Performance Liquid Chromatography-diode Array Detection Research Articles

Novel polyvinyl alcohol/gum tragacanth molecularly imprinted-electrospun nanofibers as adsorbent for selective solid phase extraction of bisphenol A

A polyvinyl alcohol/gum tragacanth molecularly imprinted nanofiber fabricated by electrospinning (PVA/GT-MIN) was used as an efficient adsorbent for the solid phase extraction (SPE) of bisphenol A (BPA) in water samples. PVA and GT were functional polymers and BPA was the template for molecular imprinting. BPA was bound to the polymer matrix through hydrogen bonding. The SEM image of PVA/GT-MIN demonstrated a rough morphology with pores and a diameter of 501 nm. The data for the adsorption of BPA on PVA/GT-MIN fitted the Freundlich isotherm and pseudo-second-order kinetics models. The proposed SPE using PVA/GT-MIN coupled with high performance liquid chromatography-diode array detection presented good linearity from 50 μg/L–5 mg/L (R2 = 0.9999) and yielded a limit of detection of 21 μg/L. The PVA/GT-MIN was applied to extract bottled water for BPA analysis and recoveries were 93.1–97.7 % (RSDs ≤ 3.6 %). This study presents a novel, easily prepared PVA/GT-MIN adsorbent for the extraction of BPA in water.

Effects of different postharvest drying processes on flavonoid content and enzymatic activity of Styphnolobium japonicum (L.) Schott flowers for industrial and medicinal use

Traditionally, fresh S. japonicum flowers (SJF) and S. japonicum flowers buds (SJFB) are dried prior to further processing and use. Here, we investigated the ways in which drying techniques, including sun drying (SD), steam drying (STD), microwave drying (MD), hot air drying (HAD, 40 °C, 60 °C, 80 °C, 100 °C), and freeze drying (FD), alter the flavonoid composition of freshly-harvested SJF and SJFB. The flavonoid content of dried samples was determined by Ultra High Performance Liquid Chromatography-Diode Array Detector (UPLC-DAD). Overall, different drying techniques had significantly different effects on the RU content, ranging from 10.63 % (HAD-80 °C) to 34.13 % (HAD-100 °C) in SJF and from 18.91 % (HAD-100 °C) to 29.16 % (HAD-40 °C) and 30.53 % (SD) in SJFB. To clarify the mechanism by which drying affects the RU content of S. japonicum flowers, we studied the activity of a rutin-hydrolyzing enzyme (RHE) isolated from SJF and SJFB using multiple separation and assay methods. According to the Sodium Dodecyl Sulfate-Polyacrylamide Gel Electrophoresis (SDS-PAGE) results, the apparent molecular weight of the purified RHE was approximately 38 kDa. According to UPLC-DAD, RHE catalyzes the production of quercetin (QU) from rutin (RU), but not from other flavonoid glycosides. Drying fresh SJF and SJFB at low and high temperatures can inhibit RHE activity and prevent RU hydrolysis. Therefore, subjecting freshly-harvest SJF to HAD-100 °C, and freshly-harvest SJFB to SD or HAD-40 °C, can greatly increase the RU content. In particular, HAD is viable for large-scale application due to its simplicity and industrial feasibility.

Comparative Pharmacokinetic Study of Standard Astaxanthin and its Micellar Formulation in HealthyMale Volunteers.

Astaxanthin is a naturally occurring carotenoid with high anti-oxidant properties, but it is a very lipophilic compound with low oral bioavailability. This study was conducted to compare the pharmacokinetic parameters of a novel astaxanthin preparation based on micellar solubilization technology, NovaSOL® 400-mg capsules (Test product), and those of astaxanthin 400-mg capsules (reference product), after single oral dose administration to healthy male adults. A single oral dose (400 mg equivalent to 8 mg astaxanthin) of test and reference astaxanthin were administered with 240 mL of water to 12 volunteers according to crossover design, in two phases, with a washout period of 1week in between. Blood samples were collected at hourly intervals for the first 12 h, then at 24.0, 48.0, and 72.0 h after administration. Aliquots of plasma were centrifuged and the clear supernatant was injected into the high performance liquid chromatography-diode array detection (HPLC-DAD) system. Plasma concentration of astaxanthin versus time profiles were constructed, and the primary pharmacokinetic parameters, maximum concentration (Cmax), area under concentration time curve from time of administration (0) to time (t) [AUC0-t] or to infinity ∞, [AUC0-∞], half-life (T½) and time to reach Cmax (Tmax)were calculated. The test micellar astaxanthin reached a Cmax of 7.21 µg/ml after 3.67 h compared to only 3.86 µg/ml after 8.5 h for the reference native astaxanthin. Micellar formulation of astaxanthin is capable of producing a high concentration of astaxanthin in plasma in a shorter time, thereby expected to provide faster potential therapeutic efficacy.

