Novel colorimetric assay for paraquat detection on-silica bead using negatively charged silver nanoparticles.

A simple, rapid, sensitive, and economical method based on colorimetry for the determination of paraquat, a widely used herbicide, was developed. Citrate-coated silver nanoparticles (AgNPs) were synthesized as the colorimetric probe. The mechanism of the assay is related to the aggregation of negatively charged AgNPs as induced by positively-charged paraquat resulting from coulombic attraction which causes the color to change from a deep greenish yellow to pale yellow in accordance with the concentrations of paraquat. Silica gel was exploited as the paraquat adsorbent for purification and pre-concentration prior to the direct determination with negatively charged AgNPs without the requirement of the elution step. The validity of the proposed approach was evaluated by spiking standard paraquat in water and plant samples. Recoveries of paraquat in water samples were 93.6% and 95.4% for groundwater and canal water, respectively, while those in plant samples were 89.5% and 86.6% for Chinese cabbage and green apple, respectively,after using the optimized extraction procedure. The absorbance of AgNPs at 400nm was linearly related to the concentration of paraquat over the range of 0.05-50mgL-1, with detection limits of 0.05mgL-1 for water samples, and 0.10mgL-1 for plant samples by naked eye determination.

Simple and fast colorimetric detection of inorganic arsenic selectively adsorbed onto ferrihydrite-coated silica gel using silver nanoplates.

The optical detection for inorganic arsenic (As) semi-quantitative determination is presented by using silver nanoplates (AgNPls). The color of AgNPs is immediately changed in the presence of As(III) and As(V) with the same sensitivity. To improve the selectivity of AgNPls for As detection, ferrihydrite-coated silica gel (SiO2-Fh) was specifically exploited as adsorbent for arsenic prior to As detection by AgNPls. The developed method provides the detection limit of 0.5ppm with the detection range between 0.5ppm and 30.0ppm for As determination observed with naked eye, and allows to determine total inorganic arsenic. This is the first report of As detection approach combining As removal technology together with nanotechnology. This combined technique provides a rapid, sensitive and selective method for monitoring As levels in aqueous samples, and can be employed as a testing field kit to screen arsenic contamination outside of a laboratory.

Selective label-free electrochemical impedance measurement of glycated haemoglobin on 3-aminophenylboronic acid-modified eggshell membranes.

We propose a novel alternative approach to long-term glycaemic monitoring using eggshell membranes (ESMs) as a new immobilising platform for the selective label-free electrochemical sensing of glycated haemoglobin (HbA1c), a vital clinical index of the glycaemic status in diabetic individuals. Due to the unique features of a novel 3-aminophenylboronic acid-modified ESM, selective binding was obtained via cis-diol interactions. This newly developed device provides clinical applicability as an affinity membrane-based biosensor for the identification of HbA1c over a clinically relevant range (2.3 - 14 %) with a detection limit of 0.19%. The proposed membrane-based biosensor also exhibited good reproducibility. When analysing normal and abnormal HbA1c levels, the within-run coefficients of variation were 1.68 and 1.83%, respectively. The run-to-run coefficients of variation were 1.97 and 2.02%, respectively. These results demonstrated that this method achieved the precise and selective measurement of HbA1c. Compared with a commercial HbA1c kit, the results demonstrated excellent agreement between the techniques (n = 15), demonstrating the clinical applicability of this sensor for monitoring glycaemic control. Thus, this low-cost sensing platform using the proposed membrane-based biosensor is ideal for point-of-care diagnostics.

Poly(dimethylsiloxane) cross-linked carbon paste electrodes for microfluidic electrochemical sensing.

Recently, the development of electrochemical biosensors as part of microfluidic devices has garnered a great deal of attention because of the small instrument size and portability afforded by the integration of electrochemistry in microfluidic systems. Electrode fabrication, however, has proven to be a major obstacle in the field. Here, an alternative method to create integrated, low cost, robust, patternable carbon paste electrodes (CPEs) for microfluidic devices is presented. The new CPEs are composed of graphite powder and a binder consisting of a mixture of poly(dimethylsiloxane) (PDMS) and mineral oil. The electrodes are made by filling channels molded in previously cross-linked PDMS using a method analogous to screen printing. The optimal binder composition was investigated to obtain electrodes that were physically robust and performed well electrochemically. After studying the basic electrochemistry, the PDMS-oil CPEs were modified with multi-walled carbon nanotubes (MWCNT) and cobalt phthalocyanine (CoPC) for the detection of catecholamines and thiols, respectively, to demonstrate the ease of electrode chemical modification. Significant improvement of analyte signal detection was observed from both types of modified CPEs. A nearly 2-fold improvement in the electrochemical signal for 100 µM dithiothreitol (DTT) was observed when using a CoPC modified electrode (4.0 ± 0.2 nA (n = 3) versus 2.5 ± 0.2 nA (n = 3)). The improvement in signal was even more pronounced when looking at catecholamines, namely dopamine, using MWCNT modified CPEs. In this case, an order of magnitude improvement in limit of detection was observed for dopamine when using the MWCNT modified CPEs (50 nM versus 500 nM). CoPC modified CPEs were successfully used to detect thiols in red blood cell lysate while MWCNT modified CPEs were used to monitor temporal changes in catecholamine release from PC12 cells following stimulation with potassium.

Thermoset polyester as an alternative material for microchip electrophoresis/electrochemistry.

Microchip CE coupled with electrochemical detection (MCE-EC) is a good method for the direct detection of many small molecule analytes because the technique is sensitive and readily miniaturized. Polymer materials are being increasingly used with MCE due to their affordability and ease of fabrication. While PDMS has become arguably the most widely used material in MCE-EC due to the simplicity of microelectrode incorporation, it suffers from a lack of separation efficiency, lower surface stability, and a tendency for analyte sorption. Other polymers, such as poly(methylmethacrylate) (PMMA) and poly(carbonate) (PC), have higher separation efficiencies but require more difficult fabrication techniques for electrode incorporation. In this report, thermoset polyester (TPE) was characterized as an alternative material for MCE-EC. TPE microchips were characterized in their native and plasma oxidized forms and after coating with polyelectrolyte multilayers (PEMs). TPE provides higher separation efficiencies when compared to PDMS microchips, while still using simple fabrication protocols. In this work, separation efficiencies as high as 295,000 N/m were seen when using TPE MCE-EC devices. Furthermore, the EOF was higher and more consistent as a function of pH for both native and plasma-treated TPE than PDMS. Finally, TPE is amenable to modification using simple PEM coatings as another way to control surface chemistry and surface charge.