Sequential injection redox or acid-base titration for determination of ascorbic acid or acetic acid

Two sequential injection titration systems with spectrophotometric detection have been developed. The first system for determination of ascorbic acid was based on redox reaction between ascorbic acid and permanganate in an acidic medium and lead to a decrease in color intensity of permanganate, monitored at 525 nm. A linear dependence of peak area obtained with ascorbic acid concentration up to 1200 mg l⁻¹ was achieved. The relative standard deviation for 11 replicate determinations of 400 mg l⁻¹ ascorbic acid was 2.9%. The second system, for acetic acid determination, was based on acid–base titration of acetic acid with sodium hydroxide using phenolphthalein as an indicator. The decrease in color intensity of the indicator was proportional to the acid content. A linear calibration graph in the range of 2–8% w v⁻¹ of acetic acid with a relative standard deviation of 4.8% (5.0% w v⁻¹ acetic acid, n=11) was obtained. Sample throughputs of 60 h⁻¹ were achieved for both systems. The systems were successfully applied for the assays of ascorbic acid in vitamin C tablets and acetic acid content in vinegars, respectively.     

Dynamic surface tension analysis of dodecyl sulfate association complexes

First, a novel calibration method is used to expand the current understanding of spherical drop growth and elongation that occurs during on-line measurements of surface pressure using the dynamic surface tension detector (DSTD). Using a novel surface tension calibration method, the drop radius is calculated as a function of time from experimental drop pressure data and compared to the theoretical drop radius calculated from volumetric flow rate. From this comparison, the drop volume at which the drop shape starts to deviate ( approximately 4 mul) from a spherical shape is readily observed and deviates more significantly by approximately 6 mul drop volume (5% deviation in the ideal spherical drop radius) for the capillary sensing tip employed in the DSTD. From this assessment of drop shape, an experimental method for precise drop detachment referred to as pneumatic drop detachment is employed at a drop volume of 2 mul (two second drops at 60 mul/min) in order to provide rapid dynamic surface tension measurements via the novel on-line calibration methodology. Second, the DSTD is used to observe and study kinetic information for surface-active molecules and association complexes adsorbing to an air-liquid drop interface. Dynamic surface tension measurements are made for sodium dodecyl sulfate (SDS) in the absence and presence of either tetra butyl ammonium (TBA) or chromium (III). Sensitive, indirect detection of chromium and other multiply charged metals at low concentrations is also investigated. The DSTD is utilized in examining the dynamic nature of SDS: cation association at the air-liquid interface of a growing drop. Either TBA or Cr(III) were found to substantially enhance the surface tension lowering of dodecyl sulfate (DS), but the surface tension lowering is accompanied by a considerable kinetic dependence. Essentially, the surface tension lowering of these DS: cation complexes is found to be a fairly slow process in the context of the two second DSTD measurement. The limit of detection for both SDS and chromium (III) is in the 300-400 part-per-billion (by mass) range.     

Determination of ethanol in liquor by near-infrared spectrophotometry with flow injection

A simple procedure for the determination of ethanol in a liquor by near-infrared (NIR) spectrophotometry with flow injection (FI) is proposed. A liquor sample is equilibrated off-line with dried chloroform to extract ethanol into the organic phase. The extract is injected into a carrier stream of dried chloroform passing through a home-made flow through cell (1 mm path length) sitting in a NIR spectrophotometer for continuous monitoring of absorbance at 2305 or 2636 nm. The ethanol content can be evaluated from a calibration established by a plot of change in absorbance versus concentration of ethanol standard solutions. Optimization of the system will be discussed. A calibration is linear in the range of 20–50% (v/v) ethanol. A throughput of 240 injections h⁻¹ can be obtained. The procedure is validated by comparing the results with an analysis using gas chromatography.     

A Simple Minimized System Based on Moving Drops for Antioxidant Analysis Using a Smartphone

In this paper, a novel antioxidant analysis is proposed using a simple minimized device based on moving drops as solution handling and a smartphone as a detector. This approach is based on the colorimetric determination of the scavenging activity against 2,2-diphenyl-1-picrylhydrazyl radical (DPPH^•), expressed as the half-maximal inhibitory concentration (IC₅₀), vitamin C equivalent antioxidant capacity (VCEAC), and Trolox equivalent antioxidant capacity (TEAC). A small drop of the positive control or the samples moves by eluting an ethanol drop down by the force of gravity to react with a DPPH^• drop in the detection zone. The color change of DPPH^• is monitored by a smartphone camera, and the color signals are processed using Adobe Photoshop software. The magenta-to-yellow ratio was successfully applied to evaluate the percentage of DPPH^• inhibition with no significant difference compared with the reference spectrophotometric method at a confidence level of 95%. The total phenolic content (TPC) was measured using the Folin–Ciocalteu assay. An application to Miang (fermented tea leaf extract) showed the consonant relationship between the scavenging activity of DPPH^• and TPC.     