Melamine sponges incorporated azo-linked porous organic polymer as adsorbent for extraction and determination of six B vitamins using pipette tip micro solid-phase extraction

A novel azo-linked porous organic polymer (AL-POP) was synthesized from caffeic acid and benzidine via an azo-coupling reaction and characterized by FTIR, SEM-EDS, BET, TGA, XRD and zeta potential analysis. AL-POPs were incorporated into melamine sponges and used for pipette tip micro solid-phase extraction (PT-MSPE) of six types of B vitamins (including thiamine, riboflavin, nicotinamide, pyridoxine, folic acid, and cyanocobalamin). After extraction, the samples were analyzed using high performance liquid chromatography-diode array detection (HPLC-DAD) system. The effect of AL-POP composition on the extraction efficiency (EE) of vitamins was investigated and benzidine to caffeic acid mol ratio of 1.5, 3.35 mmol of NaNO2, and reaction time of 8 h were selected as optimum conditions. The efficiency of the extraction process was improved by optimizing various parameters such as the amount of sorbent, pH and ionic strength of the sample, sample volume, number of sorption and desorption cycles, type of wash solvent, and type and volume of eluent solvent. Linearity (R2≥0.9987), Limit of detection (LOD) (11.88–18.97 ng/mL), limit of quantification (LOQ) (39.62–63.23 ng/mL), and enrichment factor (EF) (1.27–4.31) were obtained using calibration curves plotted under optimum conditions. Recovery values of these six B vitamins in the spiked multivitamin syrup samples varied from 80.01% to 108.35%, with a relative standard deviation (RSD) below 5.44%. Eventually, the optimized method was successfully used to extract and quantify the B vitamins in multivitamin syrup and non-alcoholic beer.

Quantification of phenolic compounds in dietary supplements and antioxidant activities

Dietary supplements (DS) are products that are recommended for the treatment of various health issues, especially during the global pandemic, and the accuracy of the labeling information of these supplements plays a significant role in human health. In this study, a novel high performance liquid chromatography-diode array detector (HPLC-DAD) method was developed and validated to determine the accuracy of the labeling information of commercial dietary supplements containing phenolic compounds (rutin, quercetin, and resveratrol). The mobile phase, flow rate, and column temperature were optimized. Validation studies were carried out to prove the validity of the developed method. The limit of detection (LOD) and limit of quantification (LOQ) values ​​of rutin, quercetin, and resveratrol were found in the range of 4.83-6.62 ng/mL and 16.09-22.07 ng/mL, respectively. Recoveries% were calculated in the range of 99.52-100.19% and 99.78-100.34% in the intra-day and inter-day analysis, respectively. The IC50 values of the dietary supplement extracts obtained by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) method ranged from 0.08 to 0.76 mg/mL. Total Antioxidant Capacity (TAC) values of DS1, DS2, DS3, DS4, DS5, measured employing the Cupric Reducing Antioxidant Capacity (CUPRAC) method, were found to be 0.09, 0.03, 0.10, 0.10 and 0.40 mmol trolox per gram of extract, respectively. KEY WORDS: Dietary supplement, HPLC-DAD, Phenolic compound, Antioxidant activity Bull. Chem. Soc. Ethiop. 2024, 38(4), 853-862. DOI: https://dx.doi.org/10.4314/bcse.v38i4.3

Application of continuous magnetic solid phase extraction in the extraction of tetracycline antibiotics from honey samples

