Miniaturized capillary ion chromatograph with UV light‐emitting diode based indirect absorbance detection for anion analysis in potable and environmental waters

A miniaturized, flexible, and low‐cost capillary ion chromatography system has been developed for anion analysis in water. The ion chromatography has an open platform, modular design, and allows for ease of modification. The assembled platform weighs ca. 0.6 kg and is 25 × 25 cm in size. Isocratic separation of common anions (F^–, Cl^–, NO₂^–, Br^–, and NO₃^–) could be achieved in under 15 min using sodium benzoate eluent at a flow rate of 3 μL/min, a packed capillary column (0.150 × 150 mm) containing Waters IC‐Pak 10 μm anion exchange resin, and light‐emitting diode based indirect UV detection. Several low UV light‐emitting diodes were assessed in terms of sensitivity, including a new 235 nm light‐emitting diode, however, the highest sensitivity was demonstrated using a 255 nm light‐emitting diode. Linear calibration ranges applicable to typical natural water analysis were obtained. For retention time and peak area repeatability, relative standard deviation values ranged from 0.60–0.95 and 1.95–3.53%, respectively. Several water samples were analysed and accuracy (recovery) was demonstrated through analysis of a prepared mixed anion standard. Relative errors of –0.36, –1.25, –0.80, and –0.76% were obtained for fluoride, chloride, nitrite, and nitrate, respectively.     

A platform for on-site environmental analysis of explosives using high performance liquid chromatography with UV absorbance and photo-assisted electrochemical detection

High-performance liquid chromatography with photo-assisted electrochemical detection (HPLC-PAED) is used in conjunction with ultraviolet absorbance (UV) detection for determining explosives in environmental samples. The system utilizes an on-line solid-phase extraction technique for sample pretreatment (i.e., fractionation and concentration), thus reducing the required ground water sample size from 1 L to 2 mL and minimizing sample handling. Limits of detection for explosives using solid-phase extraction and PAED range from 0.0007 to 0.4 μg/L, well below those achieved with UV detection for several important explosives (e.g., RDX). The method has demonstrated good accuracy, precision, and recovery for all tested explosives, thus proving that the method is suitable for evaluation of explosives in ground water with competitive advantages over the U.S. Environmental Protection Agency (EPA) Method 8330. A system adaptable for the on-site environmental analysis of explosives has been developed and validated.     

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent

Indirect ultraviolet detection was conducted in ultraviolet‐absorption‐agent‐added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li⁺, Na⁺, K⁺, and NH₄⁺ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography‐indirect ultraviolet detection. The successful separation and detection of Li⁺, Na⁺, K⁺, and NH₄⁺ within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded.     

Simultaneous determination of alcohols including diols and triols by HPLC with ultraviolet detection based on the formation of a copper(II) complex

We developed a reversed‐phase high‐performance liquid chromatography method with ultraviolet detection using on‐line complexation with Cu(II) ion for analysis of five alcohols including diols and triol (methanol, ethanol, 1,2‐propanediol, 1,3‐propanediol, and glycerol). The Cu(II) ion concentration in the mobile phase had a great influence on the peak areas of these alcohols, but not on their retention times. Column temperature (25−40°C) and pH of the mobile phase did not affect the separation of analytes. The optimum separation conditions were determined as 5 mM CuSO₄, 3 mM H₂SO₄, and 3 mM NaOH at 30°C. The ratio of the peak areas for three alcohols (methanol, 1,2‐propanediol, and glycerol) was in good agreement with that calculated from the obtained stability constants, molar absorption coefficients for the 1:1 Cu(II) complexes with the three alcohols, and the injected molar quantities. This fact strongly suggests that the observed high‐performance liquid chromatography signals resulted from formation of the 1:1 Cu(II)–alcohol complexes. Using the proposed method, these five alcohols in spirit, liquid for electronic cigarette, mouthwash, and nail enamel remover samples were successfully analyzed with only a simple pretreatment.     

