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.

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.

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.

Ultrasound-Assisted One-Pot Cloud Point Extraction for Iron Determination Using Natural Chelating Ligands from Dipterocarpus intricatus Dyer Fruit.

An ultrasound-assisted, one-pot cloud point extraction was developed for the determination of iron in vegetable samples by UV-Visible spectrophotometry. This method was based on the complexation of iron with an environmentally-friendly natural chelating agent extracted from Dipterocarpus intricatus Dyer fruit at pH 5.5 in the presence of Triton X-114. Reagent extraction, complexation, and preconcentration were performed simultaneously using ultrasound-assisted extraction at 45 °C. The surfactant-rich phase was diluted with ethanol and loaded through a syringe barrel packed with cotton that acted as a filter to trap the reagent powder. Analyte-entrapped on cotton was eluted using 0.1 mol·L-1 nitric acid solution. Filtrate and eluate solutions were measured absorbance of the dark-blue product at 575 nm. Influential parameters for the procedure were investigated. Under the optimum experimental conditions, the calibration curve was linear, ranging from 0.1 to 1.0 mg·L-1 with r2 = 0.997. Limits of detection and quantification were 0.03 and 0.09 mg·L-1, respectively while precision values of intra-day and inter-day were less than 5%. Recovery at 0.5 mg·L-1 ranged from 89.0 to 99.8%, while iron content in vegetable samples ranged from 2.45 to 13.36 mg/100 g. This method was cost-effective, reliable, eco-friendly, and convenient as a green analytical approach to determining iron content.

Dual determination of nitrite and iron by a single greener sequential injection spectrophotometric system employing a simple single aqueous extract from Areca catechu Linn. serving as a natural reagent.

Dual determination of nitrite and iron was proposed by using a single greener sequential injection (SI) spectrophotometric system employing a simple single aqueous extract from Areca catechu Linn. The extract served as a natural reagent to replace N-(1-naphthyl)ethylenediamine (NED) of the Griess reagent with nitrite and 1,10-phenanthroline with iron. The color products possessed analytical wavelengths at 430 and 560 nm, respectively. Conditions for the SI procedure were optimized using a univariate experimental design. Calibration ranges were up to 5.0 mg L-1 and 10.0 mg L-1 with limits of detection (LODs) of 0.04 mg L-1 and 0.05 mg L-1 for nitrite and iron(iii), respectively, and relative standard deviations (RSDs) being less than 3%. Recoveries of spiked standard nitrite and iron(iii) at 0.3 mg L-1 and 0.5 mg L-1 in water samples were 88 to 104% and 84 to 109%, respectively. The developed method successfully achieved dual determination of nitrite and total iron agreeing at a 95% confidence level with the reference methods of the conventional Griess assay and flame atomic absorption spectrometry (FAAS), respectively. The proposed method utilized locally available material from plants and serves the UN-SDGs.

A Simple and Reliable Dispersive Liquid-Liquid Microextraction with Smartphone-Based Digital Images for Determination of Carbaryl Residues in Andrographis paniculata Herbal Medicines Using Simple Peroxidase Extract from Senna siamea Lam. Bark.

A simple and reliable dispersive liquid-liquid microextraction (DLLME) coupled with smartphone-based digital images using crude peroxidase extracts from cassia bark (Senna siamea Lam.) was proposed to determine carbaryl residues in Andrographis paniculata herbal medicines. The method was based on the reaction of 1-naphthol (hydrolysis of carbaryl) with 4-aminoantipyrine (4-AP) in the presence of hydrogen peroxide, using peroxidase enzyme simple extracts from cassia bark as biocatalysts under pH 6.0. The red product, after preconcentration by DLLME using dichloromethane as extraction solvent, was measured for blue intensity by daily life smartphone-based digital image analysis. Under optimized conditions, good linearity of the calibration graph was found at 0.10-0.50 mg·L-1 (r2 = 0.9932). Limits of detection (LOD) (3SD/slope) and quantification (LOQ) (10SD/slope) were 0.03 and 0.09 mg·L-1, respectively, with a precision of less than 5%. Accuracy of the proposed method as percentage recovery gave satisfactory results. The proposed method was successfully applied to analyze carbaryl in Andrographis paniculata herbal medicines. Results agreed well with values obtained from the HPLC-UV method at 95% confidence level. This was simple, convenient, reliable, cost-effective and traceable as an alternative method for the determination of carbaryl.

A newly designed sticker-plastic sheet platform and smartphone-based digital imaging for protein assay in food samples with downscaling Kjeldahl digestion.

