Analysis of enantiomers giving partially overlapped peaks by using different treatments of the chromatographic ultraviolet signals: quantification of pseudoephedrine enantiomers

Abstract Different strategies for the quantification of partially coeluting optical isomers have been investigated. