Combining poly (methacrylic acid‐co‐ethylene glycol dimethacrylate) monolith microextraction and octadecyl phosphonic acid‐modified zirconia‐coated CEC with field‐enhanced sample injection for analysis of antidepressants in human plasma and urine

A method based on poly (methacrylic acid‐co‐ethylene glycol dimethacrylate) monolith microextraction and octadecylphosphonic acid‐modified zirconia‐coated CEC followed by field‐enhanced sample injection preconcentration technique was proposed for sensitive CE‐UV analysis of six antidepressants (doxepin, clozapine, imipramine, paroxetine, fluoxetine and chlorimipramine) in human plasma and urine. A poly(methacrylic acid‐co‐ethylene glycol dimethacrylate) monolithic capillary column was introduced for the extraction of antidepressants from urine and plasma samples. The hydrophobic main chains and acidic pendant groups of the monolithic column make it a superior material for extraction of basic analytes from aqueous matrix. After extraction, the desorption solvent, which normally provided an excellent medium to ensure direct compatibility for field‐enhanced sample injection in CE, was analyzed by CE directly. By the use of alkylphosphonate‐modified zirconia‐coated CEC for separation of the basic compounds of antidepressants, high separation efficiency and resolution were achieved because that both hydrophobic interaction between analytes and alkylphosphonate‐modified zirconia coat and electrophoretic effect work on the separation of antidepressants. The best separation was achieved using a buffer composed of 0.3 M ammonium acetate (adjusted to pH 4.5 with 1 M acetic acid) and 35% ACN v/v, with a temperature and voltage of 20°C and 20 kV, respectively. By applying both preconcentration procedures, LODs of 11.4–51.5 and 3.7–17.0 μg/L were achieved for the six antidepressants in human plasma and urine, respectively. Excellent method of reproducibility was found over a linear range of 50–5000 μg/L in plasma and urine sample.     

On‐site sampling and sample‐preparation approach with a portable sampler based on hollow‐fiber/graphene bars for the microextraction of nitrobenzene compounds in lake water

A novel on‐site sampling and sample‐preparation approach was developed and evaluated in the present work. In this procedure, hollow‐fiber/graphene bars (HF/GBs) were used for sampling and sample preparation. A handheld battery‐operated electric egg beater was utilized to support the HF/GBs and stir the sample solution to facilitate extraction at the sampling site. Four nitrobenzene compounds (nitrobenzene, o‐nitrophenol, m‐nitrophenol, and p‐nitrophenol) were used as model compounds. Several factors affecting performance, including types and amount of graphene used and extraction and desorption times, were investigated and optimized in the laboratory. Under optimized conditions, the enrichment factors of the four nitrobenzene compounds ranged from 46 to 69. Good linearities of 0.01–10 μg/mL with regression coefficients between 0.9917 and 0.9973 were obtained for all analytes. The LOD of the method was 0.3 ng/mL. Satisfactory recoveries (98–102%) and precision (1.0–5.8%) were also achieved. The ultrastructures and extraction mechanism of the HF/GBs were characterized and analyzed. The proposed approach coupled with high‐performance liquid chromatography was successfully applied in the extraction and determination of trace nitrobenzene compounds in lake water. Experimental results showed that the approach is simple, convenient, rapid, and practical for routine environmental monitoring.     

Development of a solid‐phase microextraction fiber coated with poly(methacrylic acid‐ethylene glycol dimethacrylate) and its application for the determination of chlorophenols in water coupled with GC

A solid‐phase microextraction (SPME) fiber coated with poly(methacrylic acid‐ethylene glycol dimethacrylate) coupled to GC with a micro electron‐capture detector was developed for the determination of four chlorphenols in water samples for the first time. A novel and simple method for the preparation of this novel SPME fiber was proposed by copolymerization of methacrylic acid and ethylene glycol dimethacrylate in an appropriate solvent using a glass capillary as a “mold”. The factors affecting the polymerization were optimized in detail. Furthermore, the extraction performance of the poly(methacrylic acid‐ethylene glycol dimethacrylate) fiber was evaluated. Moreover, experimental headspace‐SPME parameters, such as extraction temperature, extraction time, salt concentration, stirring speed, and pH, were optimized by orthogonal array experimental designs. Under the optimized conditions, the target analytes were linear in the range of 0.2–50 ng/mL, and the correlation coefficients were all greater than 0.99. RSD was less than 8.9%, and the detection limits were in the range of 0.1–10 ng/L. Four cholorphenols were detected from tap and lake water samples using the proposed method, with the recoveries of spiked natural water samples were ranged from 91.8 to 110.8, and 90.6 to 111.4% for tap and lake water samples, respectively.     

Polyaniline‐coated cigarette filters as a solid‐phase extraction sorbent for the extraction and enrichment of polycyclic aromatic hydrocarbon in water samples

Polyaniline coated cigarette filters were successfully synthesized and used as a solid‐phase extraction sorbent for the extraction and preconcentration of polycyclic aromatic hydrocarbons in water samples. The polyaniline helped to enhance the adsorption ability of polycyclic aromatic hydrocarbons on the sorbent through π–π interactions. The high porosity and large surface area of the cigarette filters helped to reduce backpressure and can be operated with high sample flow rate without loss of extraction efficiency. The developed sorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The parameters that affected the extraction efficiencies, i.e. polymerization time, type of desorption solvent and its volume, sample flow rate, sample volume, sample pH, ionic strength, and organic modifier were investigated. Under the optimal conditions, the method was linear over the range of 0.5–10 μg/L and a detection limit of 0.5 ng/L. This simple, rapid, and cost‐effective method was successfully applied to the preconcentration of polycyclic aromatic hydrocarbons from water samples. The developed method provided a high enrichment factor with good extraction efficiency (85–98%) and a relative standard deviation <10%.     

