Miniaturized liquid chromatography coupled on-line to in-tube solid-phase microextraction for characterization of metallic nanoparticles using plasmonic measurements. A tutorial.

Abstract This tutorial aims at providing guidelines for analyzing metallic nanoparticles (NPs) and their dispersions by using methods based on miniaturized liquid chromatography with diode array detection (MinLC-DAD) and coupled on-line to in-tube solid-phase microextraction (IT-SPME). Some practical advice and considerations are given for obtaining reliable results. In addition, this work outlines the potential applications that set these methodologies apart from microscopy-related techniques, dynamic light scattering, single particle ICP-MS, capillary electrophoresis, field-flow fractionation and other chromatographic configurations, which are discussed and mainly seek to accomplish size …

In Situ Colorimetric Quantification of Silver Cations in the Presence of Silver Nanoparticles

Silver ions (Ag(+)) can be quantified in situ in the presence of AgNPs by using a colorimetric sensing probe (3,3',5,5'-tetramethylbenzidine). Interestingly, it also enables detection of the Ag(+) adsorbed on the AgNP surface. This is relevant to design new methods to make AgNPs while ensuring the total reduction of Ag(+).

Fast blue B functionalized silica-polymer composite to evaluate 3,5-dihy-droxyhydrocinnamic acid as biomarker of gluten intake

Celiac disease is an immune-mediated systemic disorder elicited by gluten and related prolamines in genetically susceptible individuals. The current treatment is a strict and lifelong gluten-free diet. However, compliance with the gluten-free diet is not always adequate and many food products contain low concentrations of gluten. The determination of dietary transgressions is a challenge for patients, physicians and dietitians. Alkylresorcinols (AR) have been proposed as sensitive and specific biomarkers of gluten consumption. In this work silica-polymer composites doped with fast blue B reagent (FB) have been used to estimate alkylresorcinols in biological samples. The proposed colorimetri…

A sustainable on-line CapLC method for quantifying antifouling agents like irgarol-1051 and diuron in water samples: Estimation of the carbon footprint

In this work, in-tube solid phase microextraction (in-tube SPME) coupled to capillary LC (CapLC) with diode array detection has been reported, for on-line extraction and enrichment of booster biocides (irgarol-1051 and diuron) included in Water Frame Directive 2013/39/UE (WFD). The analytical performance has been successfully demonstrated. Furthermore, in the present work, the environmental friendliness of the procedure has been quantified by means of the implementation of the carbon footprint calculation of the analytical procedure and the comparison with other methodologies previously reported. Under the optimum conditions, the method presents good linearity over the range assayed, 0.05-1…

New micromethod combining miniaturized matrix solid-phase dispersion and in-tube in-valve solid-phase microextraction for estimating polycyclic aromatic hydrocarbons in bivalves.

Abstract Miniaturized matrix solid-phase dispersion (MSPD) was developed for the extraction of common polycyclic aromatic hydrocarbons (PAHs) from bivalve samples (100 mg, dry weight). Additional clean-up and analyte enrichment was accomplished by in-tube solid-phase microextraction (SPME). For this purpose the extracts collected after MSPD were diluted with water and injected into a capillary column coated with the extractive phase. This capillary column was connected to the analytical column by means of a switching valve. Separation and quantification of the PAHs were carried out using a monolithic LC column and fluorescence detection. Since the in-tube SPME device allowed the processing …

New Tools for Characterizing Metallic Nanoparticles: AgNPs, A Case Study.

Currently, transmission electron microscopy (TEM) is the main technique for estimating the sizes of spherical nanoparticles (NPs) and through them, their concentrations. This paper demonstrates for the first time that C18 reversed-phase capillary liquid chromatography (Cap-LC) coupled to diode array detection (DAD) has the potential to estimate mean concentrations of silver nanoparticles (AgNPs) and thereby determine their average size. Direct injection of the sample without previous extraction or separation steps is carried out. Only a unique standard with a known AgNP size is needed for the calibration. In a first approach, the new method has been tested over silver nanoparticles, produce…

o-Phthalaldehyde–N-acetylcysteine polyamine derivatives: formation and stability in solution and in C18 supports