Simultaneous determination of short‐chain fatty acids in human feces by HPLC with ultraviolet detection following chemical derivatization and solid‐phase extraction segmental elution

Short‐chain fatty acids are currently the most studied metabolites of gut microbiota, but the analysis of them, simultaneously, is still challenging due to their unique property and wide concentration range. Here, we developed a sensitive and versatile high‐performance liquid chromatography with ultraviolet detection method, using pre‐column derivatization and solid‐phase extraction segmental elution, for the quantification of both major and trace amounts of short‐chain fatty acids in human feces. Short‐chain fatty acids were converted to 3‐nitrophenylhydrazine‐derived analytes, and then solid‐phase extraction segmental elution was used for extraction of major analytes and enrichment of trace analytes. The method validation showed limits of quantitation ?0.04 mM, and coefficient of determination > 0.998 at a wide range of 0.04–8.0 mM. The intra‐ and interday precision of analytes were all within accepted criteria, and the recoveries were 96.12 to 100.75% for targeted analytes in fecal samples. This method was successfully applied in quantification of eight analytes in human feces, which therefore could provide a sensitive and versatile high‐performance liquid chromatography with ultraviolet detection method for precise and accurate quantitation of short‐chain fatty acids in human feces.     

Evaluation of potential cationic probes for the detection of proline and betaine

Osmoregulants are the substances that help plants to tolerate environmental extremes such as salinity and drought. Proline and betaine are two of the most commonly studied osmoregulants. An indirect UV CE method has been developed for simultaneous determination of these osmoregulants. A variety of reported probes and compounds were examined as potential probes for the indirect detection of proline and betaine. Mobility and UV‐absorption properties highlighted sulfanilamide as a potential probe for indirect analysis of proline and betaine. Using 5 mM sulfanilamide at pH 2.2 with UV detection at 254 nm, proline and betaine were separated in less than 15 min. The LODs for proline and betaine were 11.6 and 28.3 μM, respectively. The developed method was successfully applied to quantification of these two osmoregulants in spinach and beetroot samples.     

以离子液体为流动相的高效液相色谱-间接紫外检测法分析四甲基按根离子

建立了四甲基铵根离子的反相高效液相色谱-间接紫外检测分析法.以ZORBAX ODS反相色谱柱为分离柱,采用间接紫外检测方法,考察了紫外检测波长和离子液体+有机溶剂(乙腈、甲醇)流动相对分离和测定四甲基铵根离子的影响.最佳色谱条件为:以80% 1-乙基-3-甲基咪唑四氟硼酸盐水溶液(0.5 mmol/L,乙酸调pH 3....     

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg²⁺, Ca²⁺, and Sr²⁺ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV‐absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg²⁺, Ca²⁺, and Sr²⁺ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg²⁺, Ca²⁺, and Sr²⁺ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S /N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded.     

Enantioselective micellar electrokinetic chromatography of dl‐amino acids using (+)‐1‐(9‐fluorenyl)‐ethyl chloroformate derivatization and UV‐induced fluorescence detection

Chiral analysis of dl ‐amino acids was achieved by micellar electrokinetic chromatography coupled with UV‐excited fluorescence detection. The fluorescent reagent (+)‐1‐(9‐fluorenyl)ethyl chloroformate was employed as chiral amino acid derivatizing agent and sodium dodecyl sulfate served as pseudo‐stationary phase for separating the formed amino acid diastereomers. Sensitive analysis of (+)‐1‐(9‐fluorenyl)ethyl chloroformate‐amino acids was achieved applying a xenon‐mercury lamp for ultraviolet excitation, and a spectrograph and charge‐coupled device for wavelength‐resolved emission detection. Applying signal integration over a 30 nm emission wavelength interval, signal‐to‐noise ratios for derivatized amino acids were up to 23 times higher as obtained using a standard photomultiplier for detection. The background electrolyte composition (electrolyte, pH, sodium dodecyl sulfate concentration, and organic solvent) was studied in order to attain optimal chemo‐ and enantioseparation. Enantioseparation of 12 proteinogenic dl ‐amino acids was achieved with chiral resolutions between 1.2 and 7.9, and detection limits for most derivatized amino acids in the 13–60 nM range (injected concentration). Linearity (coefficients of determination > 0.985) and peak‐area and migration‐time repeatabilities (relative standard deviations lower than 2.6 and 1.9%, respectively) were satisfactory. The employed fluorescence detection system provided up to 100‐times better signal‐to‐noise ratios for (+)‐1‐(9‐fluorenyl)ethyl chloroformate‐amino acids than ultraviolet absorbance detection, showing good potential for d ‐amino acid analysis.     

