Transparent Cross-Flow Platform as Chemiluminescence Detection Cell in Cross Injection Analysis.

This work presents the use of a transparent 'Cross Injection Analysis' (CIA) platform as a flow system for chemiluminescence (CL) measurements. The CL-CIA flow device incorporates introduction channels for samples and reagents, and the reaction and detection channels are in one acrylic unit. A photomultiplier tube placed above the reaction channel detects the emitted luminescence. The system was applied to the analysis of (i) Co(II) via the Co(II)-catalyzed H2O2-luminol reaction and (ii) paracetamol via its inhibitory effect on the catalytic activity of Fe(CN)63- on the H2O2-luminol reaction. A linear calibration was obtained for Co(II) in the range of 0.002 to 0.025 mg L-1 Co(II) (r2 = 0.9977) for the determination of Co(II) in water samples. The linear calibration obtained for the paracetamol was 10 to 200 mg L-1 (r2 = 0.9906) for the determination of pharmaceutical products. The sample throughput was 60 samples h-1. The precision was ≤4.2% RSD. The consumption of the samples and reagents was ca. 170 µL per analysis cycle.

Multi-well plate as headspaces for paper-based colorimetric detection of sulfur dioxide gas: An alternative method of sulfite titration for determination of formaldehyde.

This work describes the analysis of formaldehyde using a 96-well microplate as multiple headspaces for the separation of sulfur dioxide gas generated from the sulfite remaining after its reaction with the formaldehyde in the sample. The quantitation of the gas is by colorimetric detection of an indicator paper placed over the microplate. The samples are aqueous extracts of various foods that are possibly adulterated with formaldehyde. A known excess amount of sulfite is added to the extract solution aliquoted in the well. The remaining sulfite is acidified with hydrochloric acid to generate sulfur dioxide gas which diffuses through the headspace above the solution to be absorbed at the moist strip of the indicator paper placed over the mouth of the wells. Anthocyanins extracted from the butterfly pea flower is used as the pH indicator giving a color change from the increase of hydrogen ions by hydrolysis of the absorbed sulfur dioxide gas. The exposed paper strip is scanned, and the digital images of the colored region analyzed using ImageJ software. The optimized method has a linear range of 200-1000 mg L-1 formaldehyde with limit of detection ((2.57*SD of intercept)/(slope of calibration line)) of the aqueous extract of 40 mg L-1 and coefficient of determination (r2) > 0.9979. Samples of fresh produce, such as seafood, meat, and vegetables, and various processed food were analyzed for their possible formaldehyde content. The results obtained from the headspace paper-based colorimetric detection are not statistically different from the values obtained from the titration method by paired t-tests.

Direct determination of ethanol in alcoholic beverages based on its anti-aggregation of melamine-silver nanoparticle assembly.

We report a new method for determination of ethanol based on anti-aggregation of silver nanoparticles (AgNPs) in the presence of melamine. In the system, ethanol and melamine act as protecting and aggregating agents, respectively. Melamine can induce citrate-stabilized AgNPs to aggregate, leading to a color change from yellow to green. However, if the AgNPs are pre-incubated in ethanol, ethanol readily surrounds the particles by forming hydrogen bonds with the citrate stabilizer. An external nanoshell of ethanol hinders particle aggregation caused by melamine. Minor aggregation of AgNPs was observed, the solution color maintained its yellow-orange color. Higher ethanol concentrations result in a lower degree of particle aggregation. The colorimetric response of AgNPs was monitored using a UV-vis spectrophotometer at 390 nm. The current method could determine ethanol concentrations over a wide dynamic range of 5-80% (v/v), with a detection limit of 3.1% (v/v) (3SD of blank/slope). This method was applied for direct quantification of ethanol in alcoholic drinks without sample pretreatment and the results are well correlated with those of gas chromatography. Our method is convenient and cost effective, making it auspicious for ethanol monitoring in alcoholic drink manufacture and control.

Foldable paper-based analytical device for membraneless gas-separation and determination of iodate based on fluorescence quenching of gold nanoclusters.

