Origami 3D-microfluidic paper-based analytical device for detecting carbaryl using mesoporous silica-platinum nanoparticles with a molecularly imprinted polymer shell.

Herein, we present a novel Origami 3D-µPAD for colorimetric carbaryl detection using a super-efficient catalyst, namely mesoporous silica-platinum nanoparticles coated with a molecularly imprinted polymer (MSN-PtNPs@MIP). Morphological and structural characterization reveals that coating MIP on the MSN-PtNPs surface significantly increases the selective area, leading to larger numbers of imprinting sites for improved sensitivity and selectivity in determining carbaryl. The as-prepared MSN-PtNPs@MIP was used for catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2. Carbaryl selectively binds to the cavities embedded on the MSN-PtNPs surface and subsequently inhibits TMB oxidation leading the color to change to light blue. The change of reaction color from dark blue to light blue depends on the concentration of carbaryl within the 3D-µPAD detection zone. This design integrates the advantages of highly efficient sample delivery through micro channels (top layer) and efficient partition/separation paths (bottom layer) of the cellulose substrate to achieve both improved detection sensitivity and selectivity. Assay on the Origami 3D-µPAD can determine carbaryl by ImageJ detection, over a dynamic range of 0.002-20.00 mg kg-1, with a very low limit of detection at 1.5 ng g-1. The developed 3D-µPAD exhibit high accuracy when applied to detect carbaryl in fruits, with satisfactory recoveries from 90.1% to 104.0% and relative differences from the reference HPLC values less than 5.0%. Furthermore, the fabricated Origami 3D-µPAD provides reliable durability and good reproducibility (3.19% RSD for fifteen devices).

Fast, sensitive and selective simultaneous determination of paraquat and glyphosate herbicides in water samples using a compact electrochemical sensor.

We report a new ready-to-use sensor for simultaneous determination of paraquat (PQ) and glyphosate (GLY) based on a graphite screen-printed electrode modified with a dual-molecularly imprinted polymer coated on a mesoporous silica-platinum core. Amino-mesoporous silica nanoparticles (MSN-NH2) were first synthesized by a simple co-condensation method using tetraethyl orthosilicate and 3-aminopropyltrimethoxysilane. PtNPs were then decorated on the surface of MSN-NH2 by chemical reduction. Finally, the dual-MIP was successfully coated on the MSN-PtNP core. This 3D-surface-imprinting strategy enhances the conductivity and monodispersity of the MSN-PtNPs@d-MIP. Quantitative analysis was performed by differential pulse voltammetry with an oxidation current appearing at -0.95 V for PQ and +0.97 V for GLY. The dual-MIP sensor shows good linear calibration curves in the range of 0.025-500 µM for both analytes with detection limits of 3.1 nM and 4.0 nM for PQ and GLY, respectively. The dual-MIP sensor shows high selectivity and specificity, attributed to the increased affinity of the imprinted cavities formed on the polymer film for the target PQ and GLY molecules. The proposed dual-MIP sensor was successfully applied to detect PQ and GLY concentrations simultaneously in water samples. The ready-to-use dual-MIP sensor is well suited for water-quality control and on-site applications without sophisticated instrumentation.

Enhanced selectivity and sensitivity for colorimetric determination of glyphosate using Mn-ZnS quantum dot embedded molecularly imprinted polymers combined with a 3D-microfluidic paper-based analytical device.

We report a novel three-dimensional microfluidic paper-based analytical device (3D-µPAD) with colorimetric detection, using Mn-ZnS quantum dot embedded molecularly imprinted polymer (Mn-ZnS QD-MIP), for selective glyphosate determination in whole grain samples. Detection is based on the catalytic activity of Mn-ZnS QD-MIP in the H2O2 oxidation of ABTS. Glyphosate imprinted polymer is successfully synthesized on the Mn-ZnS QD surface using a poly (N-isopropylacrylamide) (NIPAM) and N, N'-Methylenebisacrylamide (MBA) as the functional monomers. The catalytic activity depends on binding or non-binding of glyphosate molecules on the synthetic recognition sites of the Mn-ZnS QD-MIP. Glyphosate selectively binds to the cavities embedded on the Mn-ZnS QD surface, and subsequently turns-off or inhibits the ABTS oxidation and color change to light green. The change of reaction color from dark green to light green depends on the concentration of glyphosate. We report, for the first time, using the relatively new penguard enamel colour to create a hydrophobic barrier. The foldable 3D-µPAD comprises three layers (top/center/bottom), named as the detection zone, immobilized Mn-ZnS QD-MIP disc, and sample loading. Assay on the 3D-µPAD can determine glyphosate by ImageJ detection, over an operating range of 0.005-50 µg mL-1 and with a detection limit of 0.002 µg mL-1. Our 3D-µPAD exhibits high accuracy, with a 0.4% (intra-day) and 0.7% (inter-day) relative difference from the certified CRM value. Moreover, the fabricated 3D-µPAD provides good reproducibility (1.7% RSD for ten devices). The developed 3D-µPAD was successfully applied to determine the glyphosate concentration in whole grain samples and shows great promise as an alternative highly selective and sensitive colorimetric method. The 3D-µPAD is well suited to food-quality control and onsite environmental-monitoring applications, without sophisticated instrumentation.

