A simple microwave-assisted synthesis of cobalt ferrite nanoparticles and its application for the determination of lead ions in rooibos (Aspalathus linearis) tea.

In this study, a magnetic sorbent assisted dispersive solid phase extraction (DSPE) method was used to preconcentrate lead ions from rooibos tea samples for determination by slotted quartz tube-flame atomic absorption spectrometry (SQT-FAAS). Cobalt ferrite magnetic nanoparticles (CoFe2O4 MNPs) were synthesized by microwave assisted digestion. Limits of detection and quantification were calculated as 5.3 and 17.6 µg/L, respectively, in a linear dynamic range of 20-800 µg/L. The enhancement factor of the developed method was found to be 80-folds when compared to the detection limit of the regular FAAS system. The percent recoveries obtained for rooibos tea samples spiked at different concentrations were in the range of 77 - 125%, with high repeatability as indicated by low standard deviations. The findings of the study demonstrated that the CoFe2O4 MNPs-based extraction method is a straightforward, fast, affordable, safe, and eco-friendly approach to qualifying/quantifying lead with high precision in the selected beverage sample.

Nickel hydroxide nanoflower-based dispersive solid-phase extraction of copper from water matrix.

In this work, a dispersive solid-phase extraction method based on Ni(OH)2 nanoflowers (Ni(OH)2-NFs-DSPE) was developed to separate and preconcentrate copper ions from tap water samples for determination by flame atomic absorption spectrometry (FAAS). Ni(OH)2-NFs was synthesized using a homogeneous precipitation technique and used as sorbent for copper preconcentration. X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared spectroscopy were used to characterize the synthesized sorbent. All experimental variables were carefully optimized to achieve a high enhancement factor of 107.5-folds with respect to the detection sensitivity of the conventional FAAS. The proposed method's analytical parameters including LOD, LOQ, and linear range were determined as 1.33 µg/L, 4.42 µg/L, and 3.0-40 µg/L, respectively. To assess the applicability and reliability of the developed method, optimal conditions were applied to tap water samples and satisfactory percent recoveries (94-103%) were obtained for the samples spiked at 20 and 30 µg/L. This validated the accuracy and feasibility of the developed method to real samples. The developed method can be described as a simple, efficient, and rapid analytical approach for the accurate determination of trace copper ions in water samples.

Development and validation of dispersive liquid-liquid microextraction method for the determination of 15 polycyclic aromatic hydrocarbons in 200 Antarctica samples by gas chromatography mass spectrometry.

Antarctica has seen an increase in scientific research and tourism, and anthropogenic activities such as incineration of waste products and fuel combustion for energy and transportation are potential contamination sources to the ecosystem. Polycyclic aromatic hydrocarbons are common products of incomplete combustion of organic compounds and could be among accumulating contaminants in Antarctica. Thus, this study sought to develop a sensitive dispersive liquid-liquid microextraction method for the determination of 15 polycyclic aromatic hydrocarbons by gas chromatography mass spectrometry. Parameters that were relevant to the extraction method were carefully optimized and validated using aqueous standard solutions. The optimum method recorded detection limits in the range of 0.20-6.1 µg/L for the analytes. Spike recovery experiments were carried out on artificial seawater, rock-soil, and moss samples, using matrix matching calibration to mitigate effects of the sample matrices. The samples analyzed included seawater, lake, rock-soil, moss, seaweed, and feces samples all collected from the Horseshoe and Faure Islands in Antarctica. The percent recovery results obtained for the samples spiked at different concentrations ranged between 86 and 115%.

Removal of selected pesticides, alkylphenols, hormones and bisphenol A from domestic wastewater by electrooxidation process.

