Surfactant modified coconut husk fiber as a green alternative sorbent for micro-solid phase extraction of triazole fungicides at trace level in environmental water, soybean milk, fruit juice and alcoholic beverage samples.

In this work, micro-solid phase extraction using surfactant modified biosorbent was investigated for trace level determination of triazole fungicides prior to their analysis by high performance liquid chromatography. Coconut husk fiber (CHF) was selected as an effective biosorbent in the extraction process. Fourier transform infrared spectrometry, scanning electron microscopy and transmission electron microscopy methods were used to characterize the modified biosorbent. Various factors affecting the extraction efficiency of the proposed method were studied including the amount of coconut husk fiber biosorbent (0.1 g), kind and concentration of surfactant as a modifier (sodium dodecyl sulfate, 10 mmol L-1), kind and volume of desorption solvent (methanol, 150 µL), and extraction period (including vortex adsorption time, centrifugation adsorption time, vortex desorption time and centrifugation adsorption time approximately 10 min). Under the selected conditions, the calibration plot was found to be linear in the range of 9-300 µg L-1 with a coefficient for determination of greater than 0.99. The limits of detection and limits of quantification for the studied triazole fungicides were 3.00 and 9.00 µg L-1, respectively. Finally, the proposed method was successfully applied to determine triazole fungicides in environmental water, soybean milk, fruit juice and alcoholic beverage samples with acceptable recoveries obtained in the range of 67.0% to 105.0%.

Green application of surfactant modified silica as effective sorbent for extraction and preconcentration of sulfonamide residues in environmental water and honey samples.

Micro-solid phase extraction (µ-SPE) using surfactant coated silica for extraction and preconcentration of sulfonamide residues at trace levels in environmental water and honey samples prior their analysis by high performance liquid chronatography coupled with photodiode array detector (HPLC-PDA). The sample solution were dispersed in a small amounts of solid sorbent by vacuum manifold for sample preparation, and extraction occurred by adsorption in a short time. Finally, the analytes were subsequently desorbed using an appropriate solvent. The pure and coated silica were physicochemically and morphologically characterized by nittrogen (N2) sorptions analyses, and transmission electron microscopy (TEM). Parameters influencing extraction efficiency, such as amount of sorbent, kind, concentration and volume of surfactant, and kind and volume of desorption solvent, were investigated. The optimum conditions of the proposed method, were mixed standard/sample solution (10 mL), 0.4 g silica, 0.03 M CTAB (150 µL), and 500 µL methanol (as elution solvent). The proposed method, under optimal conditions, showed excellent linearity in different ranges (9-300 µg L-1, the a coefficient of determination (R2) of greater than 0.99), good repeatability (RSD < 6.72 %), good sensitivity (LODs in the range of 1 to 3 µg L-1), high enrichment factor (5.63-13.33), and acceptable relative recoveries (61.0-121.4 %). The developed µ-SPE method was applied to analyze sulfonamide residues in water and honey samples with relative recoveries of 60.9-119.4 % were obtained. This alternative method is simple and is also environmentally friendly which assessed using Analytical Eco-scale and Analytical GREEnness metric (AGREE).

Preconcentration of Heterocyclic Aromatic Amines in Edible Fried Insects Using Surfactant-Assisted Hydrophobic Deep Eutectic Solvent for Homogeneous Liquid-Liquid Microextraction prior to HPLC.

