMF = N, N‐dimethylformamide) was synthesized by the reaction of Eu(OH)₃ and 4‐chloro‐cinnamic acid ligand. The structure of the coordination polymer was determined by single‐crystal X‐ray diffraction analysis. It reveals that there exists two crystallographically nonequivalent europium atoms in each unit of this coordination polymer and Eu³⁺ ions are connected by two alternating bridging modes to form an endless polymer structure. The luminescent properties and energy transfer process in the complex are investigated at room temperature.     

Development of an Amperometric Biosensor for β‐N‐Oxalyl‐L‐α,β‐Diaminopropionic Acid (β‐ODAP)

An amperometric method for the determination of the neurotoxic amino acid β‐N‐oxalyl‐L ‐α,β‐diaminopropionic acid (β‐ODAP) using a screen printed carbon electrode (SPCE) is reported. The electrode material was bulk‐modified with manganese dioxide and used as a detector in flow injection analysis (FIA). The enzyme glutamate oxidase (GlOx) was immobilized in a Nafion‐film on the electrode surface. The performance of the biosensor was optimized using glutamate as an analyte. Optimum parameters were found as: operational potential 440 mV (vs. Ag/AgCl), flow rate 0.2 mL min^?1, and carrier composition 0.1 mol L^?1 phosphate buffer (pH 7.75). The same conditions were used for the determination of β‐ODAP. The signal was linear within the concentration range 53–855 μmol L^?1 glutamate and 195–1950 μmol L^?1 β‐ODAP. Detection limits (as 3σ value) for both analytes were 9.12 and 111.0 μmol L^?1, respectively, with corresponding relative standard deviations of 3.3 and 4.5%. The biosensor retained more than 73% of its activity after 40 days of on‐line use.     

Simultaneous Determination of Ascorbic Acid and Uric Acid by Using a PVC/TTF‐TCNQ Composite Electrode as Detector in a FIA System

A PVC/TTF‐TCNQ composite electrode has been employed as detector in a flow injection system. The proposed method allows the simultaneous detection of ascorbic acid (AA) and uric acid (UA) in mixtures by using a FIA system in a simple manner, without pre‐treatment or modified electrode. This method is based on the amperometric determination of (a) ascorbic acid at 0.15 V and (b) both analytes at 0.35 V, being the response linear in the range 1×10^?2–4×10^?4 M for both analytes with detection limits (S/N=3) of 1.2×10^?4 M and 8.1×10^?5 M for AA and UA, respectively.     

Electroanalytical Determination of Carbaryl in Natural Waters on Boron Doped Diamond Electrode

The anodic voltammetric behavior of carbaryl on a boron‐doped diamond electrode in aqueous solution is reported. The results, obtained by square‐wave voltammetry at 0.1 mol L^?1 Na₂SO₄ and pH 6.0, allow the development of a method to determine carbaryl, without any previous step of extraction, clean‐up, preconcentration or derivatization, in the range 2.5–30.0×10^?6 mol L^?1, with a detection limit of 8.2±0.2 μg L^?1 in pure water. The analytical sensitivity of this electrochemical method diminished slightly, from 3.07 mA mmol^?1 L to 2.90 mA mmol^?1L, when the electrolyte was prepared with water samples collected from two polluted points in an urban creek. In these conditions, the recovery efficiencies obtained were around 104%. The effect of other pesticides (fenthion and 4‐nitrophenol) was evaluated and found to exert a negligible influence on carbaryl determination. The square‐wave voltammetric data obtained for carbaryl were typical of an irreversible electrode process with mass transport control. The combination of square‐wave voltammetry and diamond electrodes is an interesting and desirable alternative for analytical determinations.     

High-precision quadruple isotope dilution method for simultaneous determination of nitrite and nitrate in seawater by GCMS after derivatization with triethyloxonium tetrafluoroborate

Quadruple isotope dilution mass spectrometry (ID⁴MS) has been applied for simultaneous determination of nitrite and nitrate in seawater. ID⁴MS allows high-precision measurements and entails the use of isotopic internal standards (¹⁸O-nitrite and ¹⁵N-nitrate). We include a tutorial on ID⁴MS outlining optimal experimental design which generates results with low uncertainties and obviates the need for direct (separate) evaluation of the procedural blank. Nitrite and nitrate detection was achieved using a headspace GCMS procedure based on single-step aqueous derivatization with triethyloxonium tetrafluoroborate at room temperature. In this paper the sample preparation was revised and fundamental aspects of this chemistry are presented. The proposed method has detection limits in the low parts-per-billion for both analytes, is reliable, precise, and has been validated using a seawater certified reference material (MOOS-2). Simplicity of the experimental design, low detection limits, and the use of quadruple isotope dilution makes the present method superior to the state-of-the-art for determination of nitrite and nitrate, and an ideal candidate for reference measurements of these analytes in seawater.     