In this study, seven compounds of environmental and health concern were treated by electrooxidation to determine their removal efficiencies from domestic wastewater. A batch type lab-scale reactor was used for the treatment process, and the analytes studied included two obsolete pesticides, two alkylphenols, two hormones, and bisphenol A. Titanium oxide and graphite electrodes were used as anode and cathode, respectively. Parameters of the electrooxidation process including pH of wastewater, ionic strength, applied current and treatment period were optimized by the univariate approach to maximize the removal efficiency of the analytes from wastewater. The optimum conditions were determined as nonadjusted pH of wastewater, 1.5 A current, 15 min treatment period and 5.0 g/L sodium chloride. Dispersive liquid-liquid microextraction was used to preconcentrate analytes before and after treatment in order to calculate the removal efficiency of analytes. The removal efficiency obtained under the optimum conditions was satisfactory for all seven analytes at different influent concentrations.

Trace level determination of eleven nervous system-active pharmaceutical ingredients by switchable solvent-based liquid-phase microextraction and gas chromatography-mass spectrometry with matrix matching calibration strategy.

This study utilized switchable solvent liquid-phase microextraction (SS-LPME) to enrich eleven nervous system active pharmaceutical ingredients (APIs) from aqueous samples for their determination at trace levels by gas chromatography mass spectrometry. The analytes selected for the study included APIs utilized in antidepressant, antipsychotic, antiepileptic, and anti-dementia drugs. Parameters of the microextraction method including switchable solvent volume, concentration and volume of the trigger agent (sodium hydroxide), and sample agitation period were optimized univariately to boost extraction efficiency. Under the optimum conditions, the detection limits calculated for the analytes were in the range of 0.20-8.0 ng/mL, and repeatability for six replicate measurements as indicated by percent relative standard deviation values were below 10%. Matrix matching calibration strategy was used to enhance quantification accuracy for the analytes. The percent recovery results calculated for the eleven analytes ranged between 86 and 117%.

Modular peptide binders - development of a predictive technology as alternative for reagent antibodies.

Current biomedical research and diagnostics critically depend on detection agents for specific recognition and quantification of protein molecules. Monoclonal antibodies have been used for this purpose over decades and facilitated numerous biological and biomedical investigations. Recently, however, it has become apparent that many commercial reagent antibodies lack specificity or do not recognize their target at all. Thus, synthetic alternatives are needed whose complex designs are facilitated by multidisciplinary approaches incorporating experimental protein engineering with computational modeling. Here, we review the status of such an engineering endeavor based on the modular armadillo repeat protein scaffold and discuss challenges in its implementation.

Surface modified iron magnetic nanoparticles assisted Fenton digestion and extraction method for cadmium determination.

This study presents a Fenton digestion method for milk samples based on UV irradiation for cadmium determination using flame atomic absorption spectrometry. The method was developed as an alternative to microwave digesters, using very basic apparatus and easy to acquire chemicals. Fenton digestion process was performed by the help of citric acid coated magnetic nanoparticles. Optimum conditions of the digestion process were applied to milk samples to evaluate analytical performance of the method. Limit of detection and limit of quantification values calculated for cadmium in milk were 0.53 and 1.8 mg/L, respectively. The method was applied to three different milk samples to validate the method's suitability and accuracy. Percent recovery values calculated for the samples spiked at two different concentrations ranged between 86 and 111%. Due to differences in the content of the spiked and control/standard milk samples, exact matrix matching calibration strategy using the same brand of milk sample in the preparation of calibration standard was employed and the accuracy of cadmium quantification was greatly enhanced (≈100%).

Dispersive Liquid-Liquid Microextraction Based Preconcentration of Selected Pesticides and Escitalopram Oxalate, Haloperidol, and Olanzapine from Wastewater Samples Prior to Determination by GC-MS.