Thermal processing techniques are often accompanied by the production of many harmful compounds such as heterocyclic aromatic amines (HAAs). To protect human health, an efficient and environmentally friendly method, namely, homogeneous liquid-liquid microextraction (HLLME), was investigated. This method is based on a surfactant-assisted hydrophobic deep eutectic solvent for the determination of HAAs in edible fried insect samples prior to their analysis by high-performance liquid chromatography coupled with UV detection. A hydrophobic deep eutectic solvent (as extraction solvent) was synthesized using decanoic acid as a hydrogen bond donor and tetrabutylammonium bromide (TBABr) as a hydrogen bond acceptor and then characterized by Fourier transform infrared (FTIR) spectroscopy. The surfactant was used as the emulsifier and induces mass transfer, resulting in an increasing extraction efficiency of the proposed method. Various factors affecting the extraction performance were investigated and optimized. A matrix-match calibration method was used to analyze HAAs in high heat-treated edible fried insect samples. Under optimized conditions, the proposed method showed good linearity (R2 ≥ 0.99) with satisfactory limits of detection and satisfactory reproducibility with relative standard deviation of less than 10.0%. Furthermore, the procedure greenness was assessed using the Analytical Eco-Scale. This paper represents the first application of HLLME based on a surfactant-assisted hydrophobic deep eutectic solvent to analyze HAAs in edible fried insect samples.

Green hairy basil seed mucilage biosorbent for dispersive solid phase extraction enrichment of tetracyclines in bovine milk samples followed by HPLC analysis.

Unmodified hairy basil seed mucilage (Ocimum basilicum L.), with attractive features as structural functionality and adsorption capacity, was employed as a green biosorbent for dispersive solid phase extraction and enrichment of oxytetracycline, tetracycline, and doxycycline before quantitation by HPLC-UV for the first time. Hairy basil crushed seed increased the contacting surface area and was completely dispersed in the sample solution to extract tetracyclines under acidic condition with the assistance of ultrasonic waves. The analytes in the extraction phase were separated on a C18 column under isocratic condition with a mobile phase consisted of acetonitrile and trifluoroacetic acid. Influence of chemical and physical variables on the extraction efficiency of the developed method was investigated and optimized systematically. Under the optimal condition of all experimental parameters, good linear ranges were obtained at 15.0-500 µg L-1 for tetracyclines with determination coefficients more than 0.9994. Limits of detection (LODs) and limits of quantitation (LOQs) ranged 5.0-7.0 and 15.0 µg L-1, respectively. Relative standard deviations (RSDs) of the proposed method at 100 and 300 µg L-1 for TCs were less than 13 % and 10 %, respectively with percentage TC recoveries from spiked standard ranging 83.1-109.9 %. This simple, reliable, cost-effective, and environmentally friendly method was successfully applied for the analysis of tetracycline residues in milk. The greenness of the proposed method was assessed using the Analytical Eco-Scale and AGREE protocol.

Trace-Level Determination of Triazole Fungicides Using Effervescence-Assisted Liquid-Liquid Microextraction Based on Ternary Deep Eutectic Solvent Prior to High-Performance Liquid Chromatography.

A simple and sensitive preconcentration method, namely, effervescence-assisted liquid-liquid microextraction based on the ternary deep eutectic solvent method, was developed for enrichment of triazole fungicide residues prior to their determination by high-performance liquid chromatography coupled with UV detection. In this method, a ternary deep eutectic solvent (as extractant) was prepared by combination of octanoic acid, decanoic acid, and dodecanoic acid. The solution was well dispersed with sodium bicarbonate (as effervescence powder) without using auxiliary devices. In order to obtain relatively high extraction efficiency, analytical parameters were investigated and optimized. Under optimum conditions, the proposed method showed good linearity within the range of 1-1000 µg L-1 with a coefficient for determination (R2) greater than 0.997. The low limits of detection (LODs) were in the range of 0.3-1.0 µg L-1. The precisions were assessed from the relative standard deviations (RSDs) of retention time and peak area obtained from intra- (n = 3) and inter-day (n = 5 × 5) experiments, which were greater than 1.21 and 4.79%, respectively. Moreover, the proposed method provided high enrichment factors ranging from 112 to 142 folds. A matrix-match calibration method was used for analysis of real samples. Finally, the developed method was successfully applied for determination of the triazole fungicide in environmental water (near agricultural area), honey, and bean samples, and it represents a promising alternative method for analysis of triazoles. The recoveries of the studied triazoles were obtained in the range of 82-106% with an RSD less than 4.89.

