An Environmentally Friendly Compact Microfluidic Hydrodynamic Sequential Injection System Using Curcuma putii Maknoi & Jenjitt. Extract as a Natural Reagent for Colorimetric Determination of Total Iron in Water Samples.

The miniaturization of analytical systems and the utilization of nontoxic natural extract from plants play significant roles for green analytical chemistry methodology. In this work, the microfluidic hydrodynamic sequential injection (HSI) with the LED-phototransistor colorimetric detection system has been proposed to create an ecofriendly and low-cost miniaturized analytical system for online determination of iron in water samples using Curcuma putii Maknoi & Jenjitt. extracts as high stability and good selectivity of a natural reagent. The proposed method was designed for online solution mixing and colorimetric detection on a microfluidic platform. The Curcuma putii Maknoi & Jenjitt. extracts and standard/samples were sequentially aspirated to fill the channel before entering the built-in flow cell. The intensity of iron-Curcuma putii Maknoi & Jenjitt. extract complex was monitored under the optimum conditions of flow rate, sample volume, mixing zone length, and aspiration sequences, by altering the gain control of the colorimetric detector to achieve good sensitivity. The results demonstrated a good performance of the green analytical systems. A linear calibration graph in the range of 0.5-6.0 mg L-1 was obtained with a limit of detection at an adequate level of 0.11 mg L-1 for water samples with a sample throughput of 30 h-1. The precise and accurate measurement results were achieved with relative standard deviations in the range of 1.61-1.72%, and percent recoveries were found in the range of 90.6-113.4. The proposed method offers cost-effective, easy operation over an appropriate analysis time (2 min/injection) with good sensitivity and is environmentally friendly with low consumption of solutions and the use of high stability and good selectivity of nontoxic reagents. The achieved method was demonstrated to be a good choice for routine analysis.

Reliable Sensing Platform for Plasmonic Enzyme-Linked Immunosorbent Assays Based on Automatic Flow-Based Methodology.

Plasmonic enzyme-linked immunosorbent assays (ELISA) using the localized surface plasmon resonance (LSPR) of metal nanoparticles has emerged as an appealing alternative to conventional ELISA counterparts for ultrasensitive naked-eye detection of biomolecules and small contaminants. However, batchwise plasmonic ELISA involving end-point detection lacks ruggedness inasmuch as the generation or etching of NP is greatly dependent on every experimental parameter of the analytical workflow. To tackle the above shortcomings, this paper reports on an automatic flow methodology as a reliable detection scheme of hydrogen peroxide related enzymatic bioassays for ultrasensitive detection of small molecules. Here, a competitive ELISA is combined with the in-line generation of plasmonic gold nanoparticles (AuNPs) followed by the real-time monitoring of the NP nucleation and growth rates and size distribution using a USB miniaturized photometer. Glucose oxidase was labeled to the secondary antibody and yielded hydrogen peroxide that acted as the measurand and the reducing agent of the Au(III)/citrate system in the flow network. High-throughput plasmonic assays were feasible by assembling a hybrid flow system composed of two microsyringe pumps, a perfluoroalkoxy alkane reaction coil, and a 26-port multiposition valve and operated under computer-controllable flow conditions. The ultratrace determination of diclofenac in high matrix samples, e.g., seawater, without any prior sample treatment was selected as a proof-of-concept application of the flow-based platform for determination of emerging contaminants via plasmonic ELISA. The detection limit (0.001 µg L-1) was 1 order of magnitude lower than that endorsed by the first EU Watch List for diclofenac as a potentially emerging contaminant in seawater and also than that of a conventional colorimetric ELISA, which in turn is inappropriate for determination of diclofenac in seawater at the levels endorsed by the EU regulation. The proposed automatic fluidic approach is characterized by the reproducible timing in AuNPs nucleation and growth along with the unsupervised LSPR absorbance detection of AuNPs with a dynamic range for diclofenac spanning from 0.01 to 10 µg L-1. Repeatability and intermediate precision (given as normalized signal readouts) in seawater were <4% and <14%, respectively, as compared to RSDs as high as 30% as obtained with the batchwise plasmonic ELISA counterpart.

Sequential injection system with multi-parameter analysis capability for water quality measurement.

A simple sequential injection (SI) system with capability to determine multi-parameter has been developed for the determination of iron, manganese, phosphate and ammonium. A simple and compact colorimeter was fabricated in the laboratory to be employed as a detector. The system was optimized for suitable conditions for determining each parameter by changing software program and without reconfiguration of the hardware. Under the optimum conditions, the methods showed linear ranges of 0.2-10 mg L(-1) for iron and manganese determinations, and 0.3-5.0 mg L(-1) for phosphate and ammonium determinations, with correlation coefficients of 0.9998, 0.9973, 0.9987 and 0.9983, respectively. The system provided detection limits of 0.01, 0.14, 0.004 and 0.02 mg L(-1) for iron, manganese, phosphate and ammonium, respectively. The proposed system has good precision, low chemical consumption and high throughput. It was applied for monitoring water quality of Ping river in Chiang Mai, Thailand. Recoveries of the analysis were obtained in the range of 82-119%.