Separation and indirect ultraviolet detection of ferrous and trivalent iron ions by using ionic liquids in ion chromatography

A method of simultaneous separation and indirect ultraviolet detection of different valence iron ions Fe²⁺ and Fe³⁺ by using ionic liquids as mobile phase additives and ultraviolet absorption reagents on a cation exchange column functionalized with carboxylic acid group was developed. The effects of ionic liquids, organic acids, detection wavelength, etc. on separation and detection of Fe²⁺ and Fe³⁺ were investigated and the mechanism was discussed. The pyridinium and imidazolium ionic liquids were not only ultraviolet absorption reagents of indirect ultraviolet detection but also effective components for separating Fe²⁺ and Fe³⁺. The separation and detection of Fe²⁺ and Fe³⁺ can be achieved using 0.5 mmol/L pyridinium ionic liquid?1.2 mmol/L methanesulfonic acid as the mobile phase. The determination of Fe²⁺ and Fe³⁺ had a good linear relationship in the concentration range of 1?100 mg/L. The limits of detection of Fe²⁺ and Fe³⁺ were 0.12 and 0.09 mg/L, respectively. This method was applied to the actual sample detection in the field of medical analysis. The spiked recoveries were between 97.3 and 99.5%, and the relative standard deviations were less than 0.6%. The method is simple, accurate, and reliable, and is an analytical method with universal and practical value.     

Amino functionalized magnetic covalent organic framework for magnetic solid-phase extraction of sulfonylurea herbicides in environmental samples from tobacco land

An amino-functionalized magnetic covalent organic framework composite TpBD-(NH₂)₂@Fe₃O₄ (Tp=Tp1,3,5-triformylphloroglucinol, BD-(NH₂)₂ is 3,3',4,4'-biphenyltetramine) was prepared by post-synthesis modification. Due to its abundant benzene rings and amino groups, large specific surface area and porous structure, the prepared TpBD-(NH₂)₂@Fe₃O₄ exhibits high extraction efficiency toward sulfonylurea herbicides. Based on this, a new method of magnetic solid-phase extraction with TpBD-(NH₂)₂@Fe₃O₄ as the sorbent combined with high-performance liquid chromatography and ultraviolet detection was developed for trace analysis of sulfonylurea herbicides in environmental water, soil and tobacco leaves samples from tobacco land. Under the optimized conditions, the limits of detection within 0.05–0.14 μg/L were achieved with a high enrichment factor of 217-260-fold, and the relative standard deviations were 4.9–7.5% (n = 7, c = 0.5 μg/L). The linear range was around three orders of magnitude with the square of correlation coefficient higher than 0.9936. The method was applied to analyze five sulfonylurea herbicides in the environmental water, soil, and tobacco leave samples collected from tobacco land. No sulfonylurea herbicides were detected in these samples. The recoveries of target sulfonylurea herbicides in spiked environmental water, soil, and tobacco leaf samples were found in the range of 90.7–104, 70.7–99.0, and 59.3–97.8%, respectively. The results illustrate that the established TpBD-(NH₂)₂@Fe₃O₄-magnetic solid-phase extraction- high-performance liquid chromatography–ultraviolet detection method is efficient for the analysis of trace sulfonylurea herbicides in environmental samples.     