Lead Assays with Smartphone Detection Using a Monolithic Rod with 4-(2-Pyridylazo) Resorcinol

A monolithic rod of polyurethane foam–[4-(2-pyridylazo) resorcinol] (PUF–PAR) as a simple chemical sensor for lead assays with smartphone detection and image processing was developed. With readily available simple apparatus such as a plastic cup and a stirrer rod, the monolithic PUF rod was synthesized in a glass tube. The monolithic PUF–PAR rod could be directly loaded by standard/sample solution without sample preparation. A one-shot image in G/B value from a profile plot in ImageJ for a sample with triplicate results via a single standard calibration approach was obtained. A linear single standard calibration was: [G/B value] = −0.038[µg Pb²⁺] + 2.827, R² = 0.95 for 10–30 µg Pb²⁺ with a limit of quantitation (LOQ) of 33 µg L⁻¹. The precision was lower than 15% RSD. The proposed method was tested by an assay for Pb²⁺ contents in drinking water samples from Bangkok. The results obtained by the proposed method agree with those of ICP-OES and with 100–120% recovery, demonstrating that the method is useful for screening on-site water monitoring.     

Sequential injection titration with spectrophotometric detection for the assay of acidity in fruit juices.

A simple sequential injection analysis (SIA) with spectrophotometric detection for an assay of acidity in fruit juice was investigated. An alkaline reagent (sodium hydroxide), a sample and an indicator (phenolphthalein) were first aspirated and stacked as adjacent zones in a holding coil. With flow reversal through a reaction coil to the detector, zone penetration occurred, leading to a neutralization reaction that caused a decrease in the color intensity of the indicator being monitored for absorbance at 552 nm. The effects of various parameters were studied. Linear calibration graphs for acidities of 0.2 - 1.0 and 0.5 - 2.5% w/v citric acid as a standard, with a relative standard deviation of 1% (acidity of 0.3 - 0.6% w/v as citric acid, n=11) and a sample throughput of 30 samples h(-1), were achieved. The developed method was validated by a standard titrimetric method for assaying the acidity of fruit juice samples.     

Flow-injection and sequential-injection determinations of paracetamol in pharmaceutical preparations using nitrosation reaction.

A simple FI and two different SI systems have been investigated for the determination of paracetamol by employing a simple reagent for a nitrosation reaction. It is based on the on-line nitrosation of paracetamol with sodium nitrite in an acidic medium. The formed nitroso derivative species reacts further with sodium hydroxide to convert it to a more stable compound. The yellow product is continuously monitored at 430 nm. The FI system is very simple and cost effective for fast manual operation (60 injections/h; y = 0.268x + 44.314, r2 = 0.9910 for 400 - 1000 mg/l and y = 0.1687x + 145.72, r2 = 0.9970 for 1000 - 2500 mg/l). The two SI systems with different components and configurations are automated and optimized for the conditions for which no extra dilution is to be required for sample handling: one with a syringe pump and two selection valves (60 samples/h; y = 0.1488x - 4.7297, r2 = 0.9946 for 400 - 1000 mg/l and y = 0.0858x + 63.933, r2 = 0.9849 for 1000 - 2500 mg/l); the other is simpler and more cost-effective, with an autoburette and only one selection valve (15 samples/h; y = 0.0072x + 1.1467, r2 = 0.9977 for 200 - 1000 mg/l and y = 0.0028x + 5.4699, r2 = 0.9879 for 1000 - 2500 mg/l). They have all been applied to assay paracetamol in pharmaceutical preparations. The obtained results agree with those by the US Pharmacopeia method.     

Employing peroxidase from Thai indigenous plants for the application of hydrogen peroxide assay

Thai local plants known as banana stalk, banana blossom, banana, sugar-cane, oroxylum indicum fruit, sesbania grandiflora fruit, and pigeon pea fruit were utilized for screening peroxidase enzyme to replace costly horseradish peroxidase in the hydrogen peroxide assay. The highest peroxidase activity was found in banana stalk extracted solution. The kinetic parameters, i.e., Michaelis–Menten constant (Km) and maximum velocity (Vmax) of banana stalk peroxidase were carried out. The optimum pH and thermal stability of this enzyme were also studied. Furthermore, crude banana stalk peroxidase was applied for the determination of hydrogen peroxide in a disinfection solution without any purification. The influent parameters affecting the developed method were cautiously studied and optimized. The calibration curve of standard hydrogen peroxide was achieved between 2.0 and 10.0 μmol L^?1 with correlation coefficient (r ²) 0.995. The method validations of detection limit (LOD), limit of quantification (LOQ) and precision were investigated. The concentrations of hydrogen peroxide achieved by the developed method were correlated with the enzymatic method using commercial available horseradish peroxidase.     

Fast and simultaneous detection of heavy metals using a simple and reliable microchip-electrochemistry route: An alternative approach to food analysis

This paper reports, for the first, the fast and simultaneous detection of prominent heavy metals, including: lead, cadmium and copper using microchip CE with electrochemical detection. The direct amperometric detection mode for microchip CE was successfully applied to these heavy metal ions. The influences of separation voltage, detection potential, as well as the concentration and pH value of the running buffer on the response of the detector were carefully assayed and optimized. The results clearly show that reliable analysis for lead, cadmium, and copper by the degree of electrophoretic separation occurs in less than 3min using a MES buffer (pH 7.0, 25mM) and l-histidine, with 1.2kV separation voltage and -0.8V detection potential. The detection limits for Pb(2+), Cd(2+), and Cu(2+) were 1.74, 0.73 and 0.13microM (S/N=3). The %R.S.D. of each peak current was <6% and migration times <2% for prolonged operation. To demonstrate the potential and future role of microchip CE, analytical possibilities and a new route in the raw sample analysis were presented. The results obtained allow the proposed microchip CE-ED acts as an alternative approach for metal analysis in foods.     

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.