This study aimed to develop a continuous magnetic solid phase extraction method in a narrow bore tube for the extraction of tetracycline antibiotics from honey samples before their determination with high performance liquid chromatography–diode array detector. In this work, a magnetic covalent organic framework is used as the sorbent. The extraction method is performed in a narrow bore tube by adding 25 mg of a magnetic sorbent prepared from melamine, barbituric acid, and Fe3O4 into the diluted honey sample solution. By using a magnet, the sorbent is moved up and down through the narrow bore tube for five times to improve extraction efficiency. After adsorption the analytes, they are eluted from the sorbent surface using 2,2–dimethoxypropane under vortexing. Then, by using a magnet, the eluent containing the extracted analytes are taken and evaporated with continuous flow of nitrogen. Finally, the residue containing the enriched analytes is reconstituted in microliter–level of mobile phase and injected into chromatographic system for quantitative analysis. Based on the outcomes, the method demonstrated good linearity (0.37–1000 ng g−1), high enrichment factors (175–203), good extraction recoveries (70–81 %), low LODs (0.11–0.18 ng g−1) and LOQs (0.37–0.60 ng g−1). The proposed method is effectively applied for quantification of tetracyclines in twenty–four honey samples. Considering the results, none of the honey samples was contaminated with the studied antibiotics. Regarding to the above–mentioned analytical advantages of the proposed method, its simplicity and rapidity, and green synthesis of the magnetic sorbent particles, the suggested method can be used as a routine method for the extraction of tetracyclines from honey samples.

Evaluation of some sulfonamide antibiotics residues in chicken meat samples using in-syringe counter current homogenous liquid–liquid extraction and magnetic deep eutectic solvent-based dispersive liquid–liquid microextraction and HPLC–DAD

A sample pretreatment method based on the combination of counter current salting-out homogenous liquid–liquid extraction and magnetic deep eutectic solvent-based dispersive liquid–liquid microextraction was developed and employed for the extraction of some sulfonamide antibiotics from chicken meat samples. For this purpose, first, a homogenous solution of acetonitrile and deionized water was passed through a syringe barrel filled sodium chloride and chicken meat sample. By doing so, the fine droplets of acetonitrile were produced and collected on the surface of solution. In the following, this phase containing the extracted analytes was taken and injected into deionized water after mixing with [Choline: 4-chlorophenol]+[FeCl4]- magnetic deep eutectic solvent. Then, the magnetic deep eutectic solvent droplets were separated in the presence of an external magnetic field and injected into high performance liquid chromatography-diode array detector for quantitative analysis. Based on the validation results, low limits of detection (0.15–0.24 ng g−1) and quantification (0.51–0.80 ng g−1), high extraction recovery (67–78 %), and good precision (relative standard deviations ≤ 5.7 %) were obtainable by using the offered method. Finally, the suggested method was employed for the quantification of the studied sulfonamide antibiotics in various chicken meat samples.

Preparation of ionic porous polymers for extraction of four phenolic endocrine disrupting chemicals from fish and water samples

In this paper, series of ionic polymers were synthesized by crosslinking alkyl quaternary ammonium salts with 1,4-bis(chloromethyl)benzene. Among them, hyper-crosslinked polymer fabricated with dodecyl dimethyl benzyl ammonium chloride (HCP-DD) as monomer delivered superior adsorption performance for endocrine disrupting chemicals (EDCs). The adsorption mechanism mainly includes π-π stacking, hydrophobic and electrostatic interaction. With HCP-DD as solid phase extraction sorbent, a high performance liquid chromatography-diode array detection method was developed for the detection of four phenolic EDCs in water and fish samples. The detection limits of the method were 0.005–0.02 ng mL−1 for water samples and 3–30 ng g−1 for fish samples. The recoveries of EDCs in water samples and fish samples were 80–119% and 81.3–117% (relative standard deviations <4.4%), respectively. The study not only provides a route for preparation ionic porous polymers, but also highlights the applications of ionic polymers as efficient adsorbent to enrich organic pollutants.