BACKGROUND: Determination of emerging pollutants including pharmaceuticals, pesticides, industrial chemicals and hormones in different environmental samples is very important for human health. OBJECTIVE: Experimental design enabled parameters to be evaluated for their effects onextraction output as well as their interactive effects. METHOD: A multivariate experimental design was used to attain optimum conditions of a dispersive liquid-liquid microextraction method for preconcentration of pesticides and pharmaceuticals for determination by GC-MS. RESULTS: The optimum parameters suggested by the design model were 200 µL of chloroform, 1.96 mL of ethanol, and 40 s vortexing period. LOD and LOQ were calculated using linear calibration plots of the analytes developed in the standard concentration range of 2.0 µg/L-2.0 mg/L. CONCLUSIONS: Enhancement in detection power of the analytes recorded by the optimized method with respect to direct GC-MS determination (based on LOD values) was in the range of 3.6 and 539 folds. Spiked recovery experiments for municipal, medical, and synthetic wastewater samples yielded low recovery results when calculated against aqueous standard solutions. Matrix matched calibration standards were used to mitigate interferences from the waste samples and the percent recoveries obtained were close to 100%. This established accuracy and applicability of the developed method. HIGHLIGHTS: The detection limits were found between 0.50 ng/mL and 37 ng/mL. An accurate, simple and sensitive analytical method was developed for the analytes.

Accurate Quantification of Nervous System Drugs in Aqueous Samples at Trace Levels by Binary Solvent Dispersive Liquid-Liquid Microextraction-Gas Chromatography Mass Spectrometry.

Pharmaceutical products are widely consumed globally and are commonly found in wastewaters as a result of constant excretion and disposal into sewers. The present study proposes an efficient binary solvent dispersive liquid-liquid microextraction (BS-DLLME) method that was developed for preconcentration of 7 nervous system drug active compounds from aqueous media for their determination at trace levels by gas chromatography-mass spectrometry. The drug analytes included 3 antidepressants, 2 antipsychotics, 1 antiepileptic, and 1 antidementia. Optimum conditions of the BS-DLLME method were acquired by univariate optimization of parameters including type of binary solvents, ratio of binary solvents, type of disperser solvent, volume of binary solvents, and volume of disperser solvent. Detection and quantification limits were calculated in the range of 0.28 to 6.5 µg/L. Municipal wastewater, medical wastewater, synthetic domestic wastewater, and lake water were utilized as real samples in spike recovery experiments; and the results (94-106%) indicated the method's applicability and accuracy at quantifying the analytes in complex matrices. Environ Toxicol Chem 2021;40:1570-1575. © 2021 SETAC.

The relationship between carbon dioxide emission and crop and livestock production indexes: a dynamic common correlated effects approach.

Rapid increase in carbon dioxide emission triggers climate change, while climate change poses a threat to food security. On the other hand, emission increase as a result of agricultural production continues. Considering this cycle, it is thought that examining the relationship between agricultural production and carbon dioxide emissions can help countries take emission-reducing measures and develop policies to ensure food safety. With this thought, a common correlated effect estimator was used in this study to explain the relationship between crop and livestock production index and carbon dioxide emission of 184 countries with the use of data for the period of 1998-2014. Countries were classified under four categories: low-income countries, lower middle-income countries, upper middle-income countries and high-income countries. According to DCCE test results, it was reported that a 1% increase in crop production index had effect on CO2 emission only in lower middle-income countries. A 1% increase in livestock production index, on the other hand, was reported to increase CO2 emission rates by 0.28, 0.49, and 0.39 in lower middle-income, upper middle-income, and high-income countries, respectively. When evaluated in general, it could be stated that livestock breeding has a higher effect on CO2 emission in agricultural production. The findings of the present study revealed that countries need to improve agricultural production methods in ways to minimize the positive association between vegetative and livestock production in accordance with their level of development, to adopt more environment-friendly agricultural technologies and to endorse international environmental policies.

Determination of copper in traditional coffee pot water samples by flame atomic absorption spectrometry and matrix matching calibration strategy after switchable solvent based liquid-phase microextraction.