A low-cost and reliable analytical method based on the combination of a newly designed sticker-plastic sheet platform, digital image-based colorimetry and down scaled Kjeldahl digestion is proposed for the determination of protein content in food samples. The yellowish-brown colloidal products, obtained from the reaction between the ammonium-nitrogen after digestion and the working Nessler's reagent on the miniaturized sticker-plastic sheet platform, were captured for imaging with a smartphone camera. The operational parameters and reaction conditions were optimized. A down scaled Kjeldahl digestion procedure was performed using the newly designed digestion block. The parameters influencing the digestion efficiency, including the mass of the sample, volume of acid, mass of the catalyst and digestion time, were evaluated. Under the selected conditions, a linear calibration in the range of 5-60 mg L-1 ammonium-nitrogen was obtained with limits of detection and quantification of 2.8 and 7.6 mg L-1, respectively. The repeatability and reproducibility were 6.7% and 8.8%, respectively. The accuracy of the proposed method was evaluated by applying the developed procedure for milk powder and feeding stuff reference materials and comparing it with the conventional Kjeldahl method. The proposed method was successfully applied for the determination of protein contents in soy foods and protein-based foods. The results agreed well with those obtained from the conventional Kjeldahl method.

Employing natural reagents from turmeric and lime for acetic acid determination in vinegar sample.

A simple, rapid and environmentally friendly sequential injection analysis system employing natural extract reagents was developed for the determination of acetic acid following an acid-base reaction in the presence of an indicator. Powdered lime and turmeric were utilized as the natural base and indicator, respectively. Mixing lime and turmeric produced an orange to reddish-brown color solution which absorbed the maximum wavelength at 455 nm, with absorbance decreasing with increasing acetic acid concentration. Influential parameters including lime and turmeric concentrations, reagent and sample aspirated volumes, mixing coil length and dispensing flow rate were investigated and optimized. A standard calibration graph was plotted for 0-5.0 mmol/L acetic acid with r2 = 0.9925. Relative standard deviations (RSD) at 2.0 and 4.0 mmol/L acetic acid were less than 3% (n = 7), with limit of detection (LOD) and limit of quantification (LOQ) at 0.12 and 0.24 mmol/L, respectively. The method was successfully applied to assay acetic acid concentration in cooking vinegar samples. Results achieved were not significantly different from those obtained following a batchwise standard AOAC titration method.

Quality assessment of trace Cd and Pb contaminants in Thai herbal medicines using ultrasound-assisted digestion prior to flame atomic absorption spectrometry.

A simple, efficient, and reliable ultrasound-assisted digestion (UAD) procedure was used for sample preparation prior to quantitative determination of trace Cd and Pb contaminants in herbal medicines using flame atomic absorption spectrometry. The parameters influencing UAD such as the solvent system, sample mass, presonication time, sonication time, and digestion temperature were evaluated. The efficiency of the proposed UAD procedure was evaluated by comparing with conventional acid digestion (CAD) procedure. Under the optimum conditions, linear calibration graphs in a range of 2-250 µg/L for Cd, and 50-1000 µg/L for Pb were obtained with detection limits of 0.56 µg/L and 10.7 µg/L for Cd and Pb, respectively. The limit of quantification for Cd and Pb were 1.87 µg/L and 40.3 µg/L, respectively. The repeatability for analysis of 10 µg/L for Cd and 100 µg/L for Pb was 2.3% and 2.6%, respectively. The accuracy of the proposed method was evaluated by rice flour certified reference materials. The proposed method was successfully applied for analysis of trace Cd and Pb in samples of various types of medicinal plant and traditional medicine consumed in Thailand. Most herbal medicine samples were not contaminated with Cd or Pb. The contaminant levels for both metals were still lower than the maximum permissible levels of elements in medicinal plant materials and finished herbal products sets by the Ministry of Public Health of Thailand. The exception was the high level of Cd contamination found in two samples of processed medicinal plants.

A green analytical method for benzoyl peroxide determination by a sequential injection spectrophotometry using natural reagent extracts from pumpkin.

A green and environmental friendly method with simple sequential injection spectrophotometry using natural reagent extract from pumpkin (Cucurbita moschata Decne) for determination of benzoyl peroxide (BPO) was developed. The maximum absorption of the yellow crude extract containing the ß-carotene compound occurred at a wavelength of 450nm. The yellow extract solution was bleached by BPO to change the color to a colorless solution. The optimum conditions of the proposed method, such as extraction solvent influence of pH, dilution of pumpkin extracts solution, aspiration volume of reagent and sample, flow reversal, incubation time, mixing coil length, and dispensing flow rate were studied and optimized. The linear calibration graph under the optimum conditions in the range of 9.4-100mgL-1 BPO was obtained with good linearity (r2=9985). The limit of detection (LOD) and the limit of quantification (LOQ) were 3.9 and 9.4mgL-1, respectively. Relative standard deviation was achieved at less than 4% (n=7). This system provided sample throughput of 9h-1. Good recoveries were found between 83.42±3.34-112.29±3.49%. The system was successfully employed as a natural reagent extract from pumpkin for determination of BPO in acne treatment samples. Also, the results agreed well with those obtained from the HPLC-UV method.

A Green Sequential Injection Spectrophotometric Approach Using Natural Reagent Extracts from Heartwood of Ceasalpinia sappan Linn. for Determination of Aluminium.