Efficient sample preparation method based on solvent‐assisted dispersive solid‐phase extraction for the trace detection of butachlor in urine and waste water samples

In this work, an efficient sample preparation method termed solvent‐assisted dispersive solid‐phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre‐concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 μL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 μg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent‐assisted dispersive solid‐phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples.     

Preparation of magnetic poly(vinylimidazole‐co‐divinylbenzene) nanoparticles and their application in the trace analysis of fluoroquinolones in environmental water samples

Nanosized spherical magnetic poly(vinylimidazole‐co‐divinylbenzene) particles were synthesized and used as a sorbent for the enrichment of trace fluoroquinolones (FQs) from environmental water samples. A suspension polymerization procedure was used to prepare the sorbent. The magnetic sorbent was characterized by SEM, transmission electron microscopy, elemental analysis, and FTIR spectroscopy. Analysis of enrofloxacin, marbofloxacin, fleroxacin, lomefloxacin, and sparfloxacin in environmental water samples by the combination of the magnetic sorbent and HPLC with diode array detection was selected as a paradigm for the practical application of the new adsorbent. Several extraction conditions, including desorption solvent, extraction and desorption time, pH value, and ionic strength in sample matrix, were optimized. Results showed that the new sorbent had high affinity for FQs and could be used to extract them effectively. Under the optimum conditions, low detection (S/N = 3) and quantification (S/N = 10) limits were achieved for the target analytes, within the ranges of 0.20–1.46 and 0.68–4.84 μg/L, respectively. Method repeatability was achieved in terms of intra‐ and interday precisions, indicated by the RSDs, which were both <10.0%. The method also showed good linearity, simplicity, practicality, and environmental friendliness for the extraction of FQs. Finally, the developed method was successfully applied to the determination of FQs in lake water, surface water, and reservoir water samples. Acceptable recoveries of spiked target compounds in these water samples were in the range of 52.1–104.5%.     

Core–shell SiO2‐coated Fe3O4 with a surface molecularly imprinted polymer coating of folic acid and its applicable magnetic solid‐phase extraction prior to determination of folates in tomatoes

A novel core–shell magnetic surface molecularly imprinted polymer with folic acid as a template was successfully synthesized by the sol–gel method. To generate Lewis acid sites in the silica matrix for the interaction of the metal coordinate with the template, 3‐aminopropyltriethoxysilane was used as a functional monomer, tetraethyl orthosilicate as a cross‐linker, and aluminum ions as a dopant. The magnetite encapsulated by the silica shell plays an important role as a magnetic‐coated polymer. The synthesized product was characterized by powder X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and FTIR and UV/Vis spectroscopy. The powder X‐ray diffraction patterns, FTIR and UV/Vis spectra confirmed the characteristics of the as‐prepared silica coated magnetite and folic acid molecularly imprinted polymer. It was successfully applied for magnetic solid‐phase extraction prior to the determination of folates in tomato samples using high‐performance liquid chromatography with photodiode array detection. The detection limit of the proposed method was 1.67 μg/L, and results were satisfactory, with a relative standard deviation of < 3.94%.     

Facile synthesis of poly(ionic liquid)‐bonded magnetic nanospheres as a high‐performance sorbent for the pretreatment and determination of phenolic compounds in water samples

Poly(ionic liquid)‐bonded magnetic nanospheres were easily synthesized and applied to the pretreatment and determination of phenolic compounds in water samples, which have detrimental effects on water quality and the health of living beings. The high affinity of poly(ionic liquid)s toward the target compounds as well as the magnetic behavior of Fe₃O₄ were combined in this material to provide an efficient and simple magnetic solid‐phase extraction approach. The adsorption behavior of the poly(ionic liquid)‐bonded magnetic nanospheres was examined to optimize the synthesis. Different parameters affecting the magnetic solid‐phase extraction of phenolic compounds were assessed in terms of adsorption and recovery. Under the optimal conditions, the proposed method showed excellent detection sensitivity with limits of detection in the range of 0.3–0.8 ng/mL and precision in the range of 1.2–3.3%. This method was also applied successfully to the analysis of real water samples; good spiked recoveries over the range of 82.5–99.2% were obtained.     

Sol–gel coating of poly(ethylene glycol)‐grafted multiwalled carbon nanotubes for stir bar sorptive extraction and its application to the analysis of polycyclic aromatic hydrocarbons in water

Poly(ethylene glycol) grafted onto carboxyl‐terminated multi‐walled carbon nanotubes were prepared by the sol–gel technique as a stationary phase for stir bars. The analytical methodology included stir bar sorptive extraction with micellar desorption followed by liquid chromatography. Polycyclic aromatic hydrocarbons were used as the model compounds to evaluate the extraction performance. The extraction efficiency, for the determination of polycyclic aromatic hydrocarbons from water samples, was optimized based on a chemometrics approach. The effect of the experimental parameters on the extraction response was investigated and the optimum extraction conditions were selected. Under the optimum conditions, the proposed method showed a good linearity within the different ranges for different analytes (e.g. 0.05–500 ng/mL for phenanthrene), a square of the correlation coefficient was higher than 0.999, and an appropriate limit of detection in the range of 0.013–0.072 ng/mL. The recoveries in all cases were above 94%, with relative standard deviations below 2.4%.