Efficient analyses of triazole fungicides in water, honey and soy milk samples by popping candy-generated CO2 and sugaring-out-assisted supramolecular solvent-based microextraction prior to HPLC determinations.

An enrichment method, namely popping candy-generated CO2 and sugaring-out-assisted supramolecular solvent-based microextraction (PGS-SUPRA), was investigated for the determination of triazole fungicide residues in water, honey and soy milk samples. The extraction process was carried out by adding popping candies into a centrifuge tube. Consequently, rapid dispersion and mass transfer of extractants can be achieved without using dispersants and auxiliary devices, and therefore, the extraction efficiency increased. The extraction parameters affecting the efficiency of the developed method were investigated. The presented method was then analysed by high-performance liquid chromatography. Under the selected condition, the wide linearity of triazole fungicides after preconcentration by the proposed microextraction method ranged from 30 to 1000 µg L-1 for triadimefon and from 90 to 1000 µg L-1 for myclobutanil, tebuconazole and hexaconazole, with a coefficient for determination (R 2) greater than 0.992. The limits of detection (LODs) and limits of quantitation (LOQs) were in the range of 10-30 µg L-1 and 30-90 µg L-1, respectively. The precisions were assessed from the relative standard deviations (RSDs) of the retention time and peak area obtained from intra- (n = 3) and inter-day (n = 3 × 5) experiments, and were greater than 1.66% and 13.52%, respectively. Moreover, the proposed method provided high enhancement factors (EnFs) ranging from 14 to 51 folds. This technique has been prosperously applied for the extraction of fungicide residues in water, honey and soy milk samples with a recovery within the range of 60-114%. Overall, the developed method was found to be advantageous as compared with other sample preparation methods.

One-pot co-extraction of dispersive solid phase extraction employing iron-tannic nanoparticles assisted cloud point extraction for the determination of tetracyclines by high-performance liquid chromatography.

Iron-tannic nanoparticles were used as a new adsorbent for dispersive solid phase extraction (DSPE) synergized with cloud point extraction (CPE) to enrich four tetracyclines (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) prior to high-performance liquid chromatographic determination. DSPE and CPE were performed simultaneously in a one-pot co-extraction to form iron-tannic nanoparticles in-situ and pre-concentrate the tetracyclines. The parameters affecting the extraction efficiency were investigated. Using the optimal parameters, linear calibrations ranging from 2.63 to 1000 ng mL-1 were obtained, with determination coefficients greater than 0.996. The limit of detection was found to be 1.06-3.19 ng mL-1, while the limit of quantification was 2.63-10.65 ng mL-1. Precision was expressed as a relative standard deviation of less than 10%. The residues of the four tetracyclines in milk, eggs, honey, chicken liver, and chicken kidney samples were determined by the proposed method. The recoveries ranged from 79.3 to 107.1%. The results indicated that the proposed method was an alternative method for the extraction and pre-concentration of tetracyclines with high extraction and enrichment efficiency. In addition, it promoted rapidity and environmental friendliness.

Simultaneous Preconcentration of Triazole Fungicide Residues Using In-Situ Coacervative Extraction Based on a Double-Solvent Supramolecular System Prior to High Performance Liquid Chromatographic Analysis.

An in situ coacervative extraction (IS-CAE) based on a double-solvent supramolecular system coupled to liquid-liquid microextraction is investigated for extraction and enrichment of triazole fungicides. The formation of a double-solvent supramolecular system was generated by in situ formation and used as an extraction solvent for the coacervative extraction method. No disperser solvent was required. This new double-solvent supramolecular system has a higher extraction ability than any of its components alone. The different factors that could affect the extraction capability were studied and optimized, including the type of double extractant and its volume, salt addition, vortex time, and centrifugation time. Under optimum extraction conditions, this method provides high enrichment factors (EFs) of 73-318 with low limits of detection (LODs) of 0.3-1 µg L-1 and limits of quantitation (LOQs) of 1-3 µg L-1. In addition, the proposed method was prosperously applied for the determination of triazole fungicides in water, fruit juice, and soy milk samples.