Green synthesis of azo-linked porous organic polymer for enrichment of nitroimidazoles from water, shrimp and Basa fish

Reliable monitoring of nitroimidazoles (NDZs) is of great significance to public health. Herein, an azo-linked porous organic polymer (Res-POPs) was prepared by green synthesis method using natural resveratrol as monomer for the first time. Using Res-POPs as sorbent, a facile method coupling solid-phase extraction with high performance liquid chromatography-diode array detection was developed for effective detecting NDZs. The method achieved good linearities (0.06 ∼ 100 ng mL−1 for water, 1.8 ∼ 200 ng g−1 for shrimp, and 1.5 ∼ 200 ng g−1 for Basa fish) with determination coefficients above 0.995, low detection limits (0.02 ∼ 0.05 ng mL−1, 0.60 ∼ 1.00 ng g−1 and 0.50 ∼ 0.90 ng g−1 for water, shrimp and Basa fish), high method recovery (85 %∼114 %) and relative standard deviations below 8.2 %. The results demonstrated the superiority and the promising potential of the established method for detection of NDZs compared with the reported method.

Development of a dispersive liquid-liquid microextraction method for the determination of plastic additives in seawater.

A method using dispersive liquid-liquid microextraction (DLLME) prior to high performance liquid chromatography-diode array detection (HPLC-DAD) was developed to determine seven additives from the plastics industry (butylated hydroxytoluene, diisodecyl phthalate, irgafos 168, lawsone, quercetin, triclosan and vitamin E) in seawater samples. These compounds can reach seawater due to direct discharge from wastewater treatment plants and leaching from plastics and microplastics. The extraction was performed using 25 mL of seawater, 500 μL of 1-octanol (extraction solvent) and a stirring step instead of dispersive solvent. Additive concentrations were determined by LC-DAD on a C18 column with a mobile phase of acetonitrile and phosphoric acid aqueous solution (pH 3.5) by gradient elution. The analytical recoveries ranged from 82 to 93% for all compounds, except for lawsone (60%). Repeatability and intermediate precision were adequate with RSD < calculated values following the Horwitz equation at the concentration levels evaluated (0.06 and 0.24 mg L-1). All additives exhibited linear matrix calibration curves (R2 > 0.99). Detection limits ranged from 0.009 to 0.028 mg L-1 and quantification limits ranged from 0.027 to 0.084 mg L-1. Finally, the application of the method to real samples verified the method as accurate and applicable to seawater.

A quality evaluation method of lotus leaf based on its lipid lowering components using QAMS and chemometrics

IntroductionLotus leaf has long been used as food and medicine in China and is well-known for its lipid-lowering effects. However, there is a lack of a comprehensive quality evaluation for lotus leaf due to the absence of consideration of the correlation between various components and their efficacy. ObjectivesThis study aims to find out the key bioactive components that can be used for quality evaluation of lotus leaf on lipid-lowering effect. MethodsThirteen compounds were characterized in the lotus leaf using ultra-high- performance liquid chromatography-time-of-fight mass spectrometry (UPLC-Q-TOF-MS). Five alkaloids and four flavonoids were identified according to their lipid-lowering activities reported in literatures. Then, the contents of these nine components were analyzed in 39 batches of lotus leaves growing in different locations using high performance liquid chromatography diode-array detector (HPLC-DAD), and further evaluated by quantitative analysis of multi-components by single marker (QAMS) and chemometrics. The anti-adipogenic activity of lotus leaves were evaluated for their inhibitory effect on the PPARγ expression by luciferase assay. ResultsThe 39 batches were clustered into two regions, the north and the south, based on the contents of these components. Three alkaloids, nuciferine, N-nornuciferine, and asimilobine, and three flavonoids, astragalin, hyperoside, and trifolioside, were found to serve as the key factors behind the region differences. Their contents were higher in Guangchang County of Jiangxi Province than other habitat locations. Moreover, the luciferase assay combined with chemometrics showed that these components were positively correlated with lipid-lowering activity of lotus leaf. ConclusionsThree alkaloids and three flavonoids were screened out and could be used as key compounds for quality evaluation of lotus leaf on lipid-lowering effect.

Pentaclethra macrophylla leaves reduce blood glucose level, improve sexual behavior and modulate critical enzymes associated with diabetes-erectile dysfunction morbidity in rats.