Acid-base titration using a microfluidic thread-based analytical device (µTAD).

This work presents the development and application of a novel analytical approach for the determination of acid and base concentrations by titration using a microfluidic thread-based analytical device (µTAD). This approach proved to be a simple to fabricate and to use, high precision, and cost-efficient means of acid-base quantification. The µTAD was fabricated by immobilizing the untreated cotton threads onto a wood frame, followed by pre-coating with an indicator (20 µL) and a primary standard solution (3 µL), and was tested using real samples including drug, food, and household products where 3 µL of each sample was dropped onto the center of a thread. Afterward, the distance of color change on the thread, easily observed and measured using the naked eye and a ruler, was used for analysis. The analysis using the µTAD, completed within 2 minutes and validated by the conventional titration, showed high accuracy and precision (RSD < 12.9%), good linearity ranges and low limit of quantification. The fabricated µTAD also remained stable for an extended period of time (>2 weeks under various storage conditions).

Novel amperometric flow-injection analysis of creatinine using a molecularly-imprinted polymer coated copper oxide nanoparticle-modified carbon-paste-electrode.

We report a novel amperometric flow-injection (FI) analysis of creatinine based on a sensor comprising copper oxide nanoparticles (CuO) coated with a molecularly-imprinted polymer (CuO@MIP) and decorating a carbon-paste electrode (CPE) to form the CuO@MIP/CPE electrode. The CuO@MIP was synthesized by using CuO as the supporting core, creatinine as the template, methacrylic acid (MAA) as monomer, N, N'-(1,2-dihydroxyethylene)bis(acrylamide) (DHEBA) as cross-linker, and 2,2'-azobis (2-methylpropionitrile) (AIBN) as initiator. Morphology and structural characterization reveal that CuO nanoparticle imprinted sites (CuO) synthesized using a precipitation method, exhibits features that are well suited to creatinine detection: high surface area, good analyte diffusion and adsorption characteristics that provide shorter response times, and large numbers of specific cavities for enhanced analyte capacity and sensitivity. Cyclic voltammetric measurements indicate that our sensor provides excellent performance toward electro-oxidation of creatinine. The amperometric FI system was used to quantitatively determine creatinine at the CuO@MIP/CPE sensor, in a phosphate buffer carrier. The imprinted sensor exhibits excellent performance for creatinine oxidation at an applied potential of +0.35 V and flow rate of 0.6 mL.min-1. The as-prepared sensor exhibits a linear dynamic range for creatinine detection from 0.5 to 200 µM (r2 = 0.995) with a limit of detection of 0.083 µM (S/N = 3). The system exhibits satisfactorily good precision (%RSD = 1.94%, n = 30) and selectivity toward creatinine. There is only approximately 20% loss from initial response after 2 weeks when stored at 4 oC. We successfully applied the FI detection system to detect creatinine in human urine samples.

Highly sensitive and selective electrochemical paper-based device using a graphite screen-printed electrode modified with molecularly imprinted polymers coated Fe3O4@Au@SiO2 for serotonin determination.

