Nuanlaor Ratanawimarnwong

A reagent-free SIA module for monitoring of sugar, color and dissolved CO2 content in soft drinks.

This work presents a new sequential injection analysis (SIA) method and a module for simultaneous and real-time monitoring of three key parameters for the beverage industry, i.e., the sugar content (measured in Brix), color and dissolved CO(2). Detection of the light reflection at the liquid interface (the schlieren effect) of sucrose and water was utilized for sucrose content measurement. A near infrared LED (890+/-40 nm) was chosen as the light source to ensure that all the ingredients and dyes in soft drinks will not interfere by contributing light absorption. A linear calibration was obtained for sucrose over a wide concentration range (3.1-46.5 Brix). The same module can be used to monitor the color of the soft drink as well as the dissolved CO(2) during production. For measuring the color, the sample is segmented between air plugs to avoid dispersion. An RGB-LED was chosen as the light source in order to make this module applicable to a wide range of colored samples. The module also has a section where dissolved CO(2) is measured via vaporization of the gas from the liquid phase. Dissolved CO(2), in a flowing acceptor stream of water resulting in the change of the acceptor conductivity, is detected using an in-house capacitively coupled contactless conductivity detector (C(4)D). The module includes a vaporization unit that is also used to degas the carbonated drink, prior the measurements of sucrose and color within the same system. The method requires no chemicals and is therefore completely friendly to the environment.

Sequential injection system for simultaneous determination of sucrose and phosphate in cola drinks using paired emitter-detector diode sensor

This work presents the simultaneous determination of sucrose and phosphate by using sequential injection (SI) system with a low cost paired emitter-detector diode (PEDD) light sensor. The PEDD uses two 890 nm LEDs. Measurement of sucrose in Brix unit was carried out based on the detection of light refraction occurring at the liquid interface (the schlieren effect) between the sucrose solution and water. Phosphate was measured from the formation of calcium phosphate with turbidimetric detection. With careful design of the loading sequence and volume (sample--precipitating reagent--sample), simultaneous detection of sucrose and phosphate was accomplished with the single PEDD detector. At the optimized condition, linear calibrations from 1 to 7 Brix sucrose and from 50 to 200mg PO4(3-)L(-1) were obtained. Good precision at lower than 2% RSD (n=10) for both analytes with satisfactory throughput of 21 injections h(-1) was achieved. The method was successfully applied for the determination of sucrose and phosphate in cola drinks. The proposed method is readily applicable for automation and is found to be an alternative method to conventional procedures for on-line quality control process in cola drink industry.

Reagent-free analytical flow methods for the soft drink industry: Efforts for environmentally friendly chemical analysis

The evolution of an entirely green analytical system for industrial quality control of carbonated drinks is described. The developed flow system is capable of providing analytical data of the dissolved CO2, sucrose, and color of a sample consecutively in real-time. The system has been carefully designed on the basis of “reagent-free”, meaning that no added chemicals are required for the analysis. The system first vaporizes CO2 from the soft drink in a gas–liquid separation chamber, with a channel for a flow of pure water as the CO2 acceptor. The dissolved CO2 alters the conductivity of the water stream, which is directly related to the concentration of CO2 in the soft drink. The sucrose content is measured based on the “schlieren effect”, the sample plug flows out of the vaporization chamber into a colorimeter with a near-infrared/light-emitting diode (NIR/LED) as light source. The schlieren effect arises at the boundary of pure water and soft drink with refraction of light in proportion to the sugar concentration. The system also measures the absorbance of the sample using an RGB-LED. The related principles and preliminary experiments as proof of concept are described as well as the construction of the flow system for this completely reagent-free analyzer. A simple flow injection system using the schlieren effect was also developed for rapid quantitative analysis of sugar in noncarbonated soft drinks.

New membraneless vaporization unit coupled with flow systems for analysis of ethanol.

This work presents the development of a new design for a membraneless vaporization (MBL-VP) unit, called dual chamber MBL-VP for measurement of volatile compounds. With this unit, exact volumes of sample and reagent are introduced into their respective cone-shaped chambers from the base of the cones. Diffusion of volatile analyte then takes place. After an appropriate time interval, the acceptor solution is withdrawn from the chamber into the detector flow-cell, while the sample solution is withdrawn to waste. Unlike the previous MBL-VP design, problems with overflow of solutions are eliminated by precise control of the input volume to be less than the volume of the chamber. The developed flow system with the dual chamber MBL-VP unit was applied to the determination of the ethanol content of various liquid samples, using the oxidation reaction between potassium dichromate and the diffused ethanol. In addition, in order to accelerate the gas diffusion process, the donor chamber was aerated. As the result, relatively short analysis time of 144 s was achieved for ethanol content in the range of 5-50% (v/v). The proposed method was successfully validated against a gas chromatographic method for 17 alcoholic samples. Percentage recovery was in the range of 96-109%.

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.