This research work studied the phenolic composition of Pentaclethra macrophylla (PM), the inclusion of dietary supplementation of PM leaves on sexual functions and its connection to inhibit enzymes (arginase and phosphodiesterase-5) and nitric oxide level, linked to type 2 diabetes-induced erectile dysfunction in rats. Gallic acid, chlorogenic and ellagic acids, Kaempferol, and epicatechin etc. was spotted with High performance liquid chromatography-diode array detector from PM extract. Twenty-five (25) rats were used for the study. Five rats were placed with basal diet; diets not supplemented with PM leaves (normal rat group) while twenty rats were made diabetic by feeding them with high fat diet for two weeks, prior to single injection with 35 mg/kg of streptozotocin (STZ). After checking with glucometer, experimental animals with blood glucose level >250 mg/dL were accepted as diabetic. The diabetic rats were subsequently divided into four groups of five rats each (n=5). The diabetic rats were placed on basal diet, or diets supplemented with PM leaves (10 % or 5 % inclusion) or sildenafil citrate (SC). The result revealed that PM supplemented diets caused significant (p<0.05) reduction in blood glucose level, and augmented erectile function by inhibiting arginase and PDE5 activities as well as enhancing nitric oxide level. In conclusion, dietary inclusion of PM leavescould serve as a potent nutraceutical source in hyperglycemia induced erectile dysfunction management.

Hydroxyl and carboxyl group functionalized conjugated microporous nanomaterial as adsorbent for the solid-phase extraction of phenolic endocrine disrupting chemicals from freshwater fish samples

Endocrine disruption chemicals (EDCs) in food can seriously harm human health. In this study, a hydroxyl and carboxyl group functionalized conjugated microporous nanomaterial (CMP) was prepared by Friedel-Crafts reaction and used as solid-phase extraction (SPE) adsorbent. A functionalized CMP based SPE combined with high performance liquid chromatography-diode array detection was built for the determination of phenolic EDCs from nine fish samples. The extraction conditions were optimized by both single factor and response surface methodology (Box-Behnken Design). The established method performed well in terms of the response linearity (in the range of 0.50–100 ng g−1 with coefficient of determination larger than 0.9942), limits of detection (0.15–0.30 ng g−1, S/N of 3), limits of quantification (0.50–1.00 ng g−1, S/N = 10), method recoveries (78.4–121 %) and repeatability (relative standard deviation < 11 %). It can be used as an efficient method to detect trace phenolic EDCs in real fish samples.

Phenolic composition and correlation with antioxidant properties of various organic fractions from Hertia cheirifolia extracts

Hertia cheirifolia L. is a medicinal plant that has been used for a long time in folk Mediterranean medicine. The aim of the present study was to analyze and compare the phenolic profile and the antioxidant potential of organic fractions from H. cheirifolia extracts. Crude methanolic extracts were firstly prepared from the different parts of the plant. Then four different organic fractions were obtained by fractioning each extract, using different solvents with increasing polarity (hexane, chloroform, and ethyl acetate). The Phenolic content was analyzed using a UV–Vis colorimetric methods followed by a qualitative and quantitative analysis by high performance liquid chromatography-diode array detector (HPLC-DAD) system. After that, the antioxidant potential of the different organic fractions was evaluated using DPPH and ABTS free radical scavenging assays, reducing power of iron (FRAP) and inhibition of β-carotene oxidation tests. Our results revealed that ethyl acetate fractions (EA) contained the highest content of total phenolics (100–250 mg GAE/g). Indeed, the ethyl acetate fraction from the flower extract (EA-F) displayed the lowest IC50 values for the scavenging of DPPH and ABTS free radicals (38.83 ± 0.34 µg/ml and 23.76 ± 0.11 µg/ml, respectively). Also, the strongest iron reducing power (2628.87 ± 16.47 µmol Fe2+Eq/ml) and the best rate of inhibition of the β-carotene oxidation (58.91 ± 5.79 %) were recorded. In sum, the present study suggests that, the organic fractions from H. cherifolia are potential natural antioxidants and this is probably related to their phenolics content and structure.

Characterisation of acylated anthocyanins from red cabbage, purple sweet potato, and Tradescantia pallida leaves as natural food colourants by HPLC-DAD-ESI(+)-QTOF-MS/MS and ESI(+)-MSn analysis.