Modified Peanut Shell as an Eco-Friendly Biosorbent for Effective Extraction of Triazole Fungicide Residues in Surface Water and Honey Samples before Their Determination by High-Performance Liquid Chromatography.

An eco-friendly sample preparation method that is based on the use of a modified peanut shell as an efficient biosorbent for the extraction of triazole residues before their analysis by high-performance liquid chromatography was reported. The four triazole fungicides were separated on a Purospher STAR RP-18 endcapped (4.6 × 150 mm, 5 µm) column with a mobile phase of 50% (v/v) acetonitrile at a flow rate of 1.0 mL min-1 and detection wavelength set at 220 nm. Peanut shells modified by didodecyldimethylammonium bromide were selected as an effective biosorbent material in the microextraction method. Scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to characterize the biosorbent. The effect of dominant parameters on the proposed microextraction method including the amount of sorbent, kind and concentration of surfactant, sodium hydroxide concentration, kind and amount of salt, sample volume, adsorption time, kind and volume desorption solvent, and desorption time was studied. Under the optimum condition, a good analytical performance for the proposed microextraction method was obtained with a wide linear range within the range of 9-1000 µg L-1, and low limits of detection (0.03 µg L-1 for all analytes) were obtained. Enrichment factors were achieved within the range of 30-51. The intra and interday precision values were evaluated in terms of percentage relative standard deviations (%RSD) and were less than 0.09 and 5.34% for the retention time and peak area, respectively. The proposed microextraction methods were used for extraction and analysis of triazole fungicides in water and honey samples. The recoveries in a satisfactory range of 70.0-118.8% were obtained.

An In Situ Formation of Ionic Liquid for Enrichment of Triazole Fungicides in Food Applications Followed by HPLC Determination.

An in situ formation of ionic liquid was used for preconcentration of four triazole fungicides in food samples. The microextraction method was used for the first time in the literature for preconcentration of triazole fungicides. In the developed method, tributylhexadecylphosphonium bromide ([P44412]Br) and potassium hexafluorophosphate (KPF6) were used for the formation of hydrophobic ionic liquid. After centrifugation, the fine microdroplets were produced in one step, providing the extraction step in a quick and environmentally friendly manner. The functional group of the hydrophobic ionic liquid was investigated using FT-IR. Various extraction parameters were studied and optimized. In the extraction method, 0.01 g of [P44412]Br and 0.01 g of KPF6, centrifugation at 4500 rpm for 10 min were used. The optimized technique provided a good linear range (90-1000 µg L-1) and high extraction recovery, with a low limit of detection (30-50 µg L-1). Methods for the proposed in situ formation of ionic liquid were successfully applied to honey, fruit juice, and egg matrices. The recoveries were obtained in a satisfactory range of 62-112%. The results confirmed the suitability of the proposed microextraction method for selective extraction and quantification of triazole fungicides.

In-Situ Formation of Modified Nickel-Zinc-Layered Double Hydroxide Followed by HPLC Determination of Neonicotinoid Insecticide Residues.

A single-step preconcentration procedure using the in-situ formation of modified nickel-zinc-layered double hydroxides (LDHs) prior to high-performance liquid chromatography (HPLC) is investigated for the determination of neonicotinoid insecticide residues in honey samples. The LDHs could be prepared by the sequential addition of sodium hydroxide, sodium dodecyl sulfate, nickel nitrate 6-hydrate and zinc nitrate 6-hydrate, which were added to the sample solution. The co-precipitate phase and phase separation were obtained by centrifugation, and then the precipitate phase was dissolved in formic acid (concentrate) prior to HPLC analysis. Various analytical parameters affecting extraction efficiency were studied, and the characterization of the LDHs phase was performed using Fourier-transformed infrared spectroscopy and scanning electron microscopy. Under optimum conditions, the limit of detection of the studied neonicotinoids, in real samples, were 30 µg L-1, for all analytes, lower than the maximum residue limits established by the European Union (EU). The developed method provided high enrichment, by a factor of 35. The proposed method was utilized to determine the target insecticides in honey samples, and acceptable recoveries were obtained.

