A general strategy to prepare SERS active filter membranes for extraction and detection of pesticides in water.

An important feature in the fabrication of surface-enhanced Raman scattering (SERS) platforms is, together with the high efficiency, to allow the rapid collection and analysis of a vestigial analyte. Conventional substrates based on rigid solid materials or metal hydrosols are not suitable for sample extraction, limiting their application in areas such as water quality monitoring. Herein, we have developed a strategy to fabricate SERS active substrates (Ag/LCP) based on liquid-crystal polymer (LCP) textile fibers decorated with Ag nanoparticles (NPs). Two distinct methods for substrate preparation envisaging the SERS detection of the pesticide thiram have been explored in this research. In a first stage, we have investigated the usefulness of both approaches using ethanolic solutions of the pesticide thiram, and after real samples spiked with thiram were used to explore the analysis in real environment. The SERS analysis of thiram dissolved in Aveiro Estuary water and in fruit juices have provided enhancement factors of 1.67 × 107 and 3.86 × 105, respectively, using the Ag/LCP composites. Noteworthy, in the latter case, the detection limit (0.024 ppm) achieved is lower than the maximal residue limit (MRL) of 5 ppm in fruit, as prescribed by European regulations (EU) 2016/1. Moreover, the selectivity of the SERS substrates for different pesticides was also evaluated, analyzing distinct pesticides such as paraquat and sodium diethyldithiocarbamate. SERS active Ag/LCP/PA filter membranes were also prepared using Ag/LCP composites supported by a polyamide (PA) filter, which can be an easy alternative to prepare simple, highly efficient and low-cost SERS active filter membranes for water analysis.

One-step green synthetic approach for the preparation of multicolor emitting copper nanoclusters and their applications in chemical species sensing and bioimaging.

One-step green microwave synthetic approach was developed for the synthesis of copper nanoclusters (Cu NCs) and used as a fluorescent probe for the sensitive detection of thiram and paraquat in water and food samples. Unexpectedly, the prepared Cu NCs exhibited strong orange fluorescence and showed emission peak at 600 nm, respectively. Under optimized conditions, the quenching of Cu NCs emission peak at 600 nm was linearly proportional to thiram and paraquat concentrations in the ranges from 0.5 to 1000 µM, and from 0.2 to 1000 µM, with detection limits of 70 nM and 49 nM, respectively. In addition, bioimaging studies against Bacillus subtilis through confocal fluorescence microscopy indicated that Cu NCs showed strong blue and green fluorescence signals, good permeability and minimum toxicity against the various bacteria species, which demonstrates their potential feasibility for chemical species sensing and bioimaging applications.

Smartphone based visual and quantitative assays on upconversional paper sensor.

The integration of smartphone with paper sensors recently has been gain increasing attentions because of the achievement of quantitative and rapid analysis. However, smartphone based upconversional paper sensors have been restricted by the lack of effective methods to acquire luminescence signals on test paper. Herein, by the virtue of 3D printing technology, we exploited an auxiliary reusable device, which orderly assembled a 980nm mini-laser, optical filter and mini-cavity together, for digitally imaging the luminescence variations on test paper and quantitative analyzing pesticide thiram by smartphone. In detail, copper ions decorated NaYF4:Yb/Tm upconversion nanoparticles were fixed onto filter paper to form test paper, and the blue luminescence on it would be quenched after additions of thiram through luminescence resonance energy transfer mechanism. These variations could be monitored by the smartphone camera, and then the blue channel intensities of obtained colored images were calculated to quantify amounts of thiram through a self-written Android program installed on the smartphone, offering a reliable and accurate detection limit of 0.1µM for the system. This work provides an initial demonstration of integrating upconversion nanosensors with smartphone digital imaging for point-of-care analysis on a paper-based platform.

Dispersive liquid-liquid microextraction of thiram followed by microvolume UV-vis spectrophotometric determination.

A novel and simple method for the sensitive determination of trace amounts of fungicide thiram is developed by combination of dispersive liquid-liquid microextraction (DLLME) and microvolume UV-vis spectrophotometry. The method is based on the conversion of thiram to a yellow product in the presence of ethanolic potassium hydroxide and copper sulfate, and its extraction into CCL4 using DLLME technique. In this method the ethanol existing in ethanolic KOH plays as disperser solvent and a cloudy solution is formed by injection of only CCl4 as extractant solvent into sample solution. Under the optimum conditions, the calibration graph was linear over the range of 25-1000 ng mL(-1) of thiram with limit of detection of 11.5 ng mL(-1). The relative standard deviation (RSD) for 100 and 500 ng mL(-1) of thiram was 2.7 and 1.1% (n=8), respectively. The proposed method was successfully applied to determination of thiram in water and plant seed samples.

Isolation and simultaneous LC analysis of thiram and its less toxic transformation product in DS formulation.

A simple and sensitive high pressure liquid chromatographic method has been developed for the simultaneous determination of Thiram and its transformation product using isocratic mixture of methanol-water (65:35) at flow rates of 0.75 mL min(-1), PDA detector using UV absorbance (lambda(max)) at 217 nm for Thiram and 265.5 nm for the transformation product. The transformation product was isolated from the commercial DS formulation and has been tentatively assigned the structure by (1)H NMR and ESI-MS spectral data. The separation is dependent on the nature of the mobile phase, its flow rate and the nature of the HPLC column. The detection limit (signal/noise; S/N = 3) for both Thiram and its transformation product was 0.2 ppm. The method has been successfully applied to analysis of soil and soybean samples spiked with Thiram, its transformation product and a commercial sample containing these products.