A new design of a paper-based analytical device (PAD) for membraneless gas-separation with subsequent determination of iodate is presented. The rectangular PAD was invented as the folded pattern, where two circular reservoirs: the donor reservoir and the acceptor reservoir were situated in "a single paper" for convenient use. The hydrophobic barrier of each reservoir was easily fabricated by painting with a permanent marker. The PAD was demonstrated for the quantitative analysis of iodate, based on the fluorescence quenching of the bovine serum albumin-stabilized gold nanoclusters (BSA-AuNCs). The BSA-AuNCs were fast prepared by a microwave-assisted approach. The nanoclusters solution was applied into the acceptor reservoir, while the sample, iodide and sulfuric acid were sequentially aliquoted into the donor reservoir. After folding the PAD, the donor and the acceptor were mounted together via a two-sided mounting tape. The headspace between the two reservoirs allows membraneless gas-separation of free iodine from the donor to diffuse into the acceptor. Etching of gold core of the nanoclusters in the acceptor resulted in quenching of the red emission, was monitored by two methods, i.e. "fluorometric detection" (λex: 490 nm, λem: 630 nm) and "image capture" of the acceptor under the UV irradiation by a smart phone's camera. Two calibrations were plotted accordingly to their detections and good linearities (r2 ˃ 0.98) were observed from 0.005 to 0.1 mmol L-1 iodate. High accuracy (mean recovery: 95.1 (±4.6) %) and high precision (RSD < 3%) were obtained. The lower limits of detection were 0.005 mmol L-1 (with fluorometric detection) and 0.01 mmol L-1 (with image capture). The method was effectively applied for the measurement of iodate in iodized salts and fish sauces without prior sample pre-treatment.

Towards direct analysis of solid and liquid samples exploiting a 3D printed dialysis unit and sequential injection: Application for automated derivatization and determination of gamma-aminobutyric acid in foodstuff and beverages.

In this work, a new design of a dialysis unit for direct analysis of solid and liquid samples is presented. The homemade unit was constructed using a 3D printer due to its simple and fast fabrication ability. The dialysis unit is composed of cylindrical-shaped donor and acceptor chambers. A stainless steel sieve is installed inside the donor chamber. SEM images clearly showed that the sieve prevented membrane blockage by suspension particles in the sample. Multiple dialysis units were connected to a sequential injection (SI) system for serial determination of gamma-aminobutyric acid (GABA) in solid and liquid samples. The dialysate from each dialysis unit was consecutively aspirated into the SI flow line for on-line derivatization of GABA with 2-hydroxy-1-naphthaldehyde (3.0% w/v). The derivative was detected spectrophotometrically at 425 nm. The linear calibration range extended to 1000 mg L-1 GABA (r2 > 0.99) with high precision (1.2 %RSD). The developed system was applied to analysis of dietary supplements, grains of germinated brown rice and milk. The samples were directly introduced into the donor chamber either as powder or liquids. The measured GABA content using the developed method was compared using high performance liquid chromatography, with good agreement using Pearson's correlation (r2 = 0.9999). The method has high accuracy based on recovery studies (99.8 ± 1.5%) and high sample throughput (64 samples h-1).

Simple and fast fabrication of microfluidic paper-based analytical device by contact stamping for multiple-point standard addition assay: Application to direct analysis of urinary creatinine.

In this work, a microfluidic paper-based analytical device (µPAD) for simultaneous multiple-point standard addition assay was fabricated by rubber stamping the hydrophobic barrier pattern onto a laboratory filter paper. The µPAD has a central zone from which an applied sample flows into eight surrounding narrow channels to which had been added the standard solutions. Each channel is connected to a circular area loaded with the reagent. The opposite end of this reagent zone is connected by second narrow channel to the final circular detection zone. The µPAD was applied to the measurement of creatinine in human urine. After addition of a urine sample, the orange-colored product arising from the Jaffé reaction is formed at the eight detection zones. A digital image of the µPAD is then recorded and the ratio of the red/green (R/G) intensity obtained using the ImageJ™ program is used in the quantitation of creatinine. The normal standard addition calibration line is constructed using the intensity ratio against the added creatinine concentrations (50-1000 mg L-1). Good linearity was achieved (r2 ˃ 0.99). There were no significant differences between the creatinine content using an HPLC method (paired t-test at 95% confidence, tstat = 1.78, tcritical = 2.26, n = 10). The use of simultaneous multiple-point standard addition calibration allows rapid determination of creatinine in urine with elimination of matrix interference.

Simple flow system with in-line gas-diffusion unit for determination of ethanol employing hypsochromic shift of visible absorbance band of methyl orange.

The effect of solvent composition on the uv-visible spectrum of methyl orange was investigated for application to the quantitative determination of ethanol. At fixed pH, there was a hypsochromic shift of the absorbance band of methyl orange with increasing ethanol concentration. Using acetate buffer at pH 3.40 the change of absorbance at 530 nm of a solution of methyl orange containing known concentrations of standard ethanol was measured to provide a calibration curve. In order to apply this method to the analysis of alcoholic samples, such as distilled spirits, blended spirits and liquid herbal medicines, a simple gas-diffusion unit coupled with flow system was employed to separate the ethanol from sample matrices. Using the gas diffusion-flow system and employing an evaporation time of 2 min, a linear calibration range of 5-45% (v/v) ethanol was achieved ((ΔA = (0.0078 ± 0.0002)x(ethanol, %(v/v)) + (0.040 ± 0.005)), r2 = 0.998). The limit of detection (3σ blank/slope) was 2.23% (v/v). The developed gas diffusion-flow system was applied to the analysis of colorless distilled spirits, yellow blended spirits and dark brown herbal medicines that are available in the local markets of Bangkok, Thailand. Validation of the method was carried out by comparing the results with analysis using gas chromatography. There was no statistically significant difference at the 95% confidence level for all alcoholic samples analyzed.