Anthocyanins in red cabbage, sweet potato, and Tradescantia pallida leaves were characterised. A total of 18 non-, mono-, and diacylated cyanidins was identified in red cabbage by high performance liquid chromatography-diode array detection coupled to high-resolution and multi-stage mass spectrometry. Sweet potato leaves contained 16 different cyanidin- and peonidin glycosides being predominantly mono- and diacylated. In T. pallida leaves, the tetra-acylated anthocyanin tradescantin prevailed. The large proportion of acylated anthocyanins resulted in a superior thermal stability during heating of aqueous model solutions (pH 3.0) coloured with red cabbage and purple sweet potato extracts as compared to that of a commercial Hibiscus-based food dye. However, their stability was still outperformed by that of the most stable Tradescantia extract. Comparing vis spectra from pH 1-10, the latter had an additional, uncommon absorption maximum at approx. 585nm at slightly acidic to neutral pH values, yielding intensely red to purple colours.

Hydrophobic natural deep eutectic-solvent bar microextraction combined with HPLC-DAD for determination of urinary 1-hydroxypyrene of smokers

1-hydroxypyrene (1-OHP) is a metabolite of pyrene, which is a type of polycyclic aromatic hydrocarbons (PAHs) found in tobacco smoke and preferred use as a biomarker to determine exposure to PAHs from smoking. This paper reports a new and simple microextraction technique for 1-hydroxypyrene (1-OHP) determination in smokers' urines using hydrophobic natural deep eutectic solvent (HNDES) in developing solvent bar microextraction (SBME) and high performance liquid chromatography-diode array detection (HPLC-DAD). Terpenoids based-HNDES using various ratios of (thymol/menthol) were synthesized and investigated as extraction solvents. The variables affecting HNDE-SBME steps were optimized by response surface methodology (RSM) based on central composite design (CCD). Under the optimum conditions, the calibration graph of spiked urine samples was linear in the range of 0.3–25.0 μg L−1 1-OHP with a correlation coefficient of 0.999. Additionally, the detection limit, quantitation limit, and extraction recovery were found to be 0.06 μg L−1, 0.22 μg L−1, and ≥100%, respectively. In comparison with referenced methods and based on the satisfactory results of applications, the proposed method can be considered as a potential method for the detection of urinary 1-OHP for health risk assessment of PAHs exposures.

Fast surface floating organic droplets based dispersive liquid‐liquid microextraction for trace enrichment of multiclass pesticide residues from different fruit juice samples followed by high performance liquid chromatography–diode array detection analysis

AbstractThis study was designed to enable the development of a simple, fast, and environmentally friendly analytical technique utilizing dispersive liquid‐liquid microextraction based on surface floating organic droplets for selective and quantitative enrichment of trace level pesticide contaminants from different fruit juice samples for subsequent detection by high performance liquid chromatography, combined with a diode array detector. The selective extraction was necessitated in order to isolate the seven multiclass pesticide residues frequently occurring in fruit juice samples. The effects of experimental parameters such as pH of sample solution, type and volume of extraction and dispersive solvents, ionic strength and extraction time were optimized. The optimized method was validated using spiked blank sample and satisfactory results for accuracy, with recoveries ranging from 87.23% to 99.45%, with %relative standard deviation between 1.37 and 8.39, precision in terms of %relative standard deviation ≤ 10.78 and linearity at concentration levels from 3 to 1500 ng/ml, which corresponded with correlation coefficients ≥ 0.998. The limits of detection and the limits of quantification were ranged from 1.3×10−2 to 5.3×10−2 and 4.2×10−2 to 1.8×10−1 μg/L, respectively. At the end, the method was successfully applied to analyze real fruit juice samples and target analytes were not detected in real samples.

Determination of metronidazole and clarithromycin in plasma samples using surfactant-modified amorphous carbon-based DSPE combined with DLLME followed by HPLC.

