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.

Development of HPLC Method for Catechins and Related Compounds Determination and Standardization in Miang (Traditional Lanna Fermented Tea Leaf in Northern Thailand).

High performance liquid chromatography (HPLC) for catechins and related compounds in Miang (traditional Lanna fermented tea leaf) was developed to overcome the matrices during the fermentation process. We investigated a variety of columns and elution conditions to determine seven catechins, namely (+)-catechin, (-)-gallocatechin, (-)-epigallocatechin, (-)-epicatechin, (-)-epigallocatechin gallate, (-)-gallocatechin gallate, (-)-epicatechin gallate, as well as gallic acid and caffeine, resulting in the development of reproducible systems for analyses that overcome sample matrices. Among the three reversed-phase columns, column C (deactivated, with extra dense bonding, double endcapped monomeric C18, high-purity silica at 3.0 mm × 250 mm and a 5 µm particle size) significantly improved the separation between Miang catechins in the presence of acid in the mobile phase within a shorter analysis time. The validation method showed effective linearity, precision, accuracy, and limits of detection and quantitation. The validated system was adequate for the qualitative and quantitative measurement of seven active catechins, including gallic acid and caffeine in Miang, during the fermentation process and standardization of Miang extracts. The latter contain catechins and related compounds that are further developed into natural active pharmaceutical ingredients (natural APIs) for cosmeceutical and nutraceutical products.

Towards Green Titration: Batchwise Titration with Reusable Solid Sorbed Indicators.

We propose the creation of reusable indicator-sorbed-solids, using anion-exchange resins or kaolin as supports, with the aim to reduce chemical use towards green analytical chemistry. Indicators (phenolphthalein, thymol blue and butterfly pea flower extract as a natural indicator) sorbed on a solid support, were employed in acid-base titration, in both homogenous aqueous and heterogenous aqueous organic phases. Applications of the developed techniques to some real samples, such as vinegar, colored fruit juice and vegetable oil, have been demonstrated.

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.

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.

Green analytical methodology using Indian almond (Terminalia catappa L.) leaf extract for determination of aluminum ion in waste water from ceramic factories.

The use of natural reagents from plant extracts for chemical analysis is one of the approaches in the development of low cost and environmentally friendly green analytical chemistry methodology. Here, crude extract from Indian Almond (Terminalia Catappa L.) leaves was used for colorimetric determination of aluminum by monitoring the absorbance of the Al(3+)-extract complex at 435 nm. Dry leaves and freeze-dried fresh leaf extract can be kept for extended use. A simple flow injection analysis (FIA) system was also employed for rapid analysis (approximately 180 injections/h). The linear working range up to 100 mg L(-1) was established with a detection limit (blank + 3SD) of 0.8 mg L(-1), a limit of quantitation (blank + 10SD) of 2.4 mg L(-1), and a relative standard deviation of 3-5%. This simple green analytical chemistry methodology was applied for the determination of Al(3+) in waste water samples from ceramic factories. The results agreed well with the results obtained from the ICP-OES technique.

High-performance liquid chromatography with sequential injection for online precolumn derivatization of some heavy metals.

HPLC was coupled with sequential injection (SI) for simultaneous analyses of some heavy metals, including Co(II), Ni(II), Cu(II), and Fe(II). 2-(5-Nitro-2-pyridylazo)-5-[N-propyl-N-(3-sulfopropyl)amino]phenol (nitro-PAPS) was employed as a derivatizing reagent for sensitive spectrophotometric detection by online precolumn derivatization. The SI system offers an automated handling of sample and reagent, online precolumn derivatization, and propulsion of derivatives to the HPLC injection loop. The metal-nitro-PAPS complexes were separated on a C(18)-muBondapak column (3.9x300 mm(2)). Using the proposed SI-HPLC system, determination of four metal ions by means of nitro-PAPS complexes was achieved within 13 min in which the parallel of derivatization and separation were processed at the same time. Linear calibration graphs were obtained in the ranges of 0.005-0.250 mg/L for Cu(II), 0.007-1.000 mg/L for Co(II), 0.005-0.075 mg/L for Ni(II), and 0.005-0.100 mg/L for Fe(II). The system provides means for automation with good precision and minimizing error in solution handling with the RSD of less than 6%. The detection limits obtained were 2 microg/L for Cu(II) and Co(II), and 1 microg/L for Ni(II) and Fe(II). The method was successfully applied for the determination of metal ions in various samples, including milk powder for infant, mineral supplements, local wines, and drinking water.

Simple spectrophotometric flow injection system with an in-valve minicolumn for enhancement during the determination of chromium(III) using EDTA.

A simple spectrophotometric flow injection (FI) procedure for the determination of Cr(III) using ethylenediaminetetraacetic acid (EDTA) was developed. An FI system with a column packed with Amberlite IR-120(H) was employed for sample pretreatment. This leads to the possibility of a single standard calibration. A linear calibration in a range of 10-27 microg Cr(III) was obtained with a detection limit of 1 microg Cr(III) and RSD of 2% (18 microg Cr(III), n=12). The proposed procedure was applied for determination of Cr(III) in leachate and dietary supplement samples. The results agreed with those obtained by the standard methods.

Simple bead injection-flow injection system for the determination of copper.

We demonstrate the extended application of a simple bead injection-flow injection system with a modified simple colorimetric detection unit for the determination of low amount of Cu2+ in samples of different matrices (water and supplement tablet samples) with minimal sample pretreatment by employing ammonium pyrrolidinedithiocarbamate (APDC) reagent.