Herein, we propose a highly sensitive and selective three-dimensional electrochemical paper-based analytical device (3D-ePAD) to determine serotonin (Ser). It uses a graphite-paste electrode modified with nanoparticles coated with molecularly imprinted polymer (MIP). Fe3O4@Au nanoparticles were encapsulated with silica to create novel nano-sized MIP. Morphology and structural characterization reveal that silica imprinted sites (Fe3O4@Au@SiO2) synthesized via sol-gel methods provide excellent features for Ser detection, including high porosity, and greatly improve analyte diffusion and adsorption to provide a faster response by the MIP sensor. The template molecule was effectively removed by solvent extraction to provide a greater number of specific cavities that enhance analyte capacity and sensitivity. The 3D-ePAD was fabricated by alkyl ketene dimer (AKD)-inkjet printing of a circular hydrophobic detection zone on filter paper for application of aqueous samples, coupled with screen-printed electrodes on the paper, which was folded underneath the hydrophobic zone. The sensor was constructed by drop coating of Fe3O4@Au@SiO2-MIP nanocomposites on the graphite electrode (GPE) surface. The MIP sensor (Fe3O4@Au@SiO2-MIP/GPE) was used in the detection of Ser by linear-sweep voltammetry (LSV) in 0.1 M phosphate buffer at pH 8.0. The device exhibits high sensitivity toward Ser, which we attribute to synergistic effects between catalytic properties, electrical conductivity of Fe3O4@Au@SiO2, and significantly increased numbers of imprinted sites. Ser oxidation was observed at +0.39 V. Anodic peak currents for Ser show linearity from 0.01 to 1000 µM (y = 0.0075 ± 0.0049 x + 0.4071 ± 0.0052, r2 = 0.993), with a detection limit of 0.002 µM (3S/N). The device provides good repeatability (%relative standard deviations; RSD) = 4.23%, calculated from the current responses of ten different MIP sensors). The device also exhibits high selectivity and reproducibility (%RSD = 8.35%, obtained from five calibration plots). The analytical performance of the device is suitable for the determination of Ser in pharmaceutical capsules and urine samples.

Novel three-Dimensional molecularly imprinted polymer-coated carbon nanotubes (3D-CNTs@MIP) for selective detection of profenofos in food.

A new and facile method for selective measurement of profenofos (PFF) using a simple flow-injection system with a molecularly-imprinted-polymer-coated carbon nanotube (3D-CNTs@MIP) amperometric sensor is proposed. The 3D-CNTs@MIP was synthesized by successively coating the surface of carboxylated CNTs with SiO2 and vinyl end groups, then terminating with molecularly imprinted polymer (MIP) shells. MIP was grafted to the CNT cores using methacrylic acid (MAA) monomer, ethylene glycol dimethacrylate (EGDMA) as cross linker, and 2,2'-azobisisobutyronitrile (AIBN) as initiator. We constructed the PFF sensor by coating the surface of a glassy carbon electrode (GCE) with 3D-CNTs@MIP and removed the imprinting template by solvent extraction. Morphological and structural characterization reveal that blending of the MIP on the CNT surface significantly increases the selective surface area, leading to greater numbers of imprinting sites for improved sensitivity and electron transfer. The 3D-CNTs@MIP sensor exhibits a fast response with good recognition when applied to PFF detection by cyclic voltammetry and amperometry. The PFF oxidation current signal appears at +0.7 V vs Ag/AgCl using 0.1 M phosphate buffer (pH 7.0) as the carrier solution. The designed 3D-imprinted sensor provides a linear response over the range 0.01-200 µM (r2 = 0.995) with a low detection limit of 0.002 µM (3σ). The sensor was successfully applied to detection of PFF in vegetable samples.

Complexometric and argentometric titrations using thread-based analytical devices.

This work describes analytical approaches based on simple complexometric and argentometric titrations leading to the color change of a novel microfluidic thread-based analytical device (µTAD). The device was fabricated from a cotton thread (15 cm) treated with indicator solution, providing an easy-to-use platform for rapid measurement of analyte concentration in aqueous solution. The thread was immobilized onto a support, being a polypropylene sheet or box platform, to facilitate loading of liquid samples. Interaction between the deposited reagents and analytes in the samples then occurred within a few minutes. This resulted in zones of color change with different lengths along the thread depending on the analyte concentration. The interaction zones can be analyzed by human eyes based on comparison of the zone lengths with the printed scales which are correlated with the analyte concentrations. Complexometric titration using µTADs was initially investigated for Mg(II) determination in water and rubber latex samples. These devices consisted of two threads which were pretreated with Eriochrome Black T (EBT) and then treated with ethylenediaminetetraacetic acid (EDTA) in N-cyclohexyl-3-aminopropanesulfonic acid (CAPS) buffer at pH 10. Both threads were tied together with a central knot before being attached to the box platform prior to the analysis. Load of sample solution (6 µL) resulted in the length of red-violet color product on the threads being proportional to the concentration of Mg(II) in waters and rubber latex samples with the working concentration range of 25-1000 mg L-1. In addition, µTAD with a supporting polypropylene sheet consisting of several threads treated with AgNO3 and K2CrO4 indicators was applied for argentometric titration of chloride ion in water and food seasoning samples. After sample loading (3 µL), the initially red-brown threads turned into white corresponding to formation of AgCl(s) on the threads with a working concentration range of 75-600 mg L-1. Greater selectivity towards Mg(II) and chloride compared with potential interference ions was also observed. All the developed µTADs were applied for analysis of real samples which showed results being in agreement with those obtained by classical titrations.

