In-situ ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction of triazine herbicides

We report on the determination of the triazine herbicides ametryne, prometryne, terbuthylazine and terbutryn in water samples. The herbicides are extracted by in-situ ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction and then determined by high-performance liquid chromatography. This is a new method for extraction that has the advantages of requiring less volume of ionic liquid (IL) than other methods and at the same time is quite fast. The type and volume of IL, the type and volume of disperser, irradiation temperature, extraction time and salt concentration were optimized. Figures of merit include linear regression coefficients between 0.9992 and 0.9995, acceptable recoveries (88.4–114?%), relative standard deviations of 1.6–6.2?%, and limits of detection between 0.52 and 1.3?μg?L^?1.

Determination of twelve herbicides in tobacco by a combination of solid–liquid–solid dispersive extraction using multi-walled carbon nanotubes, dispersive liquid-liquid micro-extraction, and detection by GC with triple quadrupole mass spectrometry

We report on a method for the determination of twelve herbicides using solid–liquid–solid dispersive extraction (SLSDE), followed by dispersive liquid-liquid micro-extraction (DLLME) and quantitation by gas chromatography with triple quadrupole mass spectrometric detection. SLSDE was applied to the extraction of herbicides from tobacco samples using multi-walled carbon nanotubes (MWCNTs) as clean-up adsorbents. The effect of the quantity of MWCNTs on SLSDE, and of type and volume of extraction and disperser solvents and of salt effect on DLLME were optimized. Good linearity is obtained in the 5.0 - 500 μg kg^?1 concentration range, with regression coefficients of >0.99. Intra-day and inter-day repeatability, expressed as relative standard deviations, are between 3 and 9 %. The recoveries in case of herbicide-spiked tobacco at concentration levels of 20.0, 50.0 and 100.0 g kg^?1 ranged from 79 to 105 %, and LODs are between 1.5 and 6.1 μg kg^?1. All the tobacco samples were found to contain butralin and pendimethalin at levels ranging from 15.8 to 500.0 μg kg^?1.

Magnetic molecular imprint-based extraction of sulfonylurea herbicides and their determination by capillary liquid chromatography

We have developed a simple method for the extraction of sulfonylurea herbicides (SUHs) from environmental water samples. It is based on a magnetic molecular imprint (MMIP) as a sorbent. The MMIP was prepared using metsulfuron-methyl as the template molecule, methacrylic acid as the functional monomer, trimethylolpropane trimethacrylate as the cross-linking agent, and magnetite as the magnetic component. Extraction can be carried out by blending and stirring water sample, extraction solvent and MMIP. Once the extraction is completed, the MMIP containing the SUHs can be separated from the sample matrix with a magnet. The SUHs desorbed from the polymers were then quantified by capillary liquid chromatography with diode array detection. The limits of quantification are in the range of 0.08 to 0.1 ng?mL^?1. Repeatabilities of peak areas and retention times range from 2.9 % to 4.0 % and from 0.1 % to 0.3 %, respectively. The method was successfully applied to the determination of the SUHs bensulfuron-methyl, metsulfuronmethyl, pyrazosulfuron-methyl, thifensulfuron-methyl, and triasulfuron in waste water samples. Recoveries range from 94.3 % to 102.3 %.

Highly sensitive and selective voltammetric detection of mercury(II) using an ITO electrode modified with 5-methyl-2-thiouracil, graphene oxide and gold nanoparticles

We have developed an electrochemical sensor for highly selective and sensitive determination of Hg(II). It is based on the specific binding of 5-methyl-2-thiouracil (MTU) and Hg(II) to the surface of an indium tin oxide (ITO) electrode modified with a composite made from graphene oxide (GO) and gold nanoparticles (AuNPs). This leads to a largely enhanced differential pulse voltammetric response for Hg(II). Following optimization of the method, a good linear relationship (R?=?0.9920) is found between peak current and the concentration of Hg(II) in the 5.0–110.0 nM range. The limit of detection (LOD) is 0.78 nM at a signal-to-noise ratio of 3. A study on the interference by several metal ions revealed no interferences. The feasibility of this method was demonstrated by the analyses of real water samples. The LODs are 6.9, 1.0 and 1.9 nM for tap water, bottled water and lake water samples, respectively, and recoveries for the water samples spiked with 8.0, 50.0 and 100.0 nM were 83.9–96.8 %, with relative standard deviations ranging from 3.3 % to 5.2 %.

Graphene oxide functionalized magnetic nanoparticles as adsorbents for removal of phthalate esters

We show that magnetic nanoparticles can be functionalized with graphene oxide (GO-MNPs) in two reaction steps, and that such nanoparticles can be used as adsorbents for the removal of phthalate esters (PAEs) from water samples. The GO-MNPs were characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, zeta potential, and vibrating sample magnetometer. The impacts of contact time, sample pH, ionic strength and sample volume on the adsorption process were investigated. The maximum adsorption capacity for diethyl phthalate was calculated to be 8.71 mg g^?1 according to the Langmuir adsorption isotherm. The adsorption efficiency was tested by removal of PAEs. More than 99 % of the total quantity of PAEs (0.12 mg L^?1) in 500 mL real water samples can be removed when GO-MNPs (275–330 mg) were used as an adsorbent. In addition, other species (estriol and fluorene) containing benzene rings were also almost completely removed with the PAEs using GO-MNPs, indicating that GO-MNPs are suitable for the removal of the species containing π-electron system through π-π interactions.

Dual cloud point extraction coupled with hydrodynamic-electrokinetic two-step injection followed by micellar electrokinetic chromatography for simultaneous determination of trace phenolic estrogens in water samples

A dual cloud point extraction (dCPE) off-line enrichment procedure coupled with a hydrodynamic–electrokinetic two-step injection online enrichment technique was successfully developed for simultaneous preconcentration of trace phenolic estrogens (hexestrol, dienestrol, and diethylstilbestrol) in water samples followed by micellar electrokinetic chromatography (MEKC) analysis. Several parameters affecting the extraction and online injection conditions were optimized. Under optimal dCPE–two-step injection–MEKC conditions, detection limits of 7.9–8.9 ng/mL and good linearity in the range from 0.05 to 5 μg/mL with correlation coefficients R ²?≥?0.9990 were achieved. Satisfactory recoveries ranging from 83 to 108 % were obtained with lake and tap water spiked at 0.1 and 0.5 μg/mL, respectively, with relative standard deviations (n?=?6) of 1.3–3.1 %. This method was demonstrated to be convenient, rapid, cost-effective, and environmentally benign, and could be used as an alternative to existing methods for analyzing trace residues of phenolic estrogens in water samples.

Selective microextraction of carbaryl and naproxen using organic–inorganic monolithic columns containing a double molecular imprint

We report on an organic–inorganic hybrid material that was double imprinted with the insecticide carbaryl and the anti-inflammatory drug naproxen by a single-step method and that can serve for selective microextraction of the two analytes. The materials, in the form of monolithic columns, were characterized by scanning electron microscopy and Fourier transform IR spectra. A simple, rapid and sensitive method was then developed for the simultaneous determination of carbaryl and naproxen in lettuce and river water using these columns for microextraction, HPLC for separation, and a diode array for UV detection. The limits of detection (at S/N?=?3) and quantification (at S/N?=?10) are in the ranges of 2.5 – 8.8 μg kg^?1 and 2.3 – 8.0 μg L^?1 for lettuce and Yangtze River water, respectively. The recoveries of this method range from 93.0 to 108 % (in case of analyzing lettuce and river water), and relative standard deviations are <8.9 %.

Paper-based three-dimensional microfluidic device for monitoring of heavy metals with a camera cell phone

A 3D paper-based microfluidic device has been developed for colorimetric determination of selected heavy metals in water samples by stacking layers of wax patterned paper and double-sided adhesive tape. It has the capability of wicking fluids and distributing microliter volumes of samples from single inlet into affrays of detection zones without external pumps, thus a range of metal assays can be simply and inexpensively performed. We demonstrate a prototype of four sample inlets for up to four heavy metal assays each, with detection limits as follows: Cu (II)?=?0.29 ppm, Ni(II)?=?0.33 ppm, Cd (II)?=?0.19 ppm, and Cr (VI)?=?0.35 ppm, which provided quantitative data that were in agreement with values gained from atomic absorption. It has the ability to identify these four metals in mixtures and is immune to interferences from either nontoxic metal ions such as Na(I) and K(I) or components found in reservoir or beach water. With the incorporation of a portable detector, a camera mobile phone, this 3D paper-based microfluidic device should be useful as a simple, rapid, and on-site screening approach of heavy metals in aquatic environments.

Determination of chlorobenzenes in water samples based on fully automated microextraction by packed sorbent coupled with programmed temperature vaporization–gas chromatography–mass spectrometry

A fully automated method consisting of microextraction by packed sorbent (MEPS) coupled directly to programmed temperature vaporizer–gas chromatography–mass spectrometry (PTV–GC–MS) has been developed to determine the 12 chlorobenzene congeners (chlorobenzene; 1,2-, 1,3-, and 1,4-dichlorobenzene; 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzene; 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetrachlorobenzene; pentachlorobenzene; and hexachlorobenzene) in water samples. The effects of the variables on MEPS extraction, using a C18 sorbent, and the instrumental PTV conditions were studied. The internal standard 1,4-dichlorobenzene d4 was used as a surrogate. The proposed method afforded good reproducibility, with relative standard deviations (RSD %) lower than 12 %. The limits of detection varied between 0.0003 μg L^?1 for 1,2,3,4-tetrachlorobenzene and 0.07 μg L^?1 for 1,3- and 1,4-dichlorobenzene, while those of quantification varied between 0.001 μg L^?1 and 0.2 μg L^?1 for the same compounds. Accuracy of the proposed method was confirmed by applying it to the determination of chlorobenzenes in different spiked water samples, including river, reservoir, and effluent wastewater.

REMUS100 AUV with an integrated microfluidic system for explosives detection

Quantitating explosive materials at trace concentrations in real-time on-site within the marine environment may prove critical to protecting civilians, waterways, and military personnel during this era of increased threat of widespread terroristic activity. Presented herein are results from recent field trials that demonstrate detection and quantitation of small nitroaromatic molecules using novel high-throughput microfluidic immunosensors (HTMI) to perform displacement-based immunoassays onboard a HYDROID REMUS100 autonomous underwater vehicle. Missions were conducted 2–3 m above the sea floor, and no HTMI failures were observed due to clogging from biomass infiltration. Additionally, no device leaks were observed during the trials. HTMIs maintained immunoassay functionality during 2 h deployments, while continuously sampling seawater absent without any pretreatment at a flow rate of 2 mL/min. This 20-fold increase in the nominal flow rate of the assay resulted in an order of magnitude reduction in both lag and assay times. Contaminated seawater that contained 20–175 ppb trinitrotoluene was analyzed.

Fluorometric determination of paraoxon in human serum using a gold nanoparticle-immobilized organophosphorus hydrolase and coumarin 1 as a competitive inhibitor

A dimeric organophosphorus hydrolase (OPH; EC 3.1.8.1; 72 kDa) was isolated from wild-type bacteria, analyzed for its 16s rRNA sequence, purified, and immobilized on gold nanoparticles (AuNPs) to form the transducer part of a biosensor. The isolated strain was identified as Pseudomonas aeruginosa. The AuNPs were characterized by transmission electron microscopy and localized surface plasmon resonance. Covalent binding of OPH to the AuNPs was confirmed by spectrophotometry, enzymatic activity assays, and FTIR spectroscopy. Coumarin 1, a competitive inhibitor of OPH, was used as a fluorogenic probe. The bioconjugates quench the emission of coumarin 1 upon binding, but the addition of paraoxon results in an enhancement of fluorescence that is directly proportional to the concentration of paraoxon. The gold-OPH conjugates were then used to determine paraoxon in serum samples spiked with varying levels of paraoxon. The method works in the 50 to 1,050 nM concentration range, has a low standard deviation (with a CV of 5.7–11 %), and a detection limit as low as 5?×?10^?11 M.

Immunochromatographic lateral flow strip for on-site detection of bisphenol A

We have developed a lateral flow assay (LFA) for the detection of bisphenol A (BPA) in water samples. Antibody against BPA was labeled with gold nanoparticles, and these conjugates were used as the recognition probes for the construction of an LFA strip. The diameter of the gold nanoparticles, the amount of antibody, the pH of the buffer, and the categories of the conjugation pad were optimized. The resulting method has a (visual) detection limit of 5 ppb, and of 0.92 ppb if used in combination with professional software. This LFA displays excellent specificity and was applied to spiked water samples with satisfactory results.

Ionization of pesticides using a far-ultraviolet femtosecond laser in gas chromatography/time-of-flight mass spectrometry

The fourth harmonic emission (200 nm) of a femtosecond Ti:sapphire laser (35 fs) was generated and used in the multiphoton ionization of 49 pesticides in gas chromatography/time-of-flight mass spectrometry. The limit of detection was improved when the ionization source from the third harmonic emission (267 nm) was replaced with the fourth harmonic emission for several pesticide molecules that contained no conjugated double bonds since their absorption bands are located in the far-ultraviolet region. This analytical instrument was used in the analysis of a series of real samples including potatoes, carrots, and cabbage, and a signal suspected to arise from di-allate was observed for the potato sample.

Rapid extraction and preservation of genomic DNA from human samples

Simple and rapid extraction of human genomic DNA remains a bottleneck for genome analysis and disease diagnosis. Current methods using microfilters require cumbersome, multiple handling steps in part because salt conditions must be controlled for attraction and elution of DNA in porous silica. We report a novel extraction method of human genomic DNA from buccal swab and saliva samples. DNA is attracted onto a gold-coated microchip by an electric field and capillary action while the captured DNA is eluted by thermal heating at 70 °C. A prototype device was designed to handle four microchips, and a compatible protocol was developed. The extracted DNA using microchips was characterized by qPCR for different sample volumes, using different lengths of PCR amplicon, and nuclear and mitochondrial genes. In comparison with a commercial kit, an equivalent yield of DNA extraction was achieved with fewer steps. Room-temperature preservation for 1 month was demonstrated for captured DNA, facilitating straightforward collection, delivery, and handling of genomic DNA in an environment-friendly protocol.

Solid-phase microfibers based on modified single-walled carbon nanotubes for extraction of chlorophenols and organochlorine pesticides

Solid-phase microextraction (SPME) based on carboxylated single-walled carbon nanotube fibers was used to extract several chlorophenols (CPs) and organochlorine pesticides (OCPs) from aqueous samples prior to their determination by GC with electron capture detection. The main parameters affecting microextraction (temperature, time, stirring rate and salting-out effect) and the conditions of the thermal desorption in the GC injector were optimized. Compared with commercial SPME fibers, the fiber presented better selectivity and sensitivity. Linear response was found for the concentration range between 2 and 1000 ng L^?1 (20–1000 ng L^?1 for CPs), and the limits of detection were in the range from 0.07 to 4.36 ng L^?1. The repeatability expressed as relative standard deviation ranged from 4.1 % to 8.2 % and the fiber-to-fiber reproducibility for four prepared fibers was between 6.5 % and 10.8 %. The method was successfully applied to the analysis of CPs and OCPs in lake water and waste water samples. Recovery was tested with spiked lake water and waste water samples, with values ranging from 89.7 % to 101.2 % in case of waste water samples.

A highly sensitive caffeine immunoassay based on a monoclonal antibody

A new immunoassay has been developed based on a commercially available anti-caffeine monoclonal antibody and a de novo synthesized tracer, using horseradish peroxidase and UV–visible detection. Caffeine, which is frequently found in surface waters, can be quantified with a relative error lower than 20% for concentrations above 0.025 μg L^?1 (limit of quantitation, direct analysis). The limit of detection is 0.001 μg L^?1 and can be reduced by solid-phase extraction (SPE). Moreover, with minor adaptations, the assay can be used to quantify caffeine in several beverages, shampoo, and caffeine tablets. The results obtained by ELISA correlate well with those from liquid chromatography–tandem mass spectrometry (LC–MS–MS) for the tested matrices. Several surface waters from Berlin were analysed and all tested positive for caffeine, with concentrations higher than 0.030 μg L^?1. In one run 66 samples can be analysed within 2 h.

Desorption Mass Spectrometry for Nonvolatile Compounds Using an Ultrasonic Cutter

In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40 kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1 ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.

A highly selective fluorescent probe for the detection of palladium(II) ion in cells and aqueous media

We report on a fluorescent probe for the optical (and even bare eye) detection of palladium(II) ion which causes the probe to undergo a strong increase in absorbance and fluorescence. The probe is easily synthesized from rhodamine B hydrazide and 9-anthraldehyde and displays high selectivity over other metal ions. Fluorescence intensity and absorbance are linearly proportional to the concentration of Pd(II) in the 0–7 μM and 0–1 μM concentration range, respectively, with detection limits of 0.21 μM and 0.03 μM. The probe can detect Pd(II) with virtually no interferences by other metal ions and anions. It was applied to intracellular imaging of Pd(II) in living cells and to its determination in a palladium-containing catalyst and in spiked water samples.

Electrochemically controlled solid-phase micro-extraction of proline using a nanostructured film of polypyrrole, and its determination by ion mobility spectrometry

We report on a fast, simple and accurate method for the determination of proline in urine samples by employing a nanostructured film of conducting polypyrrole for electrochemically controlled solid-phase microextraction, and ion mobility spectrometry (IMS) for detection. This method has the advantages of simple sample preparation and a sensitivity of IMS to proline that is higher than that for other amino acids. The calibration curve is linear in the range of 0.5–60 μg L^?1 (4–521 nmol L^?1), and the detection limit is 0.2 μg L^?1. The electrochemical potentials for uptake and release were optimized. The method was successfully applied to the clean-up and quantitation of trace amounts of proline in urine samples.

Magnetic titanium oxide nanoparticles for hemimicelle extraction and HPLC determination of organophosphorus pesticides in environmental water

We report on a method for the extraction of organophosphorus pesticides (OPPs) from water samples using mixed hemimicelles and magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) modified by cetyltrimethylammonium. Fe₃O₄@TiO₂ nanoparticles were synthesized by a hydrothermal process and then characterized by scanning electron microscopy and Fourier transform IR spectrometry. The effects of the quantity of surfactant, extraction time, desorption solvent, pH value, extraction volume and reuse of the sorbent were optimized with respect to the extraction of OPPs including chlorpyrifos, dimethoate, and trichlorfon. The extraction method was applied to analyze OPPs in environmental water using HPLC along with UV detection. The method has a wide linear range (100–15,000 ng L^?1), good linearity (r?>?0.999), and low detection limits (26–30 ng L^?1). The enrichment factor is ~1,000. The recoveries (at spiked levels of 100, 1,000 and 10,000 ng L^?1) are in the range of 88.5–96.7 %, and the relative standard deviations range from 2.4 % to 8.7 %.