An Eco-Friendly Hydrophobic Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Neonicotinoid Insecticide Residues in Water, Soil and Egg Yolk Samples.

A green, simple and sensitive hydrophobic DES-based dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography (HPLC) was developed for the analysis of neonicotinoid insecticide residues in various samples. A hydrophobic deep eutectic solvent (DES) was synthesized using decanoic acid as a hydrogen bond donor and tetrabutylammonium bromide (TBABr) as a hydrogen bond-acceptor. DESs were synthesized and characterized by Fourier transform-infrared (FTIR) spectroscopy. Two disperser solvents were substituted with surfactants and acetonitrile, which could afford more effective emulsification and make the extraction relatively greener. The hydrophobic DES extraction phase occurred 10 min after centrifugation, being easy to be collected for analysis. Several parameters were investigated and optimized. Under the optimum condition, the calibration curve of this method was linear in the range of 0.003-1.0-µg·mL-1, with a correlation coefficient (R2) higher than 0.99 and a good repeatability, with the relative standard deviations (RSDs) were less than 5.00%. The limits of detection were in the range of 0.001-0.003 µg·mL-1; the limits of quantitation were in the range of 0.003-0.009 µg·mL·mL-1. Finally, the presented method was implemented to determine the neonicotinoid insecticide residues in water, soil, egg yolk samples and acceptable recoveries were obtained.

ß-Cyclodextrin Assisted Liquid-Liquid Microextraction Based on Solidification of the Floating Organic Droplets Method for Determination of Neonicotinoid Residues.

An efficient and environment-friendly microextraction method, namely, ß-cyclodextrin assisted liquid-liquid microextraction, based on solidification of the floating organic droplets method coupled with HPLC is investigated for the sensitive determination of trace neonicotinoid pesticide residues. In this method, ß-cyclodextrin is used as a disperser solvent, while 1-octanol is selected as an extraction solvent. ß-cyclodextrins was found to decrease interfacial tension and increase the contact area between the organic and water phases with the help of centrifugation. A cloudy solution was rapidly formed and then centrifuged to complete phase separation. Various key parameters influencing extraction efficiency were systematically investigated and optimized; they include salt addition, concentration of ß-cyclodextrin, and volume of extraction solvent (1-octanol). Under optimum conditions, good linearity was obtained with coefficient for determination (R2) greater than 0.99. A low limit of detection, high enrichment factor, and good recovery (83 - 132) were achieved. This proves that the proposed method can be applied to determine trace neonicotinoid pesticide residues in natural surface water samples.

Magnetic Stirring Assisted Demulsification Dispersive Liquid⁻Liquid Microextraction for Preconcentration of Polycyclic Aromatic Hydrocarbons in Grilled Pork Samples.

A simple microextraction method, magnetic stirring assisted demulsification dispersive liquid⁻liquid microextraction, for preconcentration of five polycyclic aromatic hydrocarbons (fluorene, phenanthrene, anthracene, fluoranthrene, and pyrene) was investigated prior to analysis by high performance liquid chromatography. In this method, a mixture of extraction solvent and disperser solvent was rapidly injected into sample solution. The magnetic stirrer agitator aided the dispersion of the extraction solvent into the sample solution. After the formation of an emulsion, the demulsifier was added, resulting in the rapid separation of the mixture into two phases. No centrifugation step was required. Several parameters affecting the extraction efficiency of the proposed method were studied, including addition of salt, kind and volume of extraction solvent, volume of demulsifier solvent, and extraction times. Under the optimum conditions, high enrichment factor, low limit of detections (LODs) and good precision were gained. The proposed method was successfully applied to analysis of polycyclic aromatic hydrocarbon residues in grilled pork samples.