Use of a Smartphone as a Colorimetric Analyzer in Paper-based Devices for Sensitive and Selective Determination of Mercury in Water Samples.

A smartphone application, called CAnal, was developed as a colorimetric analyzer in paper-based devices for sensitive and selective determination of mercury(II) in water samples. Measurement on the double layer of a microfluidic paper-based analytical device (µPAD) fabricated by alkyl ketene dimer (AKD)-inkjet printing technique with special design doped with unmodified silver nanoparticles (AgNPs) onto the detection zones was performed by monitoring the gray intensity in the blue channel of AgNPs, which disintegrated when exposed to mercury(II) on µPAD. Under the optimized conditions, the developed approach showed high sensitivity, low limit of detection (0.003 mg L-1, 3SD blank/slope of the calibration curve), small sample volume uptake (two times of 2 µL), and short analysis time. The linearity range of this technique ranged from 0.01 to 10 mg L-1 (r2 = 0.993). Furthermore, practical analysis of various water samples was also demonstrated to have acceptable performance that was in agreement with the data from cold vapor atomic absorption spectrophotometry (CV-AAS), a conventional method. The proposed technique allows for a rapid, simple (instant report of the final mercury(II) concentration in water samples via smartphone display), sensitive, selective, and on-site analysis with high sample throughput (48 samples h-1, n = 3) of trace mercury(II) in water samples, which is suitable for end users who are unskilled in analyzing mercury(II) in water samples.

Amperometric flow injection analysis of glucose using immobilized glucose oxidase on nano-composite carbon nanotubes-platinum nanoparticles carbon paste electrode.

We report a novel amperometric glucose biosensor based on glucose oxidase (GOx) immobilized on a carbon nanotube (CNTs)-poly(diallyldimethyl-ammonium chloride) (PDDA)-platinum nanoparticle (PtNPs) modified carbon-paste electrode (CNTs-PDDA-PtNPs/CPE). The CNTs-PDDA-PtNPs composite materials were characterized by TEM and electrochemical techniques. Cyclic voltammetric results reveal direct electron transfer of the immobilized GOx, indicated by two quasi-reversible redox peaks at a potential of 0.37V (vs. Ag/AgCl) in phosphate buffered solution (PBS) (0.10M, pH 7). The biosensor provides good glucose oxidation activity and retention of GOx electrocatalytic activity due to CNTs-PDDA-PtNPs enhancement of the redox response. The carbon paste electrode was installed as working electrode in a flow through electrochemical cell of a flow injection (FI) system. Glucose was quantified using amperometric measurements at 0.5V vs. Ag/AgCl and PBS carrier (0.10M, pH 7.0) at a flow rate of 1.0mLmin-1. The linear working ranges for glucose measurements were 0.1-3mM (r2=0.995) and 5-100mM (r2=0.997), with corresponding sensitivities of 0.127 and 0.060 (µAs) mM-1, respectively. The system provides good precision of 2.8% R.S.D with a calculated detection limit (3S/N) of 15µM. The proposed method was successfully applied to determination of glucose in food and pharmaceutical samples with throughput of 200 samplesh-1.

A sensitive and selective on-line amperometric sulfite biosensor using sulfite oxidase immobilized on a magnetite-gold-folate nanocomposite modified carbon-paste electrode.

We describe a novel amperometric sulfite biosensor, comprising a carbon-paste electrode (Fe3O4@Au-Cys-FA/CPE) modified with immobilized sulfite oxidase (SOx) on a gold-coated magnetite nanoparticle core, encased within a conjugated folic acid (FA) cysteine (Cys) shell. The biosensor electrode was fabricated using a polydimethylsiloxane (PDMS) and mineral oil mixture as binder, which also enhances the physical stability and sensitivity of the electrode. The developed biosensor displays good electrocatalytic activity toward oxidation of H2O2, which occurs by an enzymatic reaction between SOx and sulfite. The Fe3O4@Au-Cys-FA electrode exhibits good electrocatalytic activity, and has good retention of chemisorbed SOx on the electrode because of its large surface area. Sulfite was quantified using amperometric measurements from the Fe3O4@Au-Cys-FA/CPE biosensor, and using an in-house assembled flow cell at +0.35V (vs. Ag/AgCl), with a phosphate buffer carrier (0.10M, pH 7.0) at a flow rate of 0.8mLmin(-1). The system detects sulfite over the range 0.1-200mgL(-1) (r(2)=0.998), with a detection limit of 10µgL(-1) (3σ of blank). The system exhibits acceptable precision (%R.S.D.=3.1%), rapid sample throughput (109samplesh(-1)), and good stability (2w). The developed biosensor shows satisfactory tolerance to potential interferences, such as sugars, anions, ascorbic acid, and ethanol. We applied the developed method to the determination of sulfite content in wines and pickled food extracts, and our results are in good agreement with those obtained by the standard iodometric method.