Rapid determination of NSAIDs by capillary and microchip electrophoresis with capacitively coupled contactless conductivity detection in wastewater

A simple, rapid method using CE and microchip electrophoresis with C⁴D has been developed for the separation of four nonsteroidal anti-inflammatory drugs (NSAIDs) in the environmental sample. The investigated compounds were ibuprofen (IB), ketoprofen (KET), acetylsalicylic acid (ASA), and diclofenac sodium (DIC). In the present study, we applied for the first time microchip electrophoresis with C⁴D detection to the separation and detection of ASA, IB, DIC, and KET in the wastewater matrix. Under optimum conditions, the four NSAIDs compounds could be well separated in less than 1 min in a BGE composed of 20 mM His/15 mM Tris, pH 8.6, 2 mM hydroxypropyl-beta-cyclodextrin, and 10% methanol (v/v) at a separation voltage of 1000–1200 V. The proposed method showed excellent repeatability, good sensitivity (LODs ranging between 0.156 and 0.6 mg/L), low cost, high sample throughputs, portable instrumentation for mobile deployment, and extremely lower reagent and sample consumption. The developed method was applied to the analysis of pharmaceuticals in wastewater samples with satisfactory recoveries ranging from 62.5% to 118%.     

Determination of ticagrelol in rat plasma and tablets by micellar electrokinetic chromatography coupled with large volume sample stacking: Application to a pharmacokinetic study

A method using micellar electrokinetic chromatography coupled with large-volume sample stacking for the determination of ticagrelol was developed and validated. The analysis was performed in a fused silica capillary (41.5 cm effective length, 50 μm diameter) with ultraviolet detection at 195 nm. The background electrolytes were 30 mM phosphate buffer of pH 3.0 with 120 mM sodium dodecylsulfate and 10 % (v/v) acetonitrile (120 s X 50 mbar; 20°C; -18 kV) and 30 mM borate buffer of pH 8.5 with 75 mM sodium dodecylsulfate (120 s X 50 mbar; 20°C; 25 kV); under acidic and alkaline conditions, respectively. The method was found to be reliable with respect to specificity, linearity of the calibration line (R² > 0.99), repeatability (relative standard deviation 2.56%–3.34%), and accuracy (recovery in the range 101.21%–102.67%). The limits of detection and quantitation were 0.032, 0.071, and 0.087, 0.188 μg/mL, respectively. The method was successfully applied for the determination of ticagrelol concentrations in rat plasma and tablets with good recoveries and reproducibility. The presented method proved to be suitable for monitoring ticagrelor in rat plasma.     

Construction of zinc selenide microspheres decorated with octadecylamine-functionalized reduced graphene oxide as an effective catalyst for the dual-mode detection of chloroquine phosphate

Zinc selenide microspheres were constructed using a simple hydrothermal technique at 180°C. It was ultrasonically treated with reduced graphene oxide modified with octadecylamine alkyl amine to form a hybrid nanocomposite. The optical, structural, and functional analysis by ultraviolet (UV) absorbance, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy revealed the crystal nature of the microspheres and the successful formation of the nanocomposite. Field emission scanning electron microscopy and transmission electron microscopy were done to study the morphological properties of the material. It was further used to fabricate a dual-modality sensor using both electrochemical and absorbance techniques for the detection of antimalarial drug chloroquine phosphate (CQP), which was used for the treatment of COVID-19 (SARS-CoV-2) virus. For electrochemical detection, the sensor showed a very low detection limit of 1.43 nM at a linear working range of 0.199–250.06 μM and a high sensitivity of 43.912 μA/μM/cm². For UV-based detection, the sensor showed a very low detection limit of 6.88 nM at a linear working range of 0.045–7.324 μM. The sensor showed excellent analyte recovery rate for real-time analysis in biological as well as environmental samples. The results suggested that the sensor is effective for the detection of CQP with feasibility for future commercialization.     