Ultrasonically Modified Amended-Cloud Point Extraction for Simultaneous Pre-Concentration of Neonicotinoid Insecticide Residues.

An effective pre-concentration method, namely amended-cloud point extraction (CPE), has been developed for the extraction and pre-concentration of neonicotinoid insecticide residues. The studied analytes including clothianidin, imidacloprid, acetamiprid, thiamethoxam and thiacloprid were chosen as a model compound. The amended-CPE procedure included two cloud point processes. Triton™ X-114 was used to extract neonicotinoid residues into the surfactant-rich phase and then the analytes were transferred into an alkaline solution with the help of ultrasound energy. The extracts were then analyzed by high-performance liquid chromatography (HPLC) coupled with a monolithic column. Several factors influencing the extraction efficiency were studied such as kind and concentration of surfactant, type and content of salts, kind and concentration of back extraction agent, and incubation temperature and time. Enrichment factors (EFs) were found in the range of 20⁻333 folds. The limits of detection of the studied neonicotinoids were in the range of 0.0003⁻0.002 µg mL−1 which are below the maximum residue limits (MRLs) established by the European Union (EU). Good repeatability was obtained with relative standard deviations lower than 1.92% and 4.54% for retention time (tR) and peak area, respectively. The developed extraction method was successfully applied for the analysis of water samples. No detectable residues of neonicotinoids in the studied samples were found.

Preconcentration of Trace Neonicotinoid Insecticide Residues Using Vortex-Assisted Dispersive Micro Solid-Phase Extraction with Montmorillonite as an Efficient Sorbent.

In this work, we investigated montmorillonite for adsorption of neonicotinoid insecticides in vortex-assisted dispersive micro-solid phase extraction (VA-d-µ-SPE). High-performance liquid chromatography with photodiode array detection was used for quantification and determination of neonicotinoid insecticide residues, including thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid. In this method, the solid sorbent was dispersed into the aqueous sample solution and vortex agitation was performed to accelerate the extraction process. Finally, the solution was filtered from the solid sorbent with a membrane filter. The parameters affecting the extraction efficiency of the proposed method were optimized, such as amount of sorbent, sample volume, salt addition, type and volume of extraction solvent, and vortex time. The adsorbing results show that montmorillonite could be reused at least 4 times and be used as an effective adsorbent for rapid extraction/preconcentration of neonicotinoid insecticide residues. Under optimum conditions, linear dynamic ranges were achieved between 0.5 and 1000 ng mL-1 with a correlation of determination (R²) greater than 0.99. Limit of detection (LOD) ranged from 0.005 to 0.065 ng mL-1, while limit of quantification (LOQ) ranged from 0.008 to 0.263 ng mL-1. The enrichment factor (EF) ranged from 8 to 176-fold. The results demonstrated that the proposed method not only provided a more simple and sensitive method, but also can be used as a powerful alternative method for the simultaneous determination of insecticide residues in natural surface water and fruit juice samples.

Ionic Liquid-Assisted Liquid-Liquid Microextraction based on the Solidification of Floating Organic Droplet in Sample Preparation for Simultaneous Determination of Herbicide Residues in Fruits.

An ionic liquid-assisted liquid-liquid microextraction based on the solidification of floating organic droplet (ILSFODLLME) was investigated for analysis of four herbicide residues (i.e. simazine, atrazine, propazine, and linuron) by high performance liquid chromatography. For ILSFOD-LLME, the optimal extraction conditions were 5% w/v Na2SO4, 30 µL [C4MIM][PF6]RTIL, 100 µL of 1-octanol, ultrasonication time 30 s and centrifugation at 5000 rpm for 5 min. Under the optimal conditions, linearity was obtained within the range of 0.1-1000 µg kg-1, with the correlation coefficients greater than 0.999. The high enrichment factors of the target analytes were in the range of 64.5-139.9 and low limit of detection could be obtained. A modified QuEChERS was applied for fruit sample preparation before analysis. Matrix effects were also investigated using matrix matched standards for construction of the calibration graph. The proposed method has been successfully applied for extraction and preconcentration of herbicide residues in fruit samples, and good recoveries in the range of 87.32% to 99.93% were obtained.