Chromatic analysis by monitoring unmodified silver nanoparticles reduction on double layer microfluidic paper-based analytical devices for selective and sensitive determination of mercury(II).

This study demonstrates chromatic analysis based on a simple red green blue (RGB) color model for sensitive and selective determination of mercury(II). The analysis was performed by monitoring the color change of a microfluidic Paper-based Analytical Device (µPAD). The device was fabricated by using alkyl ketene dimer (AKD)-inkjet printing and doped with unmodified silver nanoparticles (AgNPs) which were disintegrated when being exposed to mercury(II). The color intensity was detected by using an apparatus consisting of a digital camera and a homemade light box generating constant light intensity. A progressive increase in color intensity of the tested area on the µPAD (3.0mm) was observed with increasing mercury(II) concentration. The developed system enabled quantification of mercury(II) at low concentration with the detection limit of 0.001mgL(-1) (3 SD blank/slope of the calibration curve) and small sample volume uptake (2µL). The linearity range of the calibration curve in this technique was demonstrated from 0.05 to 7mgL(-1) (r(2)=0.998) with good precision (RSD less than 4.1%). Greater selectivity towards mercury(II) compared with potential interference ions was also observed. Furthermore, the percentage recoveries of spiked water samples were in an acceptable range which was in agreement with the values obtained from the conventional method utilizing cold vapor atomic absorption spectrometer (CVAAS). The proposed technique allows a rapid, simple, sensitive and selective analysis of trace mercury(II) in water samples.

Simple flow injection for determination of sulfite by amperometric detection using glassy carbon electrode modified with carbon nanotubes-PDDA-gold nanoparticles.

A new approach is presented for sensitive and selective measurement of sulfite (SO3(2-)) in beverages based on a simple flow injection system with amperometric detection. In this work, the sulfite sensor was a glassy carbon electrode modified with multiwall carbon nanotubes-poly(diallyldimethylammonium chloride)-gold nanoparticles composites (CNTs-PDDA-AuNPs/GC). Electrochemical oxidation of sulfite with this electrode was first studied in 0.1M phosphate buffer (pH 7.0) using cyclic voltammetry. The results indicated that the CNTs-PDDA-AuNPs/GC electrode possesses electrocatalytic activity for the oxidation of sulfite with high sensitivity and selectivity. Sulfite was quantified using amperometric measurement with the new sensor at +0.4V vs Ag/AgCl in conjunction with flow injection. The linear working range for the quantitation of sulfite was 2-200 mg L(-1) (r(2)=0.998) with a detection limit of 0.03 mg L(-1) (3σ of blank) and an estimated precision of 1.5%.The proposed method was successfully applied to the determination of sulfite in fruit juices and wines with a sample throughput of 23 samples per hour.

Electrocatalytic oxidation of ascorbic acid using a poly(aniline-co-m-ferrocenylaniline) modified glassy carbon electrode.

A poly(aniline-co-m-ferrocenylaniline) was successfully synthesized on a glassy carbon electrode (GCE) by electrochemical copolymerization using a scan potential range from -0.3 to +0.9 V (vs. Ag/AgCl) in 0.5 M H2SO4 containing 30% acetonitrile (ACN), 0.1 M aniline (Ani) and 0.005 M m-ferrocenyaniline (m-FcAni). The field emission scanning electron microscope (FESEM) and electrochemical methods were used to characterize the poly(Ani-co-m-FcAni) modified electrode. The poly(Ani-co-m-FcAni)/GCE exhibited excellent electrocatalytic oxidation of ascorbic acid (AA) in citrate buffer solution (CBS, pH 5.0). The anodic peak potential of AA was shifted from +0.55 V at the bare GCE to +0.25 V at the poly(Ani-co-m-FcAni)/GCE with higher current responses than those seen on the bare GCE. The scan number at the 10th cycle was selected as the maximum scan cycle in electrochemical polymerization. The limit of detection (LOD) was estimated to be 2.0 µM based on the signal-to-noise ratio (S/N = 3). The amperometric responses demonstrated an excellent selectivity for AA determination over glucose (Glu) and dopamine (DA).