Label‐Free,Non‐Derivatization CRET Detection Platform for 6‐Mercaptopurine Based on the Distance‐Dependent Optical Properties of Gold Nanoparticles

A label‐free, non‐derivatization chemiluminescence resonance energy transfer (CRET) detection platform has been developed for the detection of the non‐fluorescent small molecule 6‐mercaptopurine. This CRET process arose from a chemiluminescent (CL) donor–acceptor system in which the reaction of bis(2,4,6‐trichlorophenyl)oxalate (TCPO)–H₂O₂–fluorescein (maximum emission at 521.6 nm) served as the donor and gold nanoparticles (AuNPs, maximum absorption at 520.0 nm) served as the acceptor. This process caused a significant decrease in the CL signal of the TCPO–H₂O₂–fluorescein reaction. The presence of 6‐mercaptopurine induced an aggregation of AuNPs with the assistance of Cu²⁺ ions through cooperative metal–ligand interactions that was accompanied by a distinct change in color and optical properties. The maximum absorption band of the AuNPs was red‐shifted to 721.0 nm and no longer overlapped with the CL spectrum of the reaction; as a result, the CL signal was restored. This CRET system exhibited a wide linear range, from 9.0 nmol L^?1 to 18.0 μmol L^?1, and a low detection limit (0.62 nmol L^?1) for 6‐mercaptopurine. The applicability of the proposed CRET system was evaluated by analysis of 6‐mercaptopurine in spiked human plasma samples.     

In‐vitro Aluminum Determination and Preconcentration in Blood of Dialysis Patients Based on Ionic Liquid Dispersive Liquid‐Liquid Biomicroextraction by 2‐Amino‐3‐(1H‐imidazol‐4‐yl)propanoic Acid

In this study, trace amounts of aluminum in serum of dialysis patients were chelated with 2‐Amino‐3‐(1H‐imidazol‐4‐yl)propanoic acid (Histidine) and determined by electro‐thermal atomic absorption spectrometry (ETAAS). A fast and efficient method based on ionic liquid dispersive liquid‐liquid bio‐micro‐extraction (IL‐DLLBME) was developed for the determination of Al cation in human blood serum samples. In this work, a small amount of 1‐Hexyl‐3‐methylimmidazolum hexafluorophosphate ([HMIM] [PF₆]) as an extractant solvent was dissolved in acetone as a dispersant solvent and then the binary solution was rapidly injected by a syringe into the serum containing Al³⁺,Which have already in‐vitro chelated by Histidine amino acid (Al‐His) at pH = 6.5. After separation, the settled IL‐phase was dissolved in ethanol up to 200 μL and 20 μL of samples injected into the ET‐AAS by auto‐sampler. Various parameters have been studied and optimized for 10 mL of sample. Under the optimum conditions, the enrichment factor (EF), limit of detection (LOD) and working range (peak area mode) were obtained 53, 15 ng L^?1 and 0.05‐4.1 μg L^?1 respectively. In vitro Al chelation showed that His can significantly decrease aluminum concentration in serum of dialysis patients. Validation of methodology was confirmed by standard reference material (SRM).     

Electrochemical Morphine Sensor Based on Gold Nanoparticles Metalphthalocyanine Modified Carbon Paste Electrode

Composites of gold nanoparticles (Au) electrochemically deposited and different metal phthalocyanines (Co, Ni, Cu, and Fe) were chemically prepared. The composites were used as modifiers for carbon paste electrodes and were used for the determination of morphine in presence of ascorbic acid and uric acid. Central metal atoms of phthalocyanine moiety affected the rate of electron transfer. Thus, the electroactivity of different modifiers were evaluated towards morphine oxidation. Au‐CoPcM‐CPE possessed the highest rate for charge transfer rate in all studied pH electrolytes. Limit of detection was 5.48×10^?9 mol L^?1 in the range of 4.0×10^?7 to 9.0×10^?4 mol L^?1.     

LC–MS/MS Determination of Catecholamines in Urine Using FMOC-Cl Derivatization on Solid-Phase Extraction Cartridge

A method for the determination of catecholamine derivatives in human urine is proposed that includes the derivatization of target compounds on a solid-phase extraction cartridge and determination of the analytes by a UHPLC method with tandem mass-spectrometric detection. 9-Fluorenyl-methoxycarbonyl chloride was used as the derivatization agent. The limits of detection for the analytes were 2.5 ng mL^?1 for 9-fluorenyl-methoxycarbonyl-adrenaline, 5 ng mL^?1 for 9-fluorenyl-methoxycarbonyl-octopamine, and 25 ng mL^?1 for 9-fluorenyl-methoxycarbonyl-dopamine. The proposed procedure was tested on real samples obtained from volunteers.     

Construction of an Electrochemical Cell System Based on Carbon Composite Film Electrodes and its Application for Voltammetric Determination of Triclosan

An array of carbon composite electrodes embedded in a 96 well microtitration plate was fabricated and applied for DPV determination of the environmental pollutant triclosan (5‐chloro‐2‐(2,4‐dichlorophenoxy)‐phenol). For the preparation of composite electrodes, graphite and glassy carbon conductive microparticles were tested in combination with several types of polymers as nonconductive binders. For the measurements, combinations of graphitic carbon particles with polystyrene (C‐PS) and with polycarbonate (C‐PC) were selected. The achieved limit of detection was 0.49 µmol L^?1 for C‐PS electrodes and 0.25 µmol L^?1 for C‐PC electrodes in the selected optimum medium. The method was successfully applied for practical samples of river water and toothpaste.