This work offers preparation of surfactant-modified amorphous carbon and its application in dispersive solid phase extraction of metronidazole and clarithromycin from plasma samples. The extraction procedure was combined with dispersive liquid-liquid microextraction for further preconcentration of the analytes for sensitive determination of the analytes followed by high performance liquid chromatography-diode array detector. In this work, first, the sorbent was added to the sample and the mixture vortexed to adsorb the analytes. Then, the obtained supernatant after centrifuging is discarded and the loaded analytes onto the sorbent surface were eluted with a water-miscible organic solvent. In the following, to further enrichment of the analytes the microextraction step was done. For this purpose, the eluate is taken, mixed with a water-immiscible organic solvent, and injected into deionized water. After centrifuging, an aliquat of the sedimented phase is taken and injected into the analytical instrument for the quantitative analysis. Under the optimum extraction conditions, high extraction recoveries (79 and 89% for metronidazole and clarithromycin, respectively), low limits of detection (2.1 and 1.9ngmL-1 for metronidazole and clarithromycin, respectively) and quantification (7.0 and 6.3ngmL-1 for metronidazole and clarithromycin, respectively), good repeatability (relative standard deviations less than 4.3% for intra- and 6.3% inter-day precisions), and wide linear ranges (7.3-1000 and 6.3-1000ngmL-1 for metronidazole and clarithromycin, respectively) were obtained. At the end, the introduced method was applied on the plasma samples of the patients treated with metronidazole and clarithromycin successfully.

Construction of hierarchically porous metal-organic framework HP-UiO-66-30% for sensitive determination of benzoylurea insecticides

Due to widespread application of benzoylurea insecticides (BUs) and its persistence in environment, the effective capture of benzoylurea insecticides residues in environment is an important issue of environmental safety monitoring. To obtain excellent adsorption performance, creating defective structure in metal-organic frameworks (MOFs) can be employed as the method for adjusting its properties. Zirconium(Ⅳ)-based MOF termed as UiO-66-30% was constructed with 2-aminoterephthalic acid (NH2-BDC) and terephthalic acid (H2BDC) as building blocks. After calcination and removal of thermal-sensitive ligand (NH2-BDC), hierarchically porous UiO-66-30% (HP-UiO-66-30%) with multistage pore structure and good stability was obtained. The unique structure of HP-UiO-66-30% endowed it to achieve instantaneous equilibrium (within 2 min) when it was used as a dispersed solid phase extraction (d-SPE) adsorbent to extract BUs from environmental samples, greatly reducing the operation time. A wide linear range (0.05–200 ng mL−1), good linearity (R2 ≥ 0.9980), low detection limits (0.01–0.03 ng mL−1) and quantification limits (0.05–0.1 ng mL−1) were obtained for BUs. In addition, the HP-UiO-66-30% material possessed the good reusability and the adsorption capacity did not change significantly over 16 adsorption-desorption cycles. Finally, the established dispersed solid phase extraction-high performance liquid chromatography-diode array detector (d-SPE-HPLC-DAD) method was successfully applied to determination of BUs residues in environmental soil samples. The results demonstrated that HP-UiO-66-30% was an excellent sorbent for extraction BUs from environmental samples.

Development and optimization of natural deep eutectic solvent-based dispersive liquid-liquid microextraction coupled with UPLC-UV for simultaneous determination of parabens in personal care products: evaluation of the eco-friendliness level of the developed method.

Dispersive liquid-liquid microextraction (DLLME) combined with ultra-high performance liquid chromatography-diode array detector (UHPLC-DAD) method has been developed and validated for the determination of parabens in personal care products. In this study, a natural deep eutectic solvent (NADES) composed of menthol and formic acid at a molar ratio of 1 : 2 was prepared and used as an extraction solvent. The influencing variables on the extraction efficiency such as extraction solvent type and volume, composition of NADES, salt addition, vortex and centrifugation time were investigated. The proposed method exhibited good linearity with determination coefficients of ≥0.9992. The relative recoveries for the studied analytes ranged from 82.19 to 102.45%. Limits of detection and limits of quantification were in the range of 0.17-0.33 ng mL-1 and 0.51-0.99 ng mL-1, respectively. To evaluate the applicability of the developed method, it was successfully applied to determine four parabens in personal care products. Additionally, the eco-friendliness level of the presented method was evaluated using Eco-Scale Assessment, Green Analytical Procedure Index and Analytical GREEnness metric. The developed method is simple, environmentally friendly and cost effective and it could be employed for determination of parabens in personal care products without harming the environment.