A comparative study of different derivatization procedures has been performed in order to improve the stability of the reaction products o-phthalaldehyde-N-acetylcysteine (OPA-NAC) polyamines. Procedures such as solution derivatization, solution derivatization followed by retention on a packing support, derivatization on different packing supports and on-column derivatization, have been optimized and compared. The degradation rate constant (k) of the derivative was dependent on the procedure used and on the analyte. For the spermine (the most unstable isoindol tested) k was 8 +/- 2 x 10(-2) min(-1) in solution versus 7.7 +/- 1.1 x 10(-4) min(-1) on the (C18) solid support. The results obtai…

Chemiluminescent method for detection of eutrophication sources by estimation of organic amino nitrogen and ammonium in water.

An automatic method has been developed for the estimation of organic amino nitrogen (CH2-NH) and ammonium in water samples. We propose a continuous flow system in which nitrogen compounds react with hypochlorite reagent to produce chloramines. Subsequently, the mixture is mixed with luminol, generating a chemiluminescence signal. The signal emission at 425 nm, registered as a function of time, decreases as nitrogen concentration increases, due to the decrease on hypochlorite concentration. A large number of nitrogen compounds have been assayed and their sensitivities compared, in milligrams per liter nitrogen. The ammonium calibration graph, expressed as N, can be used for most of the assay…

New silica based adsorbent material from rice straw and its in-flow application to nitrate reduction in waters: Process sustainability and scale-up possibilities.

Abstract This paper shows a particular example to move to a sustainable circular economical process from valorization of rice straw ashes by developing a green synthesis for obtaining a useful sub-product. This strategy can palliate negative effects of the agriculture waste practices on the environment and also the obtained silica reduced nitrate content in waters. It is demonstrated that the silica synthesis developed at lab was scalable more than a hundred times with good results. Adsorption studies of nitrate in standards and real well waters at lab scale and scaling-up provided similar results. Adsorption values near to 15 mg/g for nitrate standards and 8.5 mg/g for well water were obta…

NQS-Doped PDMS Solid Sensor: From Water Matrix to Urine Enzymatic Application

The development of in situ analytical devices has gained outstanding scientific interest. A solid sensing membrane composed of 1,2-naphthoquinone-4-sulfonate (NQS) derivatizing reagent embedded into a polymeric polydimethylsiloxane (PDMS) composite was proposed for in situ ammonium (NH4+) and urea (NH2CONH2) analysis in water and urine samples, respectively. Satisfactory strategies were also applied for urease-catalyzed hydrolysis of urea, either in solution or glass-supported urease immobilization. Using diffuse reflectance measurements combined with digital image processing of color intensity (RGB coordinates), qualitative and quantitative analyte detection was assessed after the colorime…

Selective and sentivive method based on capillary liquid chromatography with in-tube solid phase microextraction for determination of monochloramine in water

Abstract Due to the difficulties of working with chloramines, a critical examination of monochloramine standard preparation has been performed in order to select the best synthesis conditions. The analyte has been determined by in-tube solid phase extraction coupled to capillary liquid chromatography with UV detection (IT-SPME Capillary LC DAD). Potential factors affecting the response of monochloramine such as the pH of mobile phase and the volume of sample processed by IT-SPME Capillary LC DAD have been investigated and optimized. According to the results of the study, 0.1 mL or 4.0 mL of sample at neutral pH were loaded in the chromatographic system. A sensitive and selective method has …

Ionic-liquid doped polymeric composite as passive colorimetric sensor for meat freshness as a use case.

Abstract A composite membrane containing 1,2-naphthoquinone-4-sulfonic acid sodium salt (NQS) embedded in an ionic liquid (IL)- polydimethylsiloxane (PDMS)- tetraethyl orthosilicate (TEOS)- SiO2 nanoparticles (NPs) polymeric matrix is proposed. The selected IL was 1-methyl-3-octylimidazolium hexafluorophosphate (OMIM PF6). It is demonstrated that ILs chemical additives of PDMS influenced the sol-gel porosity. The sensor analytical performance for ammonia atmospheres has been tested as a function of sampling time (between 0.5 and 312 h), temperature (25 °C and 4 °C) and sampling volume (between 2L and 22 mL) by means of diffuse reflectance measurements and sensor photos, which can be registe…

Improving analysis of apolar organic compounds by the use of a capillary titania-based column: Application to the direct determination of faecal sterols cholesterol and coprostanol in wastewater samples.

This article reports a new procedure for the direct determination of faecal sterols coprostanol and cholesterol in wastewater samples as tracers of human sewage contamination. The method combines in-tube solid-phase microextraction (IT-SPME) for analyte enrichment and capillary liquid chromatography (LC) for separation with diode array detection for identification and quantification. A titania-based polymeric capillary column and a conventional octadecyl silica (ODS) capillary column were evaluated and compared for their ability to separate the analytes. The titania-based column allowed the separation of the analytes in much shorter chromatographic times and with better chromatographic prof…

Combining high performance thin layer chromatography with minispectrometer-fiber optic probe-coupled to smartphone for in place analysis: Lactose quantification in several matrices

ABSTRACT An in place colorimetric method has been proposed for estimation of the quantity of lactose in several matrix (milk, water effluents and surfaces). Analyzing the amount of this carbohydrate it can be control the product, the cleanliness of the parts of the dairy companies and it can avoid contamination of milk products produced there. This method combines the use of HPTLC for sugars separation with novel analytical devices as minispectrophotometer with fiber optic coupled to a smartphone. In order to measure the lactose a colorimetric reaction has been used. Variable volumes of samples or stock solutions were deposited in nano-silica gel layer, a mobile phase of acetonitrile:water:…

Off-line dansylation of amines using C18 solid-phase packings: study of the fluorescence and chemiluminescence detection by post-column derivatization with oxalic acid bis(2, 4, 6-trichloro phenyl ester)/H2O2 in liquid chromatography. Determination of amphetamines in urine samples

Abstract Dansylation of amines (primaries and secondaries) using C18 solid-phase supports is described. The time of analysis and the handing sample have been markedly improved with respect to those required for solution dansylation. The dansylated amine derivates were injected onto the liquid chromatography system and fluorescence detected. The sensitivity and selectivity is better than the other dansylation procedures described in the literature and also better than other derivatization reagents such 1,2-napthoquinone 4-sulfonate (NQS) or 3,5-dinitrobenzoyl chloride (3,5-DNB). Dansyl compounds can also form chemiluminescent derivatives, therefore a post-column derivatization procedure with…

Determination of meropenem in endotracheal tubes by in-tube solid phase microextraction coupled to capillary liquid chromatography with diode array detection.

Meropenem is a widely used antimicrobial for the treatment of infections associated with the use of invasive medical devices in intensive care unit patients. These treatments are not always effective, in fact, in-vitro studies have demonstrated the difficulty of antimicrobials to penetrate into the biofilm, however in-vivo studies of the effect of these compounds is a trend, mostly because of the complexity of pulmonary samples extracted from ETTs. Therefore, the objective of this study was to evaluate in-tube solid phase microextraction (in-tube SPME) coupled to capillary liquid chromatography (CapLC) with DAD to determine meropenem in Errs in order to estimate the penetration capability i…

Trends in Online Intube Solid Phase Microextraction

A solid device based on doped hybrid composites for controlling the dosage of the biocide N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine in industrial formulations

A colorimetric composite device is proposed to determine the widely used biocide N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine (ADP).This sensing device is based on a film of 1,2-Naphthoquinone-4-sulfonate (NQS) embedded into polydimethylsiloxane-tetraethylortosilicate-SiO2 nanoparticles composite (PDMS-TEOS-SiO2NPs). Semiquantitative analysis can be performed by visual inspection. Digitalized image or diffuse reflectance (DR) measurements can be carried out for quantitative analysis. Satisfactory detection limit (0.018%, w/v) and relative standard deviations <12% were achieved. The proposed device has been applied for the determination of ADP in detergent industrial formulations with reco…

H-Point Curve Isolation Method for Coupled Liquid Chromatography and UV−Visible Spectrophotometry

The H-point curve isolation method (HPCIM) for the detection of unknown interferences in chromatography is proposed. The method allows one to estimate the UV-vis spectra of interfering species in a sample as well as to test the purity of the chromatographic peaks. Besides the detection of the unknown interferences in a sample, this method allows one to calculate the concentration of an analyte in the presence of unknown compounds. To illustrate the reliability of the proposed method, samples of diuretics and amphetamines have been analyzed by normal- and reversed-phase high-performance chromatography.

Development of a polydimethylsiloxane–thymol/nitroprusside composite based sensor involving thymol derivatization for ammonium monitoring in water samples

This report describes a polydimethylsiloxane (PDMS)-thymol/nitroprusside delivery composite sensor for direct monitoring of ammonium in environmental water samples. The sensor is based on a PDMS support that contains the Berthelot's reaction reagents. To prepare the PDMS-thymol/nitroprusside composite discs, thymol and nitroprusside have been encapsulated in the PDMS matrix, forming a reagent release support which significantly simplifies the analytical measurements, since it avoids the need to prepare derivatizing reagents and sample handling is reduced to the sampling step. When, the PDMS-thymol/nitroprusside composite was introduced in water samples spontaneous release of the chromophore…

Advantages of monolithic over particulate columns for multiresidue analysis of organic pollutants by in-tube solid-phase microextraction coupled to capillary liquid chromatography

Abstract The performance of a monolithic C 18 column (150 mm × 0.2 mm i.d.) for multiresidue organic pollutants analysis by in-tube solid-phase microextraction (IT-SPME)-capillary liquid chromatography has been studied, and the results have been compared with those obtained using a particulate C 18 column (150 mm × 0.5 mm i.d., 5 μm). Chromatographic separation has been carried out under isocratic elution conditions, and for detection and identification of the analytes a UV-diode array detector has been employed. Several compounds of different chemical structure and hydrophobicity have been used as model compounds: simazine, atrazine and terbutylazine (triazines), chlorfenvinphos and chlorp…

Solid glucose biosensor integrated in a multi-well microplate coupled to a camera-based detector: Application to the multiple analysis of human serum samples

Abstract In the present work, a biosensor adapted in a 96-well microplate has been coupled with a smartphone-based photometer in order to develop a low-cost colorimetric multi-sample dispositive. The strength of this biosensing system is based on the integration of the biosensor into the 96-well microplate and the use of a smartphone and free image analysis software as a microplate reader. The performance of the proposed biosensor has been demonstrated to determine glucose in several human serum samples. This method is simple, cost-effective, sensitive and selective for the determination of glucose in serum, with detection limits of 1.8 mg/dL and a good linearity over the range 6–88 mg/dL. …

Colorimetic biosensing dispositive based on reagentless hybrid biocomposite: Application to hydrogen peroxide determination

Abstract An efficient approach to enhance the performance of colorimetric biosensors has been developed. The biosensor is based on the co-immobilization of the reagent 3,3′,5,5′-teramethylbencidine (TMB) and the enzyme horseradish peroxidase (HRP) in a PDMS-TEOS-SiO2NPs support. The HRP, in presence of H2O2, catalyzes the oxidation of TMB, producing a blue color. The generated biosensor, doped with the substrate (TMB) and the enzyme (HRP) (entrapped or adsorbed), has been used to determine H2O2 in real samples. Firstly, the immobilization of TMB and HRP in the composite has been studied in order to find the best suitable configuration. The kinetic parameters Vmax (maximum reaction rate) and…

Quantifying both ammonium and proline in wines and beer by using a PDMS composite for sensoring.

Abstract Two of the reagents involved in the Berthelot's reaction, thymol and nitroprusside, were embedded in a PDMS composite in order to apply this assay to determine ammonium and proline, in wine and beers. Safety, portability, rapidity, cost-effectiveness and simplicity of the assay were improved. For the proline determination, a modified Berthelot's reaction, which included a ring cleavage of proline, was optimized. The accuracy of the assay was tested. The limits of detection for ammonium was 0.12 µg mL−1 and for proline was in the range from 0.7 to 4.1 µg mL−1, depending on the kind of wine (white, red, or sweet), for beer the LOD was 6 µg mL−1. The precision achieved was slower than…

Urine polyamines determination using dansyl chloride derivatization in solid-phase extraction cartridges and HPLC

The derivatization of biogenic amines such as putrescine, cadaverine, spermidine and spermine with dansyl chloride in solid phase extraction cartridges is described. Different types of filling materials were tested in order to have the highest retention of the different analytes. The best results were obtained by using C18 cartridges. The optimal conditions were: amine solution buffered at pH 12, 2 mM dansyl chloride (acetone-bicarbonate solution 20 mM (pH 9-9.5), 2 + 3 v/v) as reagent concentration, room temperature and 30 min reaction time. The developed procedure was applied to the determination of these polyamines in urine samples from healthy controls and cancer patients using HPLC wit…

Microextraction with phases containing nanoparticles.

In this article, the state of the art of microextraction techniques that involve nanoparticles or nanomaterials (NPs) is reviewed, with special emphasis on the applications described in the biomedical field. The uses and advantages of the different types of NPs such as carbon nanotubes (either single- and multi-walled) and other carbon-based materials, metallic NPs, including gold, silver and magnetic NPs, and silica NPs are summarized. The main strategies used to modify the selectivity, extractive capacity and/or the stability of NPs through a chemical reaction are also reviewed. The potential advantages of NPs in different forms of off-line and on-line microextraction are discussed, and …

Selective determination of ammonium in water based on HPLC and chemiluminescence detection

Abstract A selective and sensitive method has been developed for liquid chromatographic determination of ammonium in water samples. The analyte is derivatized with Dansyl Chloride prior to injection into HPLC. Optimal solution derivatization conditions have been established. The dansyl derivative is separated with the aid of a chromatographic column and post-column mixed with peroxyoxalate (TCPO) and H 2 O 2 in order to perform chemiluminescence detection. The detection limit achieved is 8 μg/L and linear response from 0.027 to 0.750 mg/L of ammonium was obtained. Ammonium ion was determined within 2.4 min under optimum chromatographic conditions. The method is fast, and near 10 derivatized…

A microscale Kjeldahl nitrogen determination for environmental waters.

A microscale Kjeldahl system has been designed which has been homemade reduced. The digestor unit of a macroKjeldahl system and a modified glassware microdistillation unit have been used. The optimal conditions for digestion and distillation have been established for ammonium and methylamine as model compound of organic amino nitrogen. The optimised procedure has been applied to the determination of Kjeldahl nitrogen in water samples. Recoveries near 100% and good precision have been achieved. This procedure combines nitrogen miniaturized system and the use of a selective ion electrode for ammonia detection. The analysis time was reduced 4.8 times and the analysis cost 6.6 times compared wi…

More about sampling and estimation of mercaptans in air samples

[EN] Several strategies have been developed for sampling and determination of volatile thiols. The selectivity and sensitivity of the proposed methodologies are achieved by using a specific derivatizing reagent. The different procedures assayed are based on air sampling followed by derivatization of the analytes with OPA and isoleucine in alkaline solution. The derivatization products are separated and determined by liquid chromatography and fluorescence detection. To start, the derivatization conditions and stability of the derivates have been studied in order to establish the storage conditions. In general, the strategies studied consisted on trapping and detivatization the thiol compound…

Designing solid optical sensors for in situ passive discrimination of volatile amines based on a new one-step hydrophilic PDMS preparation

Abstract We reported an optimal material for embedding chemoresponsive dyes based on modified commercial PDMS. A new approach to impart hydrophilicity to H-PDMS in an unique step was developed by addition of tetraethyl orthosilicate (TEOS) and in absence of basic or acid aqueous mixtures or hydroxyl-compounds during the PDMS coating process. This incorporation significantly enhances the performance of PDMS-based devices for sensing applications. New colorimetric sensors for passive detection and in situ discrimination of volatile amines have been obtained. The limit of detection achieved was 1.5 mg m −3 for both, dimethylamine and methylamine, suitable to control real working atmospheres. T…

In-tube solid-phase microextraction coupled by in valve mode to capillary LC-DAD: Improving detectability to multiresidue organic pollutants analysis in several whole waters

Abstract A simple and fast capillary chromatographic method has been developed to identify and quantify organic pollutants at sub-ppb levels in real water samples. The major groups of pesticides (organic halogens, organic phosphorous, and organic nitrogen compounds), some hydrocarbons (polycyclic aromatic hydrocarbons), phthalates and some phenols such as phenol and bisphenol A (endocrine disruptors) were included in this study. The procedure was based on coupling, in-tube solid-phase microextraction (IT-SPME) by using a conventional GC capillary column (95% methyl–5% phenyl substituted backbone, 80 cm × 0.32 mm i.d., 3 μm film thickness) in the injection valve to capillary liquid chromatog…

Polydimethylsiloxane composites containing 1,2-naphtoquinone 4-sulphonate as unique dispositive for estimation of casein in effluents from dairy industries.

A unique dispositive to determine casein which is the most abundant protein in dairy sewages has been proposed. In this sensing technology, the derivatization reagent 1,2-naphtoquininone 4-sulphonate (NQS) is embedded into a polydimethylsiloxane-tetraethylortosilicate-SiO2 nanoparticles composite (PDMS-TEOS-SiO2NPs). When the composite is immersed into the samples, casein is extracted from the solution and derivatized inside the PDMS matrix after 10 min at 100°C. The sensing support changes its color from yellow to orange depending on the casein concentration. Quantitative analysis can be carried out by measuring the absorbance with a reflection probe or by image-processing tool (GIMP). Thi…

Study of the influence of temperature and precipitations on the levels of BTEX in natural waters.

Assessment of seasonal changes in surface water quality is an important aspect for evaluating temporal variation of water due to natural or anthropogenic inputs of point and non-point sources. The objective of this paper was to investigate the influence of seasonal temperature fluctuations and precipitations on the levels of BTEX in natural waters. Principal component analysis (PCA) was used to evaluate the seasonal correlations of BTEX levels in water and to extract the parameters that are most important in assessing seasonal variations of water quality. This study was carried out as a part of VOCs monitoring program in natural water samples from Mediterranean coast. To carry out this proj…

Nylon-Supported Plasmonic Assay Based on the Aggregation of Silver Nanoparticles: In Situ Determination of Hydrogen Sulfide-like Compounds in Breath Samples as a Proof of Concept

A procedure for supporting silver nanoparticles (AgNPs) on nylon is proposed. Besides, the membrane has been developed as a solid-phase colorimetric plasmonic sensor for volatile sulfide compounds (VSCs) like H2S, CH3SH, and (CH3)2S. AgNP behavior in the membrane has been studied by UV-vis diffuse reflectance spectrometry, Raman spectrometry, High-resolution transmission electron microscopy (HR-TEM), and Scanning electron microscopy (SEM). The sensor responded by changing its color from yellow in absence of VSCs to several orange/brown colors in the function of VSC concentration as occurs in solution; an increase in the hydrodynamic diameter, estimated by both asymmetrical flow field-flow f…

Delivering Inorganic and Organic Reagents and Enzymes from Zein and Developing Optical Sensors.

Nowadays, interest in using environmentally friendly materials is increasing in many fields. However, the rational design of sensors with biodegradable materials is a challenge. The main aim of this work is to show the possibility of using zein, a protein from corn, as a biodegradable and low-cost material for immobilizing, stabilizing, and delivering different kind of reagents for developing optical sensors. Enzymes, metallic salts, and aromatic and small organic compounds were tested. In addition, different techniques of immobilization, entrapment and adsorption, were used, and different formats, such as solid devices and also multiwell platforms, were proposed. The capacity of zein for i…

Automated pre-column derivatization of amines in biological samples with dansyl chloride and with or without post-column chemiluminescence formation by using TCPO-H2O2.