Traditional copper coffee pots are widely used in these modern times and daily consumption of coffee brewed in overused/old pots increases the risk of copper ingestion. This study employed a green switchable solvent-based liquid-phase microextraction (SS-LPME) method to isolate and preconcentrate copper from water boiled in coffee pots. Copper was determined by a flame atomic absorption spectrometry (FAAS) system coupled with a slotted quartz tube (SQT). 1,5-Diphenylcarbazone was added to aqueous samples to form a complex with copper before the extraction step. Box-Behnken experimental design was applied to select optimum conditions of the extraction method that were used to validate the analytical method. The limits of quantification and detection of the optimized SS-LPME-SQT-FAAS method were determined as 9.1 and 2.7 µg/L, respectively. Water samples boiled in traditional coffee pots were spiked at different concentrations and analyzed to ascertain the method's accuracy and applicability to real samples. Satisfactory recovery results obtained in the range of 92-107% established good accuracy, and percent relative standard deviations lower than 8.0% also proved high precision.

Experimental Design of Vortex Assisted Switchable Solvent Homogeneous Liquid-Liquid Microextraction for Simultaneous Determination of Four Pesticides in Wastewater.

BACKGROUND: Pesticides are chemicals used mainly to protect plant crops in order to increase their production efficiency and quality. OBJECTIVE: Switchable-solvent homogeneous liquid-liquid microextraction was optimized using a Box-Behnken experimental design and validated on a gas chromatography mass spectrometry system for the determination of analytes. METHOD: The significance of independent variables (switchable solvent volume, sodium hydroxide volume, and vortex period) and their interactions were evaluated by analysis of variance at 95% confidence limits (α = 0.05). RESULTS: The LOD and LOQ ranges of the analytes were found to be 0.42-1.90 µg/L and 1.36-6.33 µg/L, respectively. Percentage recovery results were found to be in the range of 87-113% in spiking experiments. CONCLUSIONS: A simple, efficient, and accurate analytical method was developed for the simultaneous determination of the selected pesticides. Highlights: Matrix matching was used to enhance quantification accuracy for real samples. HIGHLIGHTS: Matrix matching was used to enhance quantification accuracy for real samples.

Accurate and simple determination of oxcarbazepine in human plasma and urine samples using switchable-hydrophilicity solvent in GC-MS.

This work presents a sensitive and rapid analytical method for the determination of oxcarbazepine in human plasma and urine samples. A vortex-assisted switchable hydrophilicity solvent-based liquid phase microextraction (VA-SHS-LPME) was used to preconcentrate oxcarbazepine from the samples before the determination by gas chromatography mass spectrometry. The switchable hydrophilicity solvent was synthesized by protonating N,N-dimethylbenzylamine with carbon dioxide to make it totally miscible with an equivalent volume of water. Parameters of the VA-SHS-LPME method including volume of switchable hydrophilicity solvent, concentration/volume of sodium hydroxide and vortex period were systematically optimized. Under the optimum conditions, good linearity ranging from 27.03 to 353.47 µg/kg was obtained for the analyte. Limit of detection and quantitation values were found to be 6.2 and 21 µg/kg (mass base), respectively. The relative standard deviation was calculated as 6.9% for six replicate measurements of the lowest concentration of the calibration plot. Satisfactory recovery results were calculated in the range of 97-100% for human plasma and urine samples spiked at five different concentrations.

Identification of Alternative Allosteric Sites in Glycolytic Enzymes for Potential Use as Species-Specific Drug Targets.

Three allosteric glycolytic enzymes, phosphofructokinase, glyceraldehyde-3 phosphate dehydrogenase and pyruvate kinase, associated with bacterial, parasitic and human species, were explored to identify potential allosteric sites that would be used as prime targets for species-specific drug design purposes using a newly developed approach which incorporates solvent mapping, elastic network modeling, sequence and structural alignments. The majority of binding sites detected by solvent mapping overlapped with the interface regions connecting the subunits, thus appeared as promising target sites for allosteric regulation. Each binding site was then evaluated by its ability to alter the global dynamics of the receptor defined by the percentage change in the frequencies of the lowest-frequency modes most significantly and as anticipated, the most effective ones were detected in the vicinity of the well-reported catalytic and allosteric sites. Furthermore, some of our proposed regions intersected with experimentally resolved sites which are known to be critical for activity regulation, which further validated our approach. Despite the high degree of structural conservation encountered between bacterial/parasitic and human glycolytic enzymes, the majority of the newly presented allosteric sites exhibited a low degree of sequence conservation which further increased their likelihood to be used as species-specific target regions for drug design studies.