A preconcentration method for analysis of neonicotinoids in honey samples by ionic liquid-based cold-induced aggregation microextraction.

A preconcentration approach based on ionic liquid-based cold-induced aggregation microextraction for determination of neonicotinoid insecticide residues in honey samples before high-performance liquid chromatographic analysis has been developed. Room temperature ionic liquid [C4MIM][PF6] (extraction solvent) and SDS (emulsifier) was used for extraction of the target analytes. The parameters affecting the extraction efficiency were optimized. The optimum microextraction conditions were 200µL room temperature ionic liquids [C4MIM][PF6] containing 0.05molL(-1) SDS, 0.75g sodium carbonate, vortex agitation speed of 1800rpm for 30s and centrifugation at 3500rpm for 10min. Under optimum conditions, the high enrichment factors of 200 could be obtained, leading to low limit of detection (0.01µgL(-1) for all analytes) with the relative standard deviations lower than 2.68% and 5.38% for retention time and peak area, respectively. Good recoveries for the spiked target neonicotinoids at three different concentrations of honey samples were obtained in 86-100% and relative standard deviations were lower than 8.1%. The results demonstrated that the proposed method can be used as an alternative powerful method for the simultaneous determination of the studied insecticides in real honey samples.

In-coupled syringe assisted octanol-water partition microextraction coupled with high-performance liquid chromatography for simultaneous determination of neonicotinoid insecticide residues in honey.

A simple and fast method namely in-coupled syringe assisted octanol-water partition microextraction combined with high performance liquid chromatography (HPLC) has been developed for the extraction, preconcentration and determination of neonicotinoid insecticide residues (e.g. imidacloprid, acetamiprid, clothianidin, thiacloprid, thiamethoxam, dinotefuran, and nitenpyram) in honey. The experimental parameters affected the extraction efficiency, including kind and concentration of salt, kind of disperser solvent and its volume, kind of extraction solvent and its volume, shooting times and extraction time were investigated. The extraction process was carried out by rapid shooting of two syringes. Therefore, rapid dispersion and mass transfer processes was created between phases, and thus affects the extraction efficiency of the proposed method. The optimum extraction conditions were 10.00 mL of aqueous sample, 10% (w/v) Na2SO4, 1-octanol (100µL) as an extraction solvent, shooting 4 times and extraction time 2min. No disperser solvent and centrifugation step was necessary. Linearity was obtained within the range of 0.1-3000 ngmL(-1), with the correlation coefficients greater than 0.99. The high enrichment factor of the target analytes was 100 fold and low limit of detection (0.25-0.50 ngmL(-1)) could be obtained. This proposed method has been successfully applied in the analysis of neonicotinoid residues in honey, and good recoveries in the range of 96.93-107.70% were obtained.

Successive determination of urinary bilirubin and creatinine employing simultaneous injection effective mixing flow analysis.

A novel four-channel simultaneous injection effective mixing flow analysis (SIEMA) system has been assembled for successive determination of bilirubin and creatinine in urinary samples. The chemical variables and physical parameters in the flow system were optimized for the enhancement of successive analytical performances. The interferences from urine matrices on the determination of bilirubin and creatinine were eliminated to dilute urine samples. The calibration graphs with the optimum conditions were achieved to be in 0.024-5.0 mg L(-1) for bilirubin and 2-100 mg L(-1) for creatinine. The relative standard deviations (RSDs) at 3 mg L(-1) of bilirubin and at 50 mg L(-1) of creatinine for 11 runs were 1.5 and 1.0%, respectively. The limits of detections (3σ of blank) for bilirubin and creatinine were 7 µg L(-1) and 0.6 mg L(-1), respectively. The sample throughput for stepwise detection was 22 h(-1). The proposed method was applied to the successive determination of bilirubin and creatinine in urine samples.