On-line automation of two different liquid chromatographic procedures, a pre-column derivatization system and a pre- and post-column system, in order to generate chemiluminescence is reported. Dansyl chloride (Dns-Cl) was used as a pre-column reagent to form fluorophores and bis(2,4,6-trichlorophenyl) oxalate (TCPO) and hydrogen peroxide (H2O2) as a post-column reagent to generate chemiluminescence. This procedure is based on the employment of a primary column packed with C18 material inserted in a multi-dimensional assembly for sample clean-up and derivatization with Dns-Cl. The dansyl derivatives formed are transferred and separated in a LiChrospher 100 RP18 analytical column (125 x 4 mm …

Solid phase extraction of amines

Abstract The objective of this paper is to provide information about solid phase extraction (SPE) as an alternative to liquid–liquid extraction of amines from several matrices. Different sorbents ranging from non-polar phases, such as C 18 silica to more polar such as cyanopropylsilica (CN) have been tested for analysis of aliphatic amines as monoamines, diamines and polyamines. Phenylalkylamines such as amphetamine or methamphetamine and heterocyclic amines such as histamine or cephalosporins (which also contain a carboxylic group), have also been studied. The different steps involved in the extraction procedure have been tested (conditioning, retention, pre-concentration, washing and elut…

New Reusable Solid Biosensor with Covalent Immobilization of the Horseradish Peroxidase Enzyme: In Situ Liberation Studies of Hydrogen Peroxide by Portable Chemiluminescent Determination.

Herein, we reported a chemiluminescent biosensor based on the covalent immobilization of the horseradish peroxidase (HRP) enzyme on a polydimethylsiloxane (PDMS) support to quantify in situ hydrogen peroxide (H2O2). The chemiluminescent reaction based on the use of luminol as an oxidizable substrate, with HRP as the catalyst, has been used in order to quantify H2O2 as the oxidizing agent. The performance of the proposed biosensor has been demonstrated to determine H2O2 liberated by cells in a culture medium and for evaluating the delivery of H2O2 from denture cleaner tablets, as examples of application. For both analyses, the results indicated that the biosensor is cost-effective, sensitive…

Solid-Phase Extraction and Clean-Up Procedures in Pharmaceutical Analysis

Solid-phase extraction (SPE) using small cartridges filled with sorbents of a small particle size has rapidly established itself as an important sample clean-up technique. It has prospered at the expense of liquid-liquid extraction (LLE), which is considered labor intensive and frequently plagued by problems, such as emulsion formation and use of large volumes of hazardous solvents. A remarkable characteristic of SPE is its easy adaptation to on-line mode by column-switching techniques; switching can be effected manually or by automated controllers. The same analyte/sorbent interactions that are exploited in liquid chromatography (LC) are of use in SPE, but particle sizes employed are great…

Recent advances of in-tube solid-phase microextraction

Abstract In-tube solid-phase microextraction (SPME) is ideally suited to developing green extraction by combining miniaturization, automation and reduction of solvent consumption. SPME has been used for the analysis of environmental, biological, and food samples, and numerous works have shown the benefits of using SPME. However, for full development of in-tube SPME, effort is still needed to overcome limitations, such as low extraction efficiency, selectivity and mechanical stability. To achieve these objectives, research on in-tube SPME is mainly focused in two scenarios: (1) the coupling of in-tube SPME with new chromatographic modalities, such as miniaturized liquid chromatography; and, …

Scaling the Analytical Information Given by Several Types of Colorimetric and Spectroscopic Instruments Including Smartphones: Rules for Their Use and Establishing Figures of Merit of Solid Chemosensors.

The analytical information given by different types of instruments was scaled in order to establish suitably the figures of merit of a given methodology based on color measurements. Different lab and portable instruments, including smartphones with and without a miniaturized spectrophotometer accessory, have been tested. In order to obtain broad information and using objective criteria, these instruments have been compared from (1) the analytical point of view, considering mainly the detection limit (limits of detection [LODs]), selectivity, accuracy and intra- and interday precision, size, components, and costs; and (2) the environmental point of view, based on their footprint as kilograms…

Amphetamine and Methamphetamine Determinations in Biological Samples by High Performance Liquid Chromatography. A Review

Abstract This critical review shows the different high performance liquid chromatography methods proposed for amphetamine and methamphetamine determinations. It is directed mainly towards sample clean up and derivatizations steps, because of their significance in such determinations.