Development of a sensitive and accurate method for the simultaneous determination of selected insecticides and herbicide in tap water and wastewater samples using vortex-assisted switchable solvent-based liquid-phase microextraction prior to determination by gas chromatography-mass spectrometry.

In this study, a switchable solvent-based liquid-phase microextraction method was developed to preconcentrate selected pesticides from tap water and wastewater matrices for determination by gas chromatography-mass spectrometry. A thorough optimization process was performed for prominent extraction parameters such as switchable solvent amount, concentration/amount of sodium hydroxide, salt type and mixing period. Optimum parameters obtained at the end of the optimization process were applied to aqueous standard solutions to validate the method. The linear dynamic ranges of all four analytes were appreciably wide with coefficient of determination values greater than 0.9997. The limits of detection and quantification (LOD and LOQ) were calculated for the analytes in the ranges of 0.38-2.0 ng/mL and 1.3-6.5 ng/mL, respectively. Spiked recovery experiments were used to validate the accuracy of the developed method and to determine the performance of the method in different sample matrices. Tap water, municipal wastewater and medical wastewater were spiked at three different concentrations and analyzed under the method's optimum conditions. The percent recovery results calculated for the samples were in the range of 79-107%, and this validated the method's accuracy and applicability to complex matrices such as municipal and medical wastewater samples.

Combination of vortex assisted binary solvent microextraction and QuEChERS for the determination of prothiofos, oxadiargyl, and gamma-cyhalothrin in water and pineapple samples by gas chromatography mass spectrometry.

An accurate and sensitive dispersive liquid-liquid microextraction method based on binary solvents was used to enrich prothiofos, oxadiargyl, and gamma-cyhalothrin for quantification by GC-MS. The combination of two extraction solvents (binary mixture) resulted in higher extraction efficiencies compared to the single solvent extraction systems. Parameters of the binary extraction method where optimized to enhance the extraction output of the analytes. The limits of detection calculated for the analytes ranged between 0.59 and 1.6 ng/mL. Linear calibration plots of the analytes covered wide concentration ranges with R2 values greater than 0.9996 and percent relative standard deviation lower than 10%. Spiked recovery experiments were performed well and wastewater at two different concentrations and satisfactory results (89-104%) were obtained. The binary solvent microextraction method was combined with QuEChERS to quantify the analytes in pineapple matrix, using matrix matching method to enhance the accuracy of the method to almost 100%.

Dispersive liquid-liquid microextraction based preconcentration of selected pesticides and escitalopram oxalate, haloperidol and olanzapine from wastewater samples prior to determination by GC-MS.

A multivariate experimental design was used to attain optimum conditions of a dispersive liquid-liquid microextraction (DLLME) method for preconcentration of pesticides and pharmaceuticals for determination by gas chromatography mass spectrometry (GC-MS). Experimental design enabled parameters to be evaluated for their effects on extraction output as well as their interactive effects. The optimum parameters suggested by the design model were 200 µL of chloroform, 1.96 mL of ethanol and 40 s vortexing period. Limits of detection and quantification (LOD and LOQ) were calculated using linear calibration plots of the analytes developed in the standard concentration range of 2.0 µg/L-2.0 mg/L. Enhancement in detection power of the analytes recorded by the optimized method with respect to direct GC-MS determination (based on LOD values) was in the range of 3.6 and 539 folds. Spiked recovery experiments for municipal, medical and synthetic wastewater samples yielded low recovery results when calculated against aqueous standard solutions. Matrix matched calibration standards were used to mitigate interferences from the waste samples, and the percent recoveries obtained were close to 100%. This established accuracy and applicability of the developed method.