A cost-effective and environmentally friendly approach using a simple sequential injection spectrophotometric system with a non-synthetic reagent from plant extracts was proposed for a green analytical-chemistry methodology. The crude aqueous extracts from heartwood of Ceasalpinia sappan Linn. in acetate buffer pH 5.5 were utilized as an alternative natural reagent for the quantification of aluminium. The extracts contained homoisoflavonoid compounds, brazilin, and brazilein, which reacted with Al(3+) to form reddish complexes with the maximum absorption wavelength at 530 nm. The optimum conditions for the sequential injection parameters, such as sequential profile, sample and reagent volumes, and the pH effect, were investigated. Under the optimum conditions, a linear calibration graph in the range of 0.075 - 1.0 mg L(-1) Al(3+) was obtained with limits of detection and quantification of 0.021 and 0.072 mg L(-1) Al(3+), respectively. Relative standard deviations of 3.2 and 2.4% for 0.1 and 0.25 mg L(-1) Al(3+) (n = 11), respectively, and sampling rate of 128 injections h(-1) were achieved. The developed system was successfully applied to pharmaceutical preparations, water, and beverage samples. The results agreed well with those obtained from the ICP-AES method. Good recoveries between 87 and 104% were obtained.

A rapid and sensitive spectrophotometric method for the determination of benzoyl peroxide in wheat flour samples.

A simple, rapid, and sensitive spectrophotometric method for the determination of benzoyl peroxide (BPO) in wheat flour samples was developed. The detection principle is based on BPO reacted with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) to obtain a blue-green colored product that was detected at 415 nm by spectrophotometry. The effect of factors influencing the color reaction was investigated. Under the selected conditions, the linear range for quantification of BPO was observed between 0.2-1.0 mg L-1 with r2 = 0.998. The limit of detection (LOD) was 0.025 mg L-1. The developed method obtained superior precision (relative standard deviation < 2%) using 11 repeatability at 0.2 mg L-1, 0.6 mg L-1, and 0.8 mg L-1. The proposed methodology was successfully applied to determine BPO in wheat flour samples.

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.

Simultaneous injection effective mixing flow analysis of urinary albumin using dye-binding reaction.

A new four-channel simultaneous injection effective mixing flow analysis (SIEMA) system has been assembled for the determination of urinary albumin. The SIEMA system consisted of a syringe pump, two 5-way cross connectors, four holding coils, five 3-way solenoid valves, a 50-cm long mixing coil and a spectrophotometer. Tetrabromophenol blue anion (TBPB) in Triton X-100 micelle reacted with albumin at pH 3.2 to form a blue ion complex with a λ(max) 625nm. TBPB, Triton X-100, acetate buffer and albumin standard solutions were aspirated into four individual holding coils by a syringe pump and then the aspirated zones were simultaneously pushed in the reverse direction to the detector flow cell. Baseline drift, due to adsorption of TBPB-albumin complex on the wall of the hydrophobic PTFE tubing, was minimized by aspiration of Triton X-100 and acetate buffer solutions between samples. The calibration graph was linear in the range of 10-50µg/mL and the detection limit for albumin (3σ) was 0.53µg/mL. The RSD (n=11) at 30µg/mL was 1.35%. The sample throughput was 37/h. With a 10-fold dilution, interference from urine matrix was removed. The proposed method has advantages in terms of simple automation operation and short analysis time.

Simultaneous injection effective mixing analysis system for the determination of direct bilirubin in urinary samples.

A novel simultaneous injection effective mixing analysis system (SIEMA) for determination of direct bilirubin in urine sample was developed. Bilirubin reacts with diazotized sulfanilic acid in the presence of n-octyl-ß-d-thioglucoside (OTG) as a solubilizing agent to form OTG-azobilirubin. The flow and chemical variables were investigated. A linear calibration graph for direct bilirubin was obtained over the range of 0-1.0 mg L(-1) (r(2)=0.994) with the limit of detection (3σ) of 4.7 µg L(-1), and the relative standard deviation (RSD) being 1.9% (n=11, 0.5 mg L(-1) of direct bilirubin). The results in healthy adult urine obtained by the proposed approach were found in good agreement with those obtained by the batch-wise diazo method.

Sequential injection Lab-at-valve (SI-LAV) segmented flow system for kinetic study of an enzyme.

A sequential injection-Lab-at-valve (SI-LAV) segmented flow system for kinetic study of an enzyme was developed. Air segments were introduced for separation of enzyme and substrate zones and separation of the stacked zones from the carrier solution which ensure the measurement of the initial rate and minimize the dilution/dispersion effect. The open- ended mixing chamber makes it possible to use air segments in the flow system without the need for additional air segment discarding steps. The enzyme horseradish peroxidase (HRP) kinetic parameters based on initial rate was used as a model study. The operation of the system is virtually the same as that of the conventional batch-wise process. The kinetic parameters (i.e. K(m) and V(max)) of HRP obtained using the proposed system agree well with those obtained using the batch-wise process as well. The proposed system offers additional benefits of volume down scaling, improved rapidity and automatic features that does not require a skillful operator.