New optical paper sensor for in situ measurement of hydrogen sulphide in waters and atmospheres

A novel and low-cost colorimetric sensor for the determination of hydrogen sulphide in environmental samples has been developed. This sensor is based on the immobilization of the reagent N,N-Dimethyl-p-phenylenediamine and FeCl3 in paper support, in which the H2S is adsorbed in order to give rise to the formation of methylene blue as reaction product. The sensor has been applied to determine H2S in water and air samples. Two different sampling systems for H2S caption from the air have been assayed: active and passive sampling. The analytical properties of the different systems have been obtained and compared. The analytical signals, corresponding to the methylene blue, have been obtained me…

Reduction of Nitrates in Waste Water through the Valorization of Rice Straw: LIFE LIBERNITRATE Project

An improved and more sustainable waste management system is required for successful development of technologies based on renewable sources. Rice straw is submitted to controlled combustion reactions and the produced ashes are chemically treated to produce silica. After a chemical activation step, the activated silica shows potential as an adsorbent agent and will be used to remove the excess of nitrates in groundwater and wells in the area of Alginet (Valencia, Spain), selected as a vulnerable zone within the Nitrates Directive. The demonstration activity aims to have a local impact on municipalities of 200 inhabitants or fewer, decreasing from current nitrate concentrations close to 50 mg/…

Monofunctional pyrenes at carbon nanotube electrodes for direct electron transfer H2O2 reduction with HRP and HRP-bacterial nanocellulose

Abstract The non-covalent modification of carbon nanotube electrodes with pyrene derivatives is a versatile approach to enhance the electrical wiring of enzymes for biosensors and biofuel cells. We report here a comparative study of five pyrene derivatives adsorbed at multi-walled carbon nanotube electrodes to shed light on their ability to promote direct electron transfer with horseradish peroxidase (HRP) for H2O2 reduction. In all cases, pyrene-modified electrodes enhanced catalytic reduction compared to the unmodified electrodes. The pyrene N-hydroxysuccinimide (NHS) ester derivative provided access to the highest catalytic current of 1.4 mA cm−2 at 6 mmol L−1 H2O2, high onset potential …

A guide for selecting the most appropriate method for ammonium determination in water analysis

Abstract We have critically evaluated the main parameters involved in determining ammonium in water samples, in order to select the most suitable method appropriate to the requirements of the analysis. We compared several methods: reference (ion-selective electrodes, Nessler and indophenol); Roth’s modified; based on luminol reaction; and, based on peroxioxalate reaction.

In Situ Analysis Devices for Estimating the Environmental Footprint in Beverages Industry

Abstract The need to calculate the environmental footprint could mean the integration of sustainability in differentiation strategies for beverages industries. The parameters for estimating the footprint are outlined and discussed. The main negative impacts are related to water pollution, atmospheric pollution, and solid waste. Agro-industrial effluents may contain pesticides, complex oils, alkaline or acidic compounds, and other organic substances. As for atmospheric emissions, particulate material, SO2, NOx, hydrocarbons, and other organic compounds, can be mentioned. The state of art of in situ analysis devices for this purpose is described. The devices are compared through the tool CALI…

Miniaturized matrix solid phase dispersion procedure and solid phase microextraction for the analysis of organochlorinated pesticides and polybrominated diphenylethers in biota samples by gas chromatography electron capture detection

Abstract This work has developed a miniaturized method based on matrix solid phase dispersion (MSPD) using C18 as dispersant and acetonitrile–water as eluting solvent for the analysis of legislated organochlorinated pesticides (OCPs) and polybrominated diphenylethers (PBDEs) in biota samples by GC with electron capture (GC-ECD). The method has compared Florisil®-acidic Silica and C18 as dispersant for samples as well as different solvents. Recovery studies showed that the combination of C18–Florisil® was better when using low amount of samples (0.1 g) and with low volumes of acetonitrile–water (2.6 mL). The use of SPME for extracting the analytes from the solvent mixture before the injectio…