Microfluidic Analysis with Front-Face Fluorometric Detection for the Determination of Total Inorganic Iodine in Drinking Water.

A microfluidic method with front-face fluorometric detection was developed for the determination of total inorganic iodine in drinking water. A polydimethylsiloxane (PDMS) microfluidic device was employed in conjunction with the Sandell-Kolthoff reaction, in which iodide catalyzed the redox reaction between Ce(IV) and As(III). Direct alignment of an optical fiber attached to a spectrofluorometer was used as a convenient detector for remote front-face fluorometric detection. Trace inorganic iodine (IO3- and I-) present naturally in drinking water was measured by on-line conversion of iodate to iodide for determination of total inorganic iodine. On-line conversion efficiency of iodate to iodide using the microfluidic device was investigated. Excellent conversion efficiency of 93 - 103% (%RSD = 1.6 - 11%) was obtained. Inorganic iodine concentrations in drinking water samples were measured, and the results obtained were in good agreement with those obtained by an ICP-MS method. Spiked sample recoveries were in the range of 86%(±5) - 128%(±8) (n = 12). Interference of various anions and cations were investigated with tolerance limit concentrations ranging from 10-6 to 2.5 M depending on the type of ions. The developed method is simple and convenient, and it is a green method for iodine analysis, as it greatly reduces the amount of toxic reagent consumed with reagent volumes in the microfluidic scale.

A "Dual-acceptor Channel" Membraneless Gas-diffusion Unit for Simultaneous Determination of Ethanol and Acetaldehyde in Liquors Using Reverse Flow Injection.

A new design of membraneless gas-diffusion unit with dual acceptor channels for separation, collection and simultaneous determination of two volatile analytes in liquid sample is presented. The unit is comprised of three parallel channels in a closed module. A sample is aspirated into the central channel and two kinds of reagents are introduced into the other two channels. Two analytes are isolated from the sample matrix by diffusion into head-space and absorbed into the specific reagents. Non-absorbed vapor is released by opening the programmable controlled lid. The unit was applied to liquors for measurement of ethanol and acetaldehyde using reverse flow injection. Dichromate and nitroprusside were exploited as reagents for colorimetric detection of ethanol and acetaldehyde, respectively. Good linearity ranges (r2 >0.99) with high precision (RSD <2%) and high accuracy (recovery: 90 - 105%) were achieved. The results were compared to the results by GC-FID and no significant difference was observed by paired t-test (95% confidence).

A Simple and Rapid Method Based on Anti-aggregation of Silver Nanoparticles for Detection of Poly(diallyldimethylammonium chloride) in Tap Water.

A simple and rapid method was developed for the detection of poly(diallyldimethylammonium chloride) (PDADMAC) using citrate-capped silver nanoparticles (AgNPs). Detection was based on anti-aggregation of AgNPs in phosphate buffer caused by PDADMAC. Due to its positive charges, PDADMAC was adsorbed onto AgNPs via electrostatic interaction with citrate, which resulted in the charges at the particle surfaces to become positive and caused repulsion among particles. Furthermore, long-chain PDADMAC provided steric hindrance. These two effects promoted the dispersion of AgNPs in the phosphate buffer. A change in the state of dispersion influenced the surface plasmon resonance (SPR) of AgNPs. Therefore, in this work, the concentration of PDADMAC was determined by monitoring changes in absorbance (at 396 nm) caused by SPR of AgNPs. Under optimal conditions, the calibration was linear over the range of 1 to 100 mg L(-1) with a detection limit of 0.7 mg L(-1). Satisfactory precision was obtained (RSD = 2.8%). This method was successfully applied to the determination of PDADMAC in tap water samples. The recoveries ranged from 86.0 - 107.5%.

A low-cost method for determination of calcium carbonate in cement by membraneless vaporization with capacitively coupled contactless conductivity detection.

This work presents a flow analysis method for direct quantitation of calcium carbonate in cement without pretreatment of the sample. The method is based on online vaporization of CO(2) gas following acidification of the sample inside a small chamber that has a flow of acceptor solution passing around it. Solubilization of the CO(2) gas into the acceptor stream changes the conductivity of the acceptor solution causing an increase of signal at the capacitively coupled contactless conductivity detection (C(4)D) placed at the outlet of the vaporization chamber. This chamber is an adaption from previous work reported on 'membraneless vaporization' (MBL-VP). The method can be used in the quality control of production of mixed cement. These cement materials usually have calcium carbonate contents at high concentration range (e.g., 33-99% (w/w) CaCO(3)). Analysis of samples by this method is direct and convenient as it requires no sample pretreatment. The method is low-cost with satisfactory accuracy and acceptable precision.