Development of flow systems incorporating membraneless vaporization units and flow-through contactless conductivity detector for determination of dissolved ammonium and sulfide in canal water

Use of membraneless vaporization (MBL-VP) unit with two cone-shaped reservoirs is presented for on-line separation and detection of non-volatile species. A flow system comprising two sets of MBL-VP units with a single in-house capacitively coupled contactless conductivity detector (C4D) was developed for dual determination of ammonium and sulfide ions. Using the continuous-flow section, two zones (280μL) of a sample, either mixed with sodium hydroxide (for ammonium) or hydrochloric acid (for sulfide), are separately delivered into the donor reservoir of the MBL-VP units. The acceptor reservoir contains either 150μL of 15μM HCl solution (for ammonia) or pure water (for hydrogen sulfide), respectively. Vaporization and trapping of the ammonia or hydrogen sulfide gas from the donor reservoir into the liquid acceptor cone occur concurrently in the two separate MBL-VP units. After trapping the gas for 3min, the two 150-μL liquid acceptors are sequentially aspirated through the C4D flow cell for recording the changes in the conductivity. Linear calibrations were obtained for ammonium from 5 to 80µM (Volt = (0.0134 ± 0.0003) [NH4+] - (0.01 ± 0.01), r2 = 0.998) and for sulfide from 5 to 200µM (Volt = (0.0335 ± 0.0009) [S2-] - (0.13 ± 0.09), r2 = 0.996). Analysis time for both analytes is only 320s. Our method was applied to analyze canal water samples. The results agree well with membrane gas-diffusion flow injection techniques, using bromothymol blue for ammonium and methylene blue for sulfide. Recoveries ranged from 95% to 104%.

Green analytical method for simultaneous determination of salinity, carbonate and ammoniacal nitrogen in waters using flow injection coupled dual-channel C4D

A flow injection analysis system (FIA) for the simultaneous determination of salinity, carbonate and ammoniacal nitrogen has been developed and reported in this paper. FIA incorporating membrane units was used, not only for the separation of the gaseous carbon dioxide and ammonia, but also for on-line dilution in the salinity measurement. The sample was injected via a 10-port valve with two sample loops. One loop was used for salinity and carbonate measurements and the second loop for ammoniacal nitrogen determination. A dual-channel capacitively coupled contactless conductivity detector was assembled in a single shielding box. Input voltage from the same AC power supply was fed to the input electrodes of both C4D cells. One channel of the C4D was used to monitor the change in conductivity of an acceptor stream that carried a zone of the water sample that has passed through the on-line dilution unit. Conductivity of this zone relates directly to the salinity of the sample. The same sample zone was next acidified to generate carbon dioxide gas that diffused through a hydrophobic membrane of the first gas diffusion (GD) unit. The zone of dissolved carbon dioxide in acceptor stream of water flowed into the same C4D cell as for the salinity measurement, but arriving at a later time. Concurrently, the second channel of the C4D monitored the change in conductivity of the acceptor stream in the second GD unit due to the diffusion of ammonia gas generated by the reaction of base with the sample injected from the second sample loop. The change in conductivity at this second C4D cell correlates with the concentration of ammoniacal nitrogen present in the sample. The proposed method is low cost, simple, rapid and sensitive. The limit of quantitation for salinity, carbonate and ammoniacal nitrogen are 0.31mmolL-1, 1.85 µmol L-1, respectively. Throughput of 20 samples h-1 for simultaneous analysis can be achieved with RSD of less than 3.8%. The system had been applied to the determination of salinity, carbonate and ammoniacal nitrogen in 15 water samples, with results in agreement with those obtained using comparison methods.

Microfluidic Paper-based Analytical Device for Quantification of Lead Using Reaction Band-length for Identification of Bullet Hole and Its Potential for Estimating Firing Distance

A low-cost and user-friendly microfluidic paper-based analytical device (μPAD) was developed for identification of bullet hole from gunshot residue (GSR) on cotton fabric target. The device (25 × 82 mm) is made of filter paper with a printed pattern consisting of a circular sample loading reservoir (6 mm i.d.), a circular waste reservoir (4 mm i.d.) and a straight flow channel (3 mm wide and 60 mm long). A sticker with a ruler scale in millimeters was mounted alongside the channel. The straight channel is first impregnated with rhodizonate and dried at ambient temperature. Tartrate extract of the target fabric is loaded on the sample reservoir. If Pb(II) ions are present in the extract, pink streak of Pb(II)-rhodizonate precipitate is formed as the sample solution flows from the reservoir along the channel. The length of the pink strip is employed to estimate the firing distance.

Green analytical flow method for the determination of total sulfite in wine using membraneless gas–liquid separation with contactless conductivity detection

A green analytical flow method was developed for the determination of total sulfite in white wine. The method employs the membraneless vaporization (MBL-VP) technique for gas–sample separation allowing direct analysis of wine. Sulfite in an aliquot of sample was converted to SO2 gas via acidification. Dissolution of the gas into the water acceptor led to a change in the conductivity of the acceptor which was monitored using a ‘capacitively coupled contactless conductivity detector’ (C4D) flow cell. Only a minute amount of common acid (100 μL of 1.5 mol L−1 H2SO4) is used. The MBL-VP unit was incorporated into the flow system to separate the SO2 gas from the wine sample using the headspace above the donor and acceptor compartments as a virtual membrane. The method provides a linear working range (10–200 mg L−1 sulfite) which is suitable for most wines with calibration equation y = (0.056 ± 0.002)x + (1.10 ± 0.22) and r2 = 0.998. Sample throughput is 26 samples h−1. The lower limit of quantitation (LLOQ = 3SD of blank per slope) is 0.3 mg L−1 sulfite for 20 s diffusion time with good precision (%RSD = 0.8 for 100 mg L−1 sulfite, n = 10). We also present a simple modification of the MBL-VP unit by the addition of a third cone-shaped reservoir to provide two acceptor zones leading to improvement in sensitivity of more than three-fold without use of heating to enhance the rate of diffusion of SO2.

Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions☆

An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures.