Ion mobility spectrometry as a fast analytical tool in benzalkonium chloride homologs determination.

Abstract A novel procedure is proposed for the determination by ion mobility spectrometry (IMS) of C 12 , C 14 and C 16 benzalkonium chloride (BAC) homologs. The proposed method requires minimum sample treatment and the measurement was made in less than one minute. A high sensitivity was obtained for BAC determination by IMS with limit of detection values from 37 to 69 µg L −1 . Accuracy of the proposed methodology was evaluated through the analysis of aqueous and alcoholic samples spiked with BAC at concentration levels from 0.002% to 20% (w/v), providing recovery values from 91% to 104%. BAC was determined in sanitary alcohols, nasal sprays, postharvest products, algaecides, and treated s…

Development of a sensitive and specific enzyme-linked immunosorbent assay for the determination of fludioxonil residues in fruit juices

Fludioxonil is a fungicide with a singular mode of action that is widely employed in the treatment of fruit crops. A competitive enzyme-linked immunosorbent assay (cELISA) has been developed and validated for the determination of residues of this fungicide in fruit juices. A collection of monoclonal antibodies (mAbs) against the fungicide fludioxonil has been produced and characterized using direct and indirect cELISAs. The high affinity achieved (IC50lower than 0.5 μg L-1) considerably improved that obtained with previous polyclonal antibodies. The proposed cELISA was applied to the analysis of fludioxonil residues in apple juice and red grape must samples with a limit of quantification of…

Amphetamine-type stimulants analysis in oral fluid based on molecularly imprinting extraction

Abstract A methamphetamine-based molecularly imprinted polymer (MIP) has been prepared by bulk polymerization to recognize new psychoactive substances (NPS) of the amphetamine, cathinones and 2C families in oral fluid samples, being the first precedent of a synthetized MIP for the extraction and preconcentration 32 NPS including amphetamine type substances and synthetic cathinones from oral fluids. Pre-polymerization complex and resulting materials were appropriately characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption-desorption isotherms. Appropriateness of the material for the specific recognition of the target analytes was also evaluated through …

Hard cap espresso extraction-stir bar preconcentration of polychlorinated biphenyls in soil and sediments.

Abstract A Nespresso © hard cap espresso machine has been employed for the quantitative extraction of polychlorinated biphenyls (PCBs) from sediments and soils. Sample extraction was performed from five grams of sample in less than 40 s, with 200 mL ethanol 40% (v/v) in water and PCBs were concentrated using stir bar sorptive extraction (SBSE) and determined by thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS-MS). Eleven PCB congeners (28, 52, 77, 80, 81, 101, 118, 138, 153,169, and 180) were determined in soils and sediments with limits of quantification in the 0.03–0.08 ng g −1 range. Extraction efficiency was established by the analysis of soil samples spiked with…

Metabolism of third generation synthetic cannabinoids using zebrafish larvae.

Synthetic cannabinoids are the second largest group of new psychoactive substances reported by the United Nations Office on Drugs and Crime in the last decade and case reports bring attention to its high potency effects and its severe toxicity, including fatalities. Moreover, synthetic cannabinoids are usually entirely metabolized and metabolic pathways for many new generation synthetic cannabinoids are still unknown. In this study, the metabolism of five third generation synthetic cannabinoids were evaluated using zebrafish (Danio rerio) larvae as 24-hours in vivo model studied within 5 days after fertilization. The studied synthetic cannabinoids were MMB-CHMICA, ADB-CHMICA, ADB-CHMINACA, …

Flavonoid determination in onion, chili and leek by hard cap espresso extraction and liquid chromatography with diode array detection

Abstract A low cost extraction procedure, based on the use of a hard cap espresso machine, has been developed for the extraction of myricetin, quercetin, luteolin and kaempferol from vegetables by using 50 mL of ethanol in water (80% v/v) in

Antibody generation and immunoassay development in diverse formats for pyrimethanil specific and sensitive analysis

Immunochemical techniques are complementary tools to modern analytical requirements. These methods rely on the production of immunoreagents with adequate binding properties. In the present study, a rationally designed and functionalized derivative of pyrimethanil-a modern anilinopyrimidine fungicide-was synthesized in order to generate for the first time high-affinity and selective antibodies to this xenobiotic. A single coupling procedure-based on hapten activation using N,N′-disuccinimidyl carbonate and purification of the active ester-was followed to prepare both immunizing and assay conjugates. Polyclonal antibodies were produced and characterized by enzyme-linked immunosorbent assay (E…

Hierarchical porous carbon with designed pore architecture and study of its adsorptive properties

Abstract Ordered mesoporous carbon nanoparticles have been synthesized by a nanocasting procedure from furfuryl alcohol impregnation into alumino–silica UVM-7 material. By a proper adjustment of the synthesis parameters, furfuryl alcohol volume vs . template pore volume, it was possible to obtain a carbonaceous templated material which keeps the hierarchical bimodal porosity of the silica together with its high surface area (>1000 m 2 /g), as it was confirmed by means of electron transmission microscopy and N 2 adsorption isotherms. This carbon material was evaluated by testing it as a sorbent for several pesticides in aqueous solutions. Its absorption efficiency was compared with typical c…

Development of competitive enzyme-linked immunosorbent assays for boscalid determination in fruit juices

Abstract Boscalid is a modern, broad-spectrum carboxamide pesticide highly efficient against most fungal diseases affecting valuable crops. In this study, a boscalid-mimicking derivative with a six-carbon spacer arm replacing the chlorine atom at the pyridine ring of the target molecule was synthesized and coupled to carrier proteins. Following rabbit immunization, antibodies against this agrochemical were obtained for the first time, and they were characterised in terms of affinity and specificity, tolerance to solvents, and robustness to changes in buffer pH and ionic strength, using two assay formats. Both of the optimised immunoassays showed limits of detection below 0.1 μg/L. Moreover,…

Immunoreagent generation and competitive assay development for cyprodinil analysis.

Cyprodinil is an anilinopyrimidine fungicide applied worldwide for the prevention and treatment of highly destructive plant diseases in a large variety of crops, including cereals, fruits, and vegetables. This paper describes the development of the first reported immunoassays for cyprodinil. Two original haptens have been synthesized and conjugated to different carrier proteins, and polyclonal antibodies have been produced. Moreover, competitive enzyme-linked immunosorbent assays have been developed and characterized for the analysis of this widely used pesticide. The influence of organic solvents and buffer conditions over the assay analytical parameters was studied. The IC 50 values of th…

In situ derivatization for double confirmation of 2C–C in oral fluids by ion mobility spectrometry

Ion mobility spectrometry (IMS) is a powerful tool to carry out quick and sensitive detection of illicit activities and has been employed for the determination of the psychedelic drug 2,5-dimethoxy-4 chlorophenethylamine (2C–C) in oral fluid samples. Saliva samples were extracted with chloroform and analysed by IMS reaching a limit of detection (LOD) of 14 μg L−1. Nevertheless, IMS has a scarce resolution and selectivity of the method can be often compromised by the presence of potential interferents with similar molecular weights and drift times. Thus, a rapid and in situ derivatization with acetone, to form the corresponding imine, has been proposed in the present study to confirm the pre…

Sample preparation strategies for the determination of psychoactive substances in biological fluids

This review focuses on the existing analytical procedures for the determination of new psychoactive substances (NPS) in biological fluids by chromatographic methods. Direct analysis of samples is scarcely employed and most proposed methodologies include a sample pre-treatment in order to remove matrix interferents and, in some cases, pre-concentrate extracts. Current extraction methods for NPS determination in plasma/serum, urine, and oral fluids have been widely discussed, such as liquid-liquid, solid-phase, and micro extraction approaches, highlighting the advantages and drawbacks of the proposed extraction methodologies. Regarding microextraction approaches, techniques like microextracti…

Determination of Third-Generation Synthetic Cannabinoids in Oral Fluids.

Abstract A procedure has been developed for the determination of third-generation synthetic cannabinoids in oral fluid samples by using a semi-automated microextraction by packed sorbent (MEPS) procedure and gas chromatography–mass spectrometry (GC–MS) determination. Five synthetic cannabinoids were employed as model compounds 5F-ADB, MMB-CHMICA, THJ-2201, CUMYL-4CN-BINACA and MDMB-CHMCZCA. The most adequate operative conditions for MEPS were evaluated giving quantitative recoveries, from 89 to 124%, in synthetic and field saliva samples spiked with 125 and 250 μg/L of the studied cannabinoids, with the exception of MDMB-CHMCZCA in field saliva samples that provided slightly lower recoverie…

Optimization of large-volume injection for the determination of polychlorinated biphenyls in children's fast-food menus by low-resolution mass spectrometry.

International audience; This study includes the determination of five indicator polychlorinated biphenyls (PCBs) (52, 101, 153, 138, and 180), six non-ortho PCBs (35, 80, 81, 77, 126, and 169), and two mono-ortho PCBs (28 and 118) in fast food for children. A freeze-dried sample of 10 g is extracted by using pressurized n-hexane in two 5 min cycles at 120 degrees C and 100 mbar. Fatty extracts were cleaned up by means of acetonitrile/n-hexane partitioning and gel-permeation chromatography. The fractionation of non-ortho, mono-ortho, and indicator PCBs was made on graphitized carbon solid-phase extraction cartridges by using n-hexane, n-hexane/toluene (99:1, v/v), and toluene as elution solv…

Moiety and linker site heterologies for highly sensitive immunoanalysis of cyprodinil in fermented alcoholic drinks

Cyprodinil is a new-generation anilinopyrimidine fungicide widely used in crop protection and frequently found in fruits. In this study, novel derivatives of cyprodinil with linker site heterologies were synthesized and employed in order to produce antibodies with enhanced affinity. Moreover, moiety-heterologous haptens were designed and prepared for assay sensitivity improvement. Two competitive enzyme-linked immunosorbent assays for the analysis of this active substance were developed using direct and indirect formats, achieving IC50 values around 0.15 μg/L. Analytical figures of merit and usability of the optimized assays were evaluated with wine and cider as model food processed matrice…

Determination of volatile organic compounds in contaminated air using semipermeable membrane devices

Abstract Semipermeable membrane devices (SPMDs) were evaluated as passive samplers for the determination of 26 volatile organic compounds (VOCs) in contaminated air of occupational environments. A direct methodology based on the use of head-space-gas chromatography–mass spectrometry (HS-GC–MS) was developed for VOCs determinations in SPMDs, without any sample pre-treatment and avoiding the use of solvents. A desorption temperature of 150 °C for 10 min was sufficient for a sensitive VOCs determination providing limits of detection in the range of 15 ng SPMD−1 for 21 of 26 studied compounds. Linear and equilibrium uptake models were established for each VOC from compound isotherms. Highly vol…

Uptake and translocation monitoring of imidacloprid to chili and tomato plants by molecularly imprinting extraction - ion mobility spectrometry

Abstract The degradation of imidacloprid in soil and its uptake and translocation to chili and tomato plants was evaluated, as a proof of concept, of the possibilities of the combination of molecularly imprinted polymers (MIPs) and ion mobility spectrometry (IMS) for a fast and sensitive bioprocesses monitoring tool. To do it, a method based on the selective extraction of imidacloprid from soil and plant materials was developed. In the selected conditions, the MIP-IMS procedure provided a recovery of imidacloprid in soil and plant samples from 102 to 114%, for spiked concentration levels from 0.2 to 2.0 μg g−1. Precision of the methodology, expressed as the relative standard deviation (RSD)…

Ready Access to Proquinazid Haptens via Cross-Coupling Chemistry for Antibody Generation and Immunoassay Development.

17 pages, 4 tables, 5 figures.-- Publisher's PDF

Development and Evaluation of Paper-Based Devices for Iron(III) Determination in an Advanced Undergraduate Laboratory

We describe a paper-based microfluidic device for iron(III) assay in an applied instrumental analysis laboratory. Simple and convenient devices were fabricated by the students using patterning of f...

Green Analytical Chemistry

Rationally designed haptens for highly sensitive monoclonal antibody-based immunoanalysis of fenhexamid.

Immunochemical methods have been consolidated during the last few years as complementary analytical strategies for chemical contaminant and residue determination. However, generation of suitable immunoreagents for small organic molecules demands adequate hapten design. In this study, fenhexamid was considered as a model compound and novel haptens were designed and synthesized in order to evaluate the influence of the linker tethering site on antibody binding properties and immunoassay parameters. Haptens were conceived with the spacer arm at different positions, while the more antigenic aromatic moiety was kept free. The synthesis of these functionalized compounds was accomplished by total …

Selective determination of clenbuterol residues in urine by molecular imprinted polymer—Ion mobility spectrometry

Abstract Clenbuterol is banned for sports use and strictly regulated in livestock industry. In this study, a procedure for the determination of clenbuterol residues in water and urine has been developed using selective supports combined with ion mobility spectrometry (IMS) determination. A molecular imprinted polymer (MIP) was used for efficient clean-up and preconcentration of clenbuterol followed to a dispersive liquid-liquid microextraction (DLLME) in order to improve selectivity and sensitivity of IMS determinations. Quantitative recoveries from 81 to 99% were obtained for water and spiked urine samples using MIP-DLLME-IMS method. A precision of 4.5%, established as the relative standar…

Environmental applications (air)

Abstract The use of solid sorbent-based devices for the monitoring of contaminants in the air is a widespread trend due to its versatility, physicochemical stability, and high enrichment factor. Active and passive sampling strategies have been developed for air monitoring using different materials, such as carbon-based organic polymers and inorganic sorbents. It has been updated in the literature regarding the most recent applications of the use of solid sorbent-based samplers for the monitoring of air in different sites such as rural, urban, industrialized, and indoor areas, including workplace environments for the evaluation of occupational exposure risks.

Development of a simple and low cost device for vapour phase Fourier Transform Infrared spectrometry determination of ethanol in mouthwashes

Abstract A new vapour phase manifold coupled with Fourier Transform Infrared (FTIR) spectroscopy was developed for ethanol determination in mouthwashes. Two microliters of samples were injected, without any previous pre-treatment into a reactor heated at 70 °C, and the vapour phase generated transported to the FTIR spectrometer using a carrier nitrogen flow of 6 ml min−1. FTIR spectra were continuously recorded, as a function of time, by accumulating two scans and employing 8 cm−1 nominal resolution. Analytical measurements for ethanol were made in the range from 1130 to 992 cm−1 with a baseline defined between 1158 and 957 cm−1. After ethanol measurement the carrier flow was increased to 3…

Assessment of air passive sampling uptakes for volatile organic compounds using VERAM devices

Abstract A calibration chamber has been designed and employed for the simple and easy determination of uptake sampling rate (RS) of volatile organic compounds (VOCs) from air using passive samplers. A flow of clean air was continuously spiked, at a constant VOC concentration, by the microinjection of a standard solution by means of a T-type tube. The developed system allowed the complete evaporation at room temperature of the standard solution in acetone and the air concentration of VOCs was easily controlled by the regulation of the clean air flow, the standard solution concentration and its flow. Active sampling was employed for monitoring the true concentration of the evaluated compounds…

Unexpected identification and characterization of a cathinone precursor in the new psychoactive substance market: 3',4'-methylenedioxy-2,2-dibromobutyrophenone.

Abstract 3′,4′-methylenedioxy-2,2-dibromobutyrophenone has been identified and fully characterized in a sample obtained from an anonymous consumer acquired as ketamine through the Internet market. The substance has been deeply characterized by using standard and high performance analytical techniques such as: attenuated total reflectance-infrared spectroscopy, gas chromatography–mass spectrometry, high-resolution mass spectrometry, elemental analysis, and nuclear magnetic resonance, including 1H, 13C, distortionless enhancement by polarization transfer, two dimensional homonuclear 1H-1H correlation spectroscopy, and 1H-13C heteronuclear single-quantum correlation spectra. 3′,4′-methylenedio…

Monoclonal antibody-based immunoassays for cyprodinil residue analysis in QuEChERS-based fruit extracts

Cyprodinil is among the most common agrochemical residues found in highly perishable fruits, such as strawberries. In the present study, high-affinity monoclonal antibodies to this anilinopyrimidine fungicide were raised for the first time with the aim to produce valuable immunochemical analytical assays. Cyprodinil bioconjugates and the generated novel monoclonal antibodies were employed for sensitive competitive immunoassay development in two different formats. The limits of detection of the optimized assays were 20 and 30 ng L-1 for the indirect and direct assay, respectively. Influence over assay parameters of different physicochemical factors was studied. Strawberry samples were extrac…

Environmental impact of Recover cotton in textile industry

A comparative evaluation of the life cycle assessment (LCA) of Recover cotton, obtained from recycled garments, and virgin one, cultivated from traditional and organic crops, has been made based on the quantification of environmental impact categories, such as abiotic depletion, global warming, water use, acidification and eutrophication potential. LCA data reported in the literature for the steps of cultivation, ginning/cutting, and dyeing were compared in order to clearly show the environmental advantages of moving from traditional practices, to organic cultivation and the use of Recover cotton, a novel procedure that involves the production of cotton yarns from coloured and well characte…

Hard Cap Espresso Machine Extraction of Polyphenolic Compounds from Pulses

A hard cap espresso machine was employed for the extraction of polyphenolic compounds from food samples as dry legumes and pulses. 100 mg of ground dry sample was mixed with a dispersing agent and placed in a refillable stainless steel capsule with a borosilicate filter. A complete polyphenol extraction was achieved by using 150 mL ethanol 50 % (v/v) in water and determined by Folin-Ciocalteu spectrophotometric method. The method provided a limit of detection of 0.4 mg g<sup>-1</sup>. The whole extraction procedure was achieved in less than one minute using the mild extraction conditions of 72°C and 19 bars given by the domestic machine. Fifteen varieties of food samples (3 lent…

Determination of the new psychoactive substance dichloropane in saliva by microextraction by packed sorbent – Ion mobility spectrometry

Abstract A simple procedure based on microextraction by packed sorbent (MEPS) has been proposed for the extraction of dichloropane in oral fluids and its determination by ion mobility spectrometry (IMS). Extraction conditions such as type of sorbent (octyl and octadecyl silica), sample pH, number of sample loadings, and elution volume were evaluated to obtain the most appropriate values. Dichloropane was extracted from saliva samples using C8 MEPS, loading with 100 μL sample (adjusted to pH 7) in 4 cycles, washing with 100 μL deionized water, and eluting with 50 μL 2-propanol in 10 cycles. The proposed MEPS procedure has been validated in terms of linearity, accuracy, and precision. A limit…

Low temperature headspace desorption of volatile organic compounds trapped in air sampling solid-supports

Environmental context. The monitoring of volatile organic compounds (VOCs) in air is of great importance for air quality on both local and global scales. The determination of VOCs can be carried out by gas chromatography–mass spectrometry (GC-MS) after active or passive sampling and (high temperature) thermal desorption. An attractive alternative would be to combine GC-MS with headspace (HS) systems as it allows simpler, faster, low temperature desorption. We present here the first report of HS-GC-MS for the determination of VOCs in air sampled using solid supports. Abstract. The use of a headspace (HS) for low temperature desorption of VOCs, previously sorbed from indoor air on solid supp…

Ion mobility spectrometry and high resolution mass-spectrometry as methodologies for rapid identification of the last generation of new psychoactive substances

A new drug trafficking trend has been observed in the last years by the introduction in the black market of new psychoactive substances (NPS) in order to difficult competent authority controls. In this study, ion mobility spectrometry (IMS) and high-resolution mass-spectrometry (HRMS) were proposed as vanguard and rearguard methodologies for the rapid identification of the last generation of NPS in seizures. The combined use of IMS and HRMS has been evaluated through the analysis of 24 NPS seized from 2016 to 2018 in Valencia (Spain) to demonstrate the utility of this approach. The characteristic reduced mobility (K0) values for seized NPS were determined and mass-mobility relationships wer…

Evaluation of working air quality by using semipermeable membrane devices

Abstract It has been evaluated the use of semipermeable membrane devices (SPMDs) as passive samplers of organophosphorus pesticides from air, in order to determine the contamination of working environments. Additionally, the use of SPMDs as portable samplers has been also considered. The analytical methodology for the determination of diazinon, chlorpyrifos-methyl, pirimiphos-methyl, chlorpyrifos and fenthion in SPMDs exposed to contaminated air was based on microwave-assisted extraction and gas chromatography with mass spectrometry determination. Limit of detection (LOD) values from 2 to 4 ng SPMD−1 and repeatability from 2 to 7% were obtained by using the aforementioned methodology. Theor…

Passive Air Sampling

Using semi-permeable membrane devices as passive samplers

Abstract We discuss the present state of, and future developments in, using semi-permeable membrane devices (SPMDs) for environmental monitoring of organic pollutants. SPMDs allow the determination of time-weighted average concentrations of bioavailable pollutants in the sampled media, reducing significantly the costs of analysis compared with active samplers. We summarize developments in SPMDs, including simplified devices and devices modified by incorporating solvents other than triolein, and applications. We review contaminants (e.g., organotin compounds, polycyclic musk, triclosan, petroleum biomarkers, nitrated PAHs, polychlorinated naphthalenes and a wide range of pesticides sampled i…

Sensitive Monoclonal Antibody-Based Immunoassays for Kresoxim-methyl Analysis in QuEChERS-Based Food Extracts

Kresoxim-methyl is nowadays widely used to combat a diversity of common diseases affecting high-value crops. In this article, we report the development and characterization of two novel immunoassays for the analysis of this pioneer strobilurin fungicide, and for the first time, a validation study with food samples was performed. A direct and an indirect competitive immunoassay based on a new anti-kresoxim-methyl monoclonal antibody were developed for sensitive and specific chemical analysis. Optimized assays showed limits of detection of 0.1 μg/L. Fruit and vegetable samples were extracted with acetonitrile by the QuEChERS procedure and analyzed by the developed immunoassays after a simple …

Magnetic molecularly imprinted polymers for the selective determination of cocaine by ion mobility spectrometry

Abstract Magnetic molecularly imprinted polymers (MMIPs) were prepared for cocaine recognition by bulk polymerization in the presence of magnetic nanoparticles (MNPs). Two reagents (polyethylene glycol (PEG) and 3-(trimethoxysilyl)propyl methacrylate (V)) were used for MNPs modification. MMIPs were characterized and compared in terms of loading capacity, reusability, accuracy and precision for the extraction of cocaine from saliva samples. It was observed that V-MMIPs gave higher physical stability than PEG-MMIPs. Thus, V-MMIP were used for the analysis of cocaine users saliva. The developed procedure based on ion mobility spectrometry (IMS) provided limits of detection and quantification o…

Analysis of hazardous chemicals by “stand alone” drift tube ion mobility spectrometry: a review

Ion mobility spectrometry (IMS) is a widely used technique based on gas phase ion separation under an electric field by differences in ion mobilities. In the last decade, IMS techniques have received increased attention due to their high operational speed and sensitivity. Currently, there are different IMS devices focused on solving different analytical performances, mainly based on linear drift tube (DT IMS), traveling wave, and field asymmetric waveform ion mobility spectrometers. In this review we summarize the main applications of DT-IMS devices for the determination of semi-volatile hazardous chemicals such as: illegal drugs, pesticides, explosives, chemical warfare agents, and others,…

Dispersive magnetic immunoaffinity extraction. Anatoxin-a determination.

Specific monoclonal antibodies were coupled with magnetic Sepharose-based beads and used, for the first time. The methodology was applied to preconcentrate anatoxin-a from water and the later determination by ion mobility spectrometry (IMS). Dispersive magnetic immunoaffinity (d-MagIA) extraction methodology provided a limit of detection of 0.02μgL-1 and a satisfactory precision with a relative standard deviation lower than 15%. Recoveries were evaluated at 0.5, 1.0 and 5.0μgL-1 anatoxin-a with quantitative values from 91 to 115%. Additionally, isobaric interferences with phenylalanine were completely avoided by the use of the developed d-MagIA extraction coupled to IMS determinations.

Headspace–mass spectrometry determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers in soil samples using chemometrics

A simple and fast method has been developed for the determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers (BTEX) in soils. Samples were introduced in 10 mL standard glass vials of a headspace (HS) autosampler together with 150 microL of 2,6,10,14-tetramethylpentadecane, heated at 90 degrees C for 10 min and introduced in the mass spectrometer by using a transfer line heated at 250 degrees C as interface. The volatile fraction of samples was directly introduced into the source of the mass spectrometer which was scanned from m/z 75 to 110. A partial least squares (PLS) multivariate calibration approach based on a classical 3(3) calibration model was build with m…

Assessing air quality inside vehicles and at filling stations by monitoring benzene, toluene, ethylbenzene and xylenes with the use of semipermeable devices

BTEX (benzene, toluene, ethylbenzene, and xylenes) were used as target molecules to evaluate the quality of air inside motor vehicles and near filling stations, using semipermeable membrane devices (SPMDs) as low-cost passive sampling devices. A direct, fast, simple methodology based on the use of headspace-gas chromatography-mass spectrometry detection (HS-GC-MS) was developed for BTEX determinations, without any sample pre-treatment. SPMDs (25.4 cm2 surface, filled with 100 microL triolein) were employed as static samplers. After the selected deployment time, the SPMDs were heated inside a HS vial at 150 degrees C for 20 min and BTEX compounds were determined by GC-MS in selected ion moni…

Fast extraction of cannabinoids in marijuana samples by using hard-cap espresso machines

Abstract A simple, quick and low cost procedure was developed for the extraction of Δ9-tetrahydrocannabinol, cannabidiol, and cannabinol from marijuana samples, based on the use of a hard-cap espresso extraction with 2-propanol. After extraction, cannabinoids were directly determined after appropriate dilution by gas-chromatography-mass spectrometry, reaching a limit of detection from 0.03 to 0.05 mg g−1. Extraction efficiency was evaluated by the comparison of results obtained for seized samples by the proposed method and a reference methodology based on ultrasound-assisted extraction. Moreover, ion mobility was proposed for the rapid and sensitive determination of Δ9-tetrahydrocannabinol …

Hapten synthesis, monoclonal antibody generation, and development of competitive immunoassays for the analysis of picoxystrobin in beer.

Abstract This paper describes the original synthesis of a functionalized derivative of the fungicide picoxystrobin and the generation of the first reported monoclonal antibodies against this strobilurin pesticide. The synthetic hapten was prepared by total synthesis from commercial chemicals and incorporating the spacer arm through a carbon–carbon single bond. Also, to obtain the immunogen, an uncommon hapten activation strategy based on N,N′-disuccinimidyl carbonate was employed, affording high activation yields and clean and reproducible coupling results. With these immunoreagents, two enzyme-linked immunosorbent assays (ELISAs) were developed: a competitive one-step assay using the antib…

Mepanipyrim haptens and antibodies with nanomolar affinity

Mepanipyrim is an anilinopyrimidine fungicide used worldwide for crop protection. With the aim of developing useful immunoreagents for mepanipyrim immunoanalysis, two new functionalized derivatives were prepared and antibodies were generated. Affinity and specificity were assessed by direct and indirect competitive ELISA using homologous and heterologous conjugates. Although all antibodies were selective for the target analyte, the immunizing hapten structure was revealed as a determinant for high-affinity antibody production (IC50 = 3 nM). © 2013 The Royal Society of Chemistry.

Development of monoclonal antibody-based competitive immunoassays for the detection of picoxystrobin in cereal and oilseed flours

Picoxystrobin is a new generation fungicide primarily developed to be used in cereal crops. In the present study a novel collection of specific monoclonal antibodies has been produced using different immunizing haptens based on a carboxy-functionalized identical spacer arm attached to alternative positions of the target pesticide molecule. Two competitive enzyme-linked immunosorbent assays have been developed employing hapten heterology, one using the antibody-coated direct format and the other in the conjugate-coated indirect format. Both immunoassays have been characterized in terms of selectivity, solvent tolerance, and buffer conditions, affording similar limits of detection at or below…

Exploring alternative hapten tethering sites for high-affinity anti-picoxystrobin antibody generation

The relevance of the linker tethering site in haptens was investigated for antibody generation and immunoassay development. Three derivatives of the strobilurin fungicide picoxystrobin were synthesized with the same functionalized spacer arm located at three different positions. Protein conjugates of those haptens were employed as immunogens, and novel polyclonal antibodies were produced and characterized. All haptens afforded highly specific antibodies, but different affinities to the free analyte were observed among the obtained antisera. Next, competitive enzyme-linked immunosorbent assays were studied in several formats, and site heterology was confirmed as an effective strategy for det…

Towards an automatic lab-on-valve-ion mobility spectrometric system for detection of cocaine abuse.

A lab-on-valve miniaturized system integrating on-line disposable micro-solid phase extraction has been interfaced with ion mobility spectrometry for the accurate and sensitive determination of cocaine and ecgonine methyl ester in oral fluids. The method is based on the automatic loading of 500μL of oral fluid along with the retention of target analytes and matrix clean-up by mixed-mode cationic/reversed-phase solid phase beads, followed by elution with 100μL of 2-propanol containing (3% v/v) ammonia, which are online injected into the IMS. The sorptive particles are automatically discarded after every individual assay inasmuch as the sorptive capacity of the sorbent material is proven to b…

New perspectives in the use of semipermeable membrane devices as passive samplers.

This review shows the state of the art, from 2000 to nowadays, of the use of semipermeable membrane devices (SPMDs) for monitoring persistent organic pollutants in both, air and aquatic environments. Since their first use in 1990, SPMDs have been employed for many environmental purposes, like air and water pollution monitoring. We have focussed the study in three subjects: (i) novel compounds accumulated by SPMDs, (ii) modifications of SPMDs to improve their specific uptake properties and (iii) alternatives in sample pre-treatment for the determination of pollutants accumulated in SPMDs.

Immunoassays for trifloxystrobin analysis. Part II. Assay development and application to residue determination in food.

Immunochemical assays constitute complementary analytical methods for small organic molecule determination. We herein describe the characterisation and optimisation of two competitive enzyme-linked immunosorbent assays in different formats using monoclonal antibodies to the Quinone outside inhibitor (QoI) fungicide trifloxystrobin. Antibody selectivity was evaluated using a variety of agrochemicals and the main trifloxystrobin metabolite. Acceptable tolerance of the immunoassay to methanol, ethanol, and acetonitrile was observed in all cases, whereas a dissimilar influence of buffer pH and ionic strength was found. Moreover, the influence of Tween 20 over the analytical parameters was studi…

Smart Sorption Materials in Green Analytical Chemistry

The use of smart materials as alternative sorption materials for their use in greening sample preparation has been reviewed. It has been taking into consideration recent advances on the use of natural products, without any modification or purification, for making analyte extraction and pre-concentration and the use of specific materials in solid-phase extraction (SPE) and solid-phase microextraction (SPME) approaches. Inorganic materials, such as metal oxides, alumina-based, silica-based, and carbon-based materials together with biomimetic sorbents such as classical immunosorbents, aptamers, and molecularly imprinted polymers, have been reviewed as examples of these materials, stressing the…

Off-line coupling of multidimensional immunoaffinity chromatography and ion mobility spectrometry: A promising partnership.

The extreme specificity of immunoaffinity chromatography (IAC) columns coupled to the high sensitivity of ion mobility spectrometry (IMS) measurements makes this combination really useful for rapid, selective, and sensitive determination of a high variety of analytes in different samples. The capabilities of the IAC-IMS coupling have been highlighted under three different scenarios: (i) multiclass residue analysis using a single IAC column, (ii) multiclass residue analysis using stacked IAC columns, and (iii) isomer analysis. In the first case, the determination of three strobilurin fungicides - azoxystrobin, picoxystrobin, and pyraclostrobin - in water and strawberry juice was considered, …

Green extraction techniques in green analytical chemistry

Abstract Green analytical chemistry concept, involving the development of analytical methodologies with an environmental concern, encourages the use of direct analysis to avoid any sample treatment that involves energy and reagent consumption and generation of wastes. However, the determination of target analytes at trace concentration levels or in complex matrices frequently requires previous extraction, pre-concentration, or clean-up steps offering thus, additional possibilities for greening classical methods. So, a green evaluation of alternative extraction techniques to currently used ones for the extraction of solid, liquid, and gaseous samples has been carried out in this study. Moreo…

Molecularly imprinted polymer-based device for field collection of oral fluid samples for cocaine identification.

In this paper, a low-cost, rapid, easy, and potentially portable tool for the identification of cocaine and its semi-quantitative determination in oral fluid has been proposed. A field collection device has been designed, based on a cotton pad with an indicator and a molecularly imprinted polymer (MIP) sorbent, to selective retain cocaine from oral fluid components. After sample collection, cocaine is transferred by using phosphate buffer to the MIP and then eluted with 2-propanol. The obtained extract is analysed by ion mobility spectrometry (IMS), providing a cut-off value of 20 µg L-1 that identifies 100 % true-positive and 95 % true-negative samples. The MIP-IMS procedure has been valid…

Dual mixed-mode poly (vinylpyridine-co-methacrylic acid-co-ethylene glycol dimethacrylate)-based sorbent for acidic and basic drug extraction from oral fluid samples.

Abstract In this study, a dual mixed-mode polymer sorbent was prepared via one-step thermally initiated polymerization of 4-vinylpyridine (VP), methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) for the solid-phase extraction (SPE) of basic and acidic drugs. The use of VP and MAA as ionizable functional monomers allowed the tailoring of ion-exchange and hydrophobic features of the polymer. The obtained polymer was characterized by Fourier-transform infrared spectroscopy and scanning electron microscopy. Next, the retention behavior of dual mixed-mode polymer towards basic and acidic drugs was investigated. Moreover, the practical capability of this novel material was tested f…

Highly sensitive monoclonal antibody-based immunoassays for boscalid analysis in strawberries

Boscalid is an agrochemical recently developed for crop protection and the most significant member of the succinate dehydrogenase inhibitor group of fungicides. In this study, a collection of high-affinity monoclonal antibodies was generated to boscalid. By using a series of haptens with a linker at alternative tethering sites of the boscalid framework, specific antibodies were isolated as well as antibodies that also recognized the main boscalid metabolite. Two immunoassays were developed using different ELISA formats. Optimized assays displayed very high sensitivities (limits of detection were near 0.01 µg/L). Trueness and precision for the determination of the target analyte in strawberr…

Polyfurfuryl alcohol composite as adsorbent of polychlorinated biphenyls and pyrethroid insecticides

Abstract Composites from furfuryl alcohol and silica gel were prepared in dichloromethane using trifluoroacetic acid as catalyst and characterized by means of thermogravimetric analysis, transmission electron microscopy and nitrogen adsorption–desorption isotherms. The polymer content in the composites ranged between 19.5% and 32.9%. The capability to adsorb polychlorinated biphenyls and pyrethroid insecticides was tested for composite samples containing different percentages of polymer. Pyrethroids are retained almost totally by composites containing around 24–33% of polymer, while recovery of PCBs close to 80% is obtained with all the composites. No selectivity between compounds of the sa…

Immunoreagents and competitive assays to fludioxonil

Fludioxonil is a new-generation fungicide widely used for postharvest fruit protection. The aim of this study was to produce hitherto unreported immunoreagents for Fludioxonil analysis by immunoassay. Derivatives of this agrochemical were synthesized with different linker tethering sites. Those functionalized haptens were activated, and the purified active esters were efficiently conjugated to different carrier proteins for immunogen and assay antigen preparation. Antibodies to Fludioxonil were raised in rabbits, and their selectivity and affinity were characterized, revealing the significance of the linker. Those antibodies were evaluated using homologous and heterologous conjugates by dir…

A passive sampling-based analytical strategy for the determination of volatile organic compounds in the air of working areas.

Abstract An analytical methodology based on the use of a polyethylene layflat tube filled with activated carbon and Florisil (ACFL-VERAM) was employed for the passive sampling of volatile organic compounds (VOCs) in the air of working areas of packing industries. VOCs amount in the ACFL-VERAM sampler was directly determined through head-space-gas chromatography–mass spectrometry (HS-GC–MS) allowing a direct determination in only 20 min without the need of any previous treatment. Uptake parameters, like sampling rate ( R S ) and sampler–air partition coefficient ( K SA ), were determined for every studied VOC from adsorption isotherm data. Additionally, experimental equations have been propo…

Hard Cap Espresso Machines in Analytical Chemistry: What Else?

A hard cap espresso machine has been used in combination with liquid chromatography with molecular fluorescence detection for the determination of polycyclic aromatic hydrocarbons (PAHs) from contaminated soils and sediments providing appropriate extraction efficiencies and quantitative results. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benz[ghi]perylene, and indeno[1,2,3-cd]pyrene were used as target compounds. It should be mentioned that the pairs benz[a]anthracene-chrysene and dibenz[a,h]anthracene-benz[ghi]perylene peaks coelute under th…

Development of pipette tip-based poly(methacrylic acid-co-ethylene glycol dimethacrylate) monolith for the extraction of drugs of abuse from oral fluid samples

Abstract In this work, a monolithic polymer based on poly(methacrylic acid-co-ethylene glycol dimethacrylate) (MAA-co-EDMA) was prepared inside 200 μL pipette tips for the extraction of drug of abuse from oral fluid samples. After an appropriate surface tip modification, several polymerization mixtures with different monomer/cross-linker ratios, and percentage of porogen were studied. The most appropriate monolith to easily flow organic solvents and oral fluid samples was prepared with a MAA/EDMA ratio of 8:92 wt/wt and dodecanol containing 10 wt% toluene, as porogenic solvent. Parameters affecting the extraction procedure were evaluated and the monolith was characterized in terms of bindin…

Analysis of drugs including illicit and new psychoactive substances in oral fluids by gas chromatography-drift tube ion mobility spectrometry

Abstract In this study, a gas chromatograph (GC) has been coupled to a drift tube ion mobility spectrometer (IMS) in order to develop an analytical procedure for the determination of psychoactive substances in oral fluids. Working parameters, including the GC-IMS interface ones, were adjusted in order to obtain sensitive and robust signals. A volume of 500 μL of oral fluid was extracted with 250 μL chloroform and, after centrifugation, were injected into the GC-IMS system. Amphetamine, methylone, α-PVP, ketamine, lidocaine, MPHP, cocaine, THJ-2201, and 5F-ADB were employed as model compounds, providing limits of detection from 6 to 15 μg L−1 and recoveries from 70 to 115% for field oral flu…

Site-heterologous haptens and competitive monoclonal antibody-based immunoassays for pyrimethanil residue analysis in foodstuffs

Pyrimethanil is a widely used post-harvest fungicide whose residues are commonly found in fruits and vegetables. We herein report the synthesis of two new functionalized derivatives of pyrimethanil carrying an equivalent spacer arm at different positions of the molecule. The influence of the linker tethering site on the affinity of monoclonal antibodies was shown. Moreover, the development of competitive immunoassays in different formats and with high sensitivity to the target analyte - IC50 values below 0.3μg/L - is described. Optimized assays were characterized by the determination of the limit of quantification, trueness, and precision using water-diluted QuEChERS extracts of fruits and …

Trace analysis by ion mobility spectrometry: From conventional to smart sample preconcentration methods. A review.

Ion mobility spectrometry (IMS) is a rapid and high sensitive technique widely used in security and forensic areas. However, a lack of selectivity is usually observed in the analysis of complex samples due to the scarce resolution of the technique. The literature concerning the use of conventional and novel smart materials in the pretreatment and preconcentration of samples previous to IMS determinations has been critically reviewed. The most relevant strategies to enhance selectivity and sensitivity of IMS determinations have been widely discussed, based in the use of smart materials, as immunosorbents, aptamers, molecularly imprinted polymers (MIPs), ionic liquids (ILs) and nanomaterial. …

Future Perspectives on the Use of Smart Materials

Hard cap espresso extraction and liquid chromatography determination of bioactive compounds in vegetables and spices

Abstract A new analytical procedure, based on liquid chromatography with diode array and fluorescence detection, has been proposed for the determination of bioactive compounds in vegetables and spices after hard cap espresso extraction. This novel extraction system has been tested for the determination of capsaicin and dihydrocapsaicin from fresh chilli and sweet pepper, piperine from ground pepper, curcumin from turmeric and curry, and myristicin from nutmeg. Extraction efficiency was evaluated by using acetonitrile:water and ethanol:water mixtures. The proposed method allows the extraction of samples with 100 mL of 60% (v/v) ethanol in water. The obtained limits of quantification for the …

Fungicide multiresidue monitoring in international wines by immunoassays

24 pages, 5 figures, 1 table. -- Available online 10 November 2015.

Use of semipermeable membrane devices for monitoring pesticides in indoor air.

Abstract In this work, 40 pesticides from different categories were analyzed in the air of 20 indoor places that have an intensive use of pesticides. Passive sampling was carried out by using semipermeable membrane devices (SPMDs) deployed for 7 days. SPMDs were analyzed using microwave-assisted extraction and GC/MS. PCB-195 was used as an internal standard. Recoveries ranged between 81 and 108 for many compounds, with RSD values <11. Typical LOD values for 7 days of sampling were from 0.1 to 3.1 ng/m. Propamocarb, propoxur, carbosulfan, pirimicarb, metribuzin, metalaxyl, pendimethalin, oxadiazon, phenothrin, and permethrin were detected in 11 sampling sites, with air concentrations …

Use of semipermeable membrane devices for assessment of air quality in Tangier (Morocco)

Semipermeable membrane devices (SPMDs) have been used for the evaluation of the contamination of air in both the urban and the industrial area in Tangier (Morocco). Benzene, toluene, ethylbenzene a...

Microwave-assisted extraction of pyrethroid insecticides from soil

Abstract An analytical method has been developed for the microwave-assisted extraction of synthetic pyrethroid insecticide residues in soils and their determination by gas chromatography with electron capture detector (ECD) and mass spectrometry (MS) detector. Clean soil samples were spiked with nine pyrethroids: tetramethrin, cyfluthrin, flucythrinate, deltamethrin, bifenthrin, permethrin, cypermethrin and fluvalinate were used for this study. Concentration levels were 50 ng g −1 for all the compounds studied except to sumitrin for which a 10 μg g −1 was evaluated. Two grams of sample were treated in a closed PTFE reactor with 10 mL toluene and 1 mL water and irradiated at 700 W during 9 m…

Development of a simulation chamber for the evaluation of dermal absorption of volatile organic compounds

Abstract An exposition chamber has been designed and developed for the production of contaminated atmospheres with fixed and known concentration of volatile organic compounds. The proposed chamber has been evaluated for the determination of in-vitro diffusion parameters, such as flux and lag time for benzene, toluene, ethylbenzene, and xylenes (BTEX). Polydimethylsiloxane (PDMS) and Strat-M® membranes were evaluated, including the effect of membrane thickness, from 0.5 to 3.0 mm, on the diffusion parameters. The obtained flux values and lag times, ranged from 0.2 to 1.5 μg cm−2 h−1 and from 10 to 130 min, respectively, for studies performed at a BTEX concentration of 51 μg L−1 in air. Diffe…

Determination of non-steroidal anti-inflammatory drugs in water and urine using selective molecular imprinted polymer extraction and liquid chromatography

Abstract A selective solid-phase extraction was employed for the improvement of the determination of non-steroidal anti-inflammatory drugs (NSAIDs) in continental water and urine samples. Ketoprofen, naproxen, diclofenac, and ibuprofen were selected as target analytes due to they are the most frequently administered and consumed NSAIDs. These compounds were extracted using molecular imprinted polymers and determined by liquid chromatography with diode array (DAD), and tandem-mass spectrometry (MS–MS) detectors. Performance of DAD and MS–MS detectors was evaluated throughout this study. The obtained limits of quantification, after a 50-fold preconcentration solid-phase extraction, varied fro…

Development of a versatile, easy and rapid atmospheric monitor for benzene, toluene, ethylbenzene and xylenes determination in air

Abstract A new procedure for the passive sampling in air of benzene, toluene, ethylbenzene and xylene isomers (BTEX) is proposed. A low-density polyethylene layflat tube filled with a mixture of solid phases provided a high versatility tool for the sampling of volatile compounds from air. Several solid phases were assayed in order to increase the BTEX absorption in the sampler and a mixture of florisil and activated carbon provided the best results. Direct head-space-gas chromatography–mass spectrometry (HS-GC–MS) measurement of the whole deployed sampler was employed for a fast determination of BTEX. Absorption isotherms were used to develop simple mathematical models for the estimation of…

Greening the wastes

Problems associated with analytical waste toxicity and waste treatment are reviewed in the frame of the water treatment, being collected a series of models, from the big-scale treatment of waste waters and adapted to the effluents generated during sample analysis. In fact to move from wastes to clean or no-contaminant wastes is a way from greening those methods in which any sample treatment and the use of reagents and solvents cannot be avoided. The last contributions in the field have been taken into account in this study and future trends have been proposed.

On-line gel permeation chromatography–attenuated total reflectance–Fourier transform infrared determination of lecithin and soybean oil in dietary supplements

Gel permeation chromatography (GPC) with attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry detection has been proposed for the simultaneous determination of lecithin and soybean oil in dietary supplements. The method involves the extraction of analytes with dichloromethane in an ultrasound water bath and the injection of 2 ml of centrifuged and filtered extracts into the system integrated by two Envirogel GPC columns (19 mm x150 mm, 19 mm x 300 mm) coupled on-line. Dichloromethane was used as mobile phase. A method has been developed to select the most appropriated wavenumber to be used for the determination of each considered compound from the calculation of a…

Determination of pyrethroid insecticide residues in vegetable oils by using combined solid-phases extraction and tandem mass spectrometry detection

Abstract A methodology has been developed for the determination of pyrethroid insecticide residues in vegetable oils, based in a solid-phase extraction (SPE) with combined solid supports phases. Several solid phases such as florisil, alumina, C18 and graphitized carbon black were tested in order to minimize fat residues, being a combination of treated alumina and C18 which provided the best results. Oil samples were partitioned with acetonitrile–hexane (1:1) and then eluted through a combined column packed with deactivated basic-alumina and C18, employing the acetonitrile extract as elution solvent. Gas chromatography tandem mass spectrometry was used for determination. Tetramethrin, Bifent…

Determination of ethyl sulfate – a marker for recent ethanol consumption – in human urine by CE with indirect UV detection

A CE method for the determination of the ethanol consumption marker ethyl sulfate (EtS) in human urine was developed. Analysis was performed in negative polarity mode with a background electrolyte composed of 15 mM maleic acid, 1 mM phthalic acid, and 0.05 mM cetyltrimethylammonium bromide (CTAB) at pH 2.5 and indirect UV detection at 220 nm (300 nm reference wavelength). This buffer system provided selective separation conditions for EtS and vinylsulfonic acid, employed as internal standard, from urine matrix components. Sample pretreatment of urine was minimized to a 1:5 dilution with water. The optimized CE method was validated in the range of 5-700 mg/L using seven lots of urine. Intra-…

Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes.

A non-destructive, fast and environmentally friendly procedure has been developed for cocaine determination in euro bank notes. Cocaine was extracted with 15 ml methanol by vortex agitation during 5 min. The extract was evaporated and reconstituted in 0.5 ml methanol. GC-MS-MS analysis was performed using as precursor ion m/z 182.2, with an excitation energy voltage of 1.60 eV, being the product ions measured m/z 150.2 and 82.0. A limit of detection of 0.15 ng per note and a repeatability of 6%, established from the relative standard deviation, of a 1 ng ml(-1) level, were achieved. Recoveries of 101+/-2 and 98+/-3% were obtained for samples spiked with 100 and 10 microg respectively. Resul…

Development of a molecularly imprinted monolithic polymer disk for agitation-extraction of ecgonine methyl ester from environmental water

Abstract In this study, a new extraction approach based on rotating molecularly imprinted polymer (MIP) disks was developed. The preparation procedure of MIP-disk is simple. Firstly, in order to immobilize MIP onto the surface of polytetrafluoroethylene (PTFE) disk, previous modification and vinylization steps of this fluoropolymer were conducted. Then, MIP synthesis was done by in situ polymerization. The resulting MIP was characterized by Fourier-transform infrared spectroscopy and scanning electron microscopy. Afterwards, two ring magnets were placed in the sides of the MIP-disk to integrate the stirring and preconcentration of sample in just one step. To demonstrate the feasibility of t…

Comprehensive analysis of airborne pesticides using hard cap espresso extraction-liquid chromatography-high-resolution mass spectrometry

A hard cap espresso extraction procedure has been developed to recover airborne pesticides in particulate matter trapped in filters. This extraction step was made for 20s at 72°C and 19bar using 50mL of 20% (v/v) acetonitrile in water. After that, based on NaCl salting out, extracts were concentrated 22 times and analysed by ultra-high performance liquid chromatography - high resolution mass spectrometry. 35 pesticides were evaluated, as a proof of concept, being validated the whole methodology and compared the extraction method with that based on microwave assisted extraction for 20min. In short, the method avoids cross-contamination of samples, it is relatively fast and consumes only 10mL…

Smart materials for sample preparation in bioanalysis: A green overview

Abstract The analysis of biological samples is a complex challenge due to the complexity of the matrix, but also to the low concentration of target analytes that must be determined. Consequently, different sample treatment procedures have been proposed in bioanalysis to clean-up and enrich sample extracts, paying special attention to microextraction approaches. In this frame, the combined use of microextraction approaches with smart materials provides environmentally friendly sample treatment strategies with improved selectivity, sensitivity, and reusability. Applications of smart solid materials includes antibody–antigen interaction based materials, aptamers, molecularly imprinted polymers…

Design and development of heterologous competitive immunoassays for the determination of boscalid residues

Boscalid is a modern agrochemical belonging to the so-called chemical class of succinate dehydrogenase inhibitor fungicides. With the aim of developing rapid analytical screening methods for this relevant compound, we herein report the synthesis of new boscalid mimics and the study of their suitability for the production of polyclonal antibodies. Aliphatic spacer arms equivalent in length and composition were tethered at two different aromatic rings of the target molecular structure. These haptens, besides being used for immunization, were employed in the development of heterologous competitive enzyme-linked immunosorbent assays (cELISAs) in order to improve assay detectability. Direct and …

Direct and fast determination of polychlorinated biphenyls in contaminated soils and sediments by thermal desorption-gas chromatography-tandem mass spectrometry

Abstract A direct procedure based on thermal desorption-gas chromatography-tandem mass spectrometry (TD–GC–MS–MS) was developed for the fast extraction of seven polychlorinated biphenyls (PCBs) from sediments and soils. PCBs were directly extracted, from 20 to 75 mg of sample, without any chemical pre-treatment or use of organic solvents, after the addition of 10 µL internal standard (PCB 195) in acetone. Sample treatment was totally automated. PCBs were extracted at 250 °C for 20 min, using a helium flow and the PCBs were trapped in a cryogenic Tenax trap at −10 °C. After that, analytes were directly desorbed at 270 °C and introduced to the GC–MS–MS system. Recoveries were established usin…

Cocaine abuse determination by ion mobility spectrometry using molecular imprinting

A cocaine-based molecular imprinted polymer (MIP) has been produced by bulk polymerization and employed as selective solid-phase extraction support for the determination of cocaine in saliva samples by ion mobility spectrometry (IMS). The most appropriate conditions for washing and elution of cocaine from MIPs were studied and MIPs were characterized in terms of analyte binding capacity, reusability in water and saliva analysis, imprinting factor and selectivity were established and compared with non-imprinted polymers. The proposed MIP-IMS method provided a LOD of 18μgL-1 and quantitative recoveries for blank saliva samples spiked from 75 to 500μgL-1 cocaine. Oral fluid samples were collec…

Development of immunoaffinity columns for pyraclostrobin extraction from fruit juices and analysis by liquid chromatography with UV detection

Abstract Pyraclostrobin belongs to a new generation of fungicides widely used to preserve high valuable crops. In the present study, three monoclonal antibodies with different affinities to this modern strobilurin have been evaluated for their usefulness in the production of immunoaffinity columns suitable for the solid-phase extraction, concentration, and clean-up of residues from food commodities. Different immunosorbents were produced and characterized in terms of antibody immobilization efficiency, immunosorbent binding capacity, optimum elution conditions, and reusability. Covalent coupling of the antibodies to Sepharose–CNBr gel took place with high yield (over 90%), whereas the immun…

Passive Sampling of Atmospheric Organic Contaminants

The state of the art of passive sampling monitoring studies of atmospheric contaminants is reviewed in this chapter. The following passive samplers were considered: badge-type diffusive samplers; diffusive tubes; semi-permeable membrane devices; Radiello samplers; solid-phase microextraction fibers; polyurethane foam disks; XAD-2 passive air samplers; stir-bar samplers; polymer-coated glass surfaces; versatile, easy and rapid atmospheric monitor; and vegetation. A summary of the passive samplers used, sampling times, sampling rates, and analyte concentrations found is provided for different organic compounds, such as: carbonyl compounds, volatile compounds, polycyclic aromatic hydrocarbons,…

Immunoassays for pyraclostrobin analysis in processed food products using novel monoclonal antibodies and QuEChERS-based extracts

Strobilurins are a family of synthetic natural-derived pesticides widely used for fungi control in many crops. As part of a larger research project, a collection of monoclonal antibodies to one of the most relevant strobilurins, i.e. pyraclostrobin, has been generated using functionalized haptens with the spacer arm located at different sites. The toxophore aliphatic moiety, as observed with other strobilurins, and the planar aromatic two-ring system characteristic of this molecule were revealed as the best tethering sites for high-affinity monoclonal antibody production. A central derivatization position did not generate a good immune response, but such derivatives were useful as heterolog…

Carbon-Based Nanomaterials in Analytical Chemistry

Methylone determination in oral fluid using microextraction by packed sorbent coupled to ion mobility spectrometry

Abstract A methodology based on microextraction by packed sorbent (MEPS) followed by ion mobility spectrometry (IMS) has been developed for the simple and automated determination of methylone in oral fluids. MEPS was carried out using a 100 µL eVol® XR hand-held automated analytical syringe filled with octadecyl silica sorbent. The effect of main experimental parameters of MEPS such as sample pH and ionic strength, number of aspirating/dispensing cycles, and elution solvent was studied to obtain a quantitative extraction of methylone. Oral fluid samples were spiked with methylone at different concentration levels from 50 to 400 µg L−1 and analyzed by the proposed MEPS-IMS procedure, giving …

Microwave-assisted extraction of pyrethroid insecticides from semi permeable membrane devices (SPMDs) used to indoor air monitoring

Abstract A rapid and environmentally friendly methodology was developed for the extraction of pyrethroid insecticides from semi permeable membrane devices (SPMDs), in which they were preconcentrated in gas phase. The method was based on gas chromatography mass–mass spectrometry determination after a microwave-assisted extraction, in front of the widely employed dialysis method. SPMDs were extracted twice with 30 mL hexane:acetone, irradiated with 250 W power output, until 90 °C in 10 min, this temperature being held for another 10 min. Clean-up of the extracts was performed by acetonitrile–hexane partitioning and solid-phase extraction (SPE) with a combined cartridge of 2 g basic-alumina, d…

A class-selective immunoassay for simultaneous analysis of anilinopyrimidine fungicides using a rationally designed hapten

he development of multianalyte immunoassays constitutes a main research issue in the field of bioanalytical techniques. In the present study, class-specific antibodies against the three members of the anilinopyrimidine family of fungicides (pyrimethanil, cyprodinil and mepanipyrim) were raised by using a bioconjugate of a rationally designed hapten [5-(6-methyl-2-(phenylamino)pyrimidin-4-yl)pentanoic acid]. Highly sensitive immunoassays were developed for the generic determination of these compounds, using the competitive enzyme-linked immunosorbent assay (ELISA). Particularly, a direct antibody-coated competitive ELISA afforded identical sensitivity for the three anilinopyrimidines, with I…

Evaluation of the Soil Contamination of Tangier (Morocco) by the Determination of BTEX, PCBs, and PAHs

Benzene, toluene, ethylbenzene, and xylenes (BTEX), twelve polycyclic aromatic hydrocarbons (PAHs) and seven polychlorinated biphenyls (PCBs), were selected as pollutants to evaluate the contamination of soils in the urban and industrial areas of Tangier (Morocco). PAHs and PCBs were determined by gas chromatography-mass spectrometry (GC-MS) after a microwave-assisted extraction (MAE) and gel permeation chromatography (GPC) clean-up. BTEX were directly determined by head-space GC-MS. Results obtained in this study show the presence of high levels of BTEX and PAHs in the soil near the urban waste deposit. However, the analysis of pollutants in the other sampling sites provided comprehensive …

Uptake and bioavailability of persistant organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of…