Determination of sulfate and chloride ions in highly saline oilfield water by capillary electrophoresis using bilayer-coated capillaries and indirect absorption detection

Analysis of highly saline oilfield waters for anions presents challenges. Traditional analytical techniques used for such analysis tend to suffer from both poor sensitivity and selectivity due to the high concentrations of salt present in the samples. A capillary electrophoresis method was developed for the simultaneous determination of chloride and sulfate anions which is relevant to the oilfield analysis industry and of economic value. Due to the extremely high concentrations of chloride in highly saline oilfield waters, it is difficult to achieve baseline electrophoretic separation necessary for accurate quantitation. By using a capillary with a noncovalently bound bilayer coating using Polybrene, a cationic polymer and sodium dodecyl sulfate (SDS), an anionic surfactant and a buffer consisting of 50 mM TRIS, 30 mM SDS, 5% methanol and 26 mM chromium trioxide (CrO₃) at pH 6.7, baseline separation (R_s > 1.5) of chloride and sulfate was achieved. To mimic possible oilfield water samples, model water solutions of 5%, 10%, 15% and 20% chloride containing low ppm sulfate were prepared and successfully analysed using the method developed. In addition, the method was applied to determine chloride and sulfate anions in highly saline oilfield water samples. The accuracy of the method developed was verified by analysing NIST certified standards of chloride and sulfate. The results obtained for chloride and sulfate with the indirect CE-UV method were in close agreement (94–100% accuracy; <2.5% relative standard deviations) with those of the certified standard analysed by ion chromatography.     

Separation of selenium species and their sensitive determination in rice samples by ion‐pairing reversed‐phase liquid chromatography with inductively coupled plasma tandem mass spectrometry

A highly sensitive method was developed for the simultaneous separation and determination of organic and inorganic selenium species in rice by ion‐pairing reversed‐phase chromatography combined with inductively coupled plasma tandem mass spectrometry. To achieve a good separation of these species, a comparison between anion‐exchange chromatography and ion‐pairing reversed‐phase chromatography was performed. The results indicated that ion‐pairing reversed‐phase chromatography was more suitable due to better separation and higher sensitivity for all analytes. In this case, a StableBond C18 column proved to be more robust or to have a better resolution than other C18 columns, when 0.5 mM tetrabutylammonium hydroxide and 10 mM ammonium acetate at pH 5.5 were used as the mobile phase. Moreover, an excellent sensitivity was obtained in terms of interferences by means of tandem mass spectrometry in the hydrogen mode. The detection limits were 0.02–0.12 μg/L, and recoveries of five selenium species were 75–114%, with relative standard deviations ≤ 9.4%. This method was successfully applied to the analysis of rice samples. Compared with previous studies, the proposed method not only gave comparable results when used for measuring selenium‐enriched rice, but it can provide greater sensitivity for the detection of low concentrations of selenium species in rice.     

Potential of microemulsion electrokinetic chromatography for the separation of priority endocrine disrupting compounds

This work examines the potential of microemulsion electrokinetic chromatography for the separation of several priority endocrine disrupting compounds (EDCs). The optimised microemulsion system comprised 25 mM phosphate buffer pH 2, 80 mM octane, 900 mM butanol, 200 mM sodium dodecyl sulphate and was further modified with 20% propanol. The use of a low pH buffer resulted in the suppression of electroosmotic flow within the capillary. Reversal of the conventional electrode polarity resulted in faster migration of hydrophobic compounds. Test analytes included the octylphenol, nonylphenol and nonylphenol diethoxylate, which are breakdown products of the alkylphenolic detergents. The synthetic oestrogens diethylstilbestrol and ethynyloestradiol were also included in the separation along with the plastic monomer bisphenol-A. Test analytes were selected due to their reported presence in environmental samples namely industrial and domestic wastewater treatment effluents and sludges. Using the optimised method a separation of six EDCs was achieved within 15 min. The optimised method was then applied to the analysis of a spiked wastewater influent sample with UV detection of all six compounds at 214 nm.     

Headspace solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the sensitive determination of benzotriazole UV stabilizers in water samples

A sensitive procedure for the determination of five ultraviolet (UV) absorbers, belonging to the benzotriazole class, in environmental water samples is proposed. Analytes were first extracted and concentrated from the matrix and then selectively determined by gas chromatography in combination with tandem mass spectrometry detection. The high lipophilic character of some of the investigated species resulted in a strong trend to remain sorbed on solid surfaces, even after addition of considerable percentages of methanol (up to 30%) to water. Thus, minimizing sample handling during the enrichment step is mandatory in order to obtain acceptable accuracy and precision. Solid-phase microextraction (SPME), as sample preparation approach, fulfilled the above requirement and provided acceptable figures of merit for the determination of target species in environmental water samples, including raw wastewater. Optimization of SPME conditions showed that the combination of headspace extraction, with a sample temperature of 100 °C and addition of 15 mg of NaCl per milliliter of sample rendered the best compromise in terms of extraction efficiency for all species. Considering a sampling time of 30 min with a poly(dimethylsiloxane)–divinylbenzene-coated SPME fiber, limits of quantification below 2 ng l⁻¹ and relative standard deviations between 5% and 12% were achieved. Three of the five species included in this research were determined in raw wastewater with a maximum concentration of 57 ng l⁻¹ for the Tinuvin 326 UV absorber.     

Determination of tetraethyl ammonium by ion-pair chromatography with indirect ultraviolet detection using 4-aminophenol hydrochloride as background ultraviolet absorbing reagent

A method was developed for the determination of tetraethyl ammonium (TEA) by reversed-phase ionpair chromatography with indirect ultraviolet detection. Chromatographic separation was achieved on a reversed-phase C18 column using background ultraviolet absorbing reagent - ion-pair reagent - organic solvent as mobile phase. The effects of the background ultraviolet absorbing reagents, detection wavelength, ion-pair reagents, organic solvents and column temperature on the determination method were investigated and the retention rules discussed. Results found that TEA could be successfully analyzed by using 0.7 μmol/L 4-aminophenol hydrochloride and 0.15 μmol/L 1-heptanesulfonic acid sodium mixed with 20% (v/v) methanol asmobile phase at a UV detection wavelength of 230 nm. Under these conditions, the retention time of tetraethyl ammonium was 2.85 min. The detection limit (S/N = 3) for TEA was 0.06 mg/L. The relative standard deviations (n = 5) for peak area and retention time were 0.35% and 0.02%, respectively. The method has been successfully applied to the determination of synthesized tetraethyl ammonium bromide. Recovery of tetraethyl ammonium after spiking was 99.1%.     

Analysis of hormone antagonists in clinical and municipal wastewater by isotopic dilution liquid chromatography tandem mass spectrometry

A comprehensive method was developed for the simultaneous trace analysis of ten hormone antagonist pharmaceuticals (raloxifene, exemestane, letrozole, anastrozole, mifepristone, finastride, tamoxifen, N-desmethyltamoxifen, clomiphene, and toremifene) in municipal sewage and hospital wastewater samples. The target compounds were firstly extracted using an Oasis HLB cartridge, followed by purification by an aminopropyl cartridge, and were then analyzed by liquid chromatography electrospray ionization tandem mass spectrometry in positive ion mode. The recoveries for the analytes based on internal standard calibration in different test matrices ranged from 67.6 to 118.6% (with the exception of mifepristone in clinical wastewater samples), with relative standard deviations less than 20%. The method quantification limits of the ten pharmaceuticals were in the range 0.10–2.0 ng/L. Excluding exemestane and N-desmethyltamoxifen, eight drugs were detected at 0.20–195.0 ng/L in hospital wastewater and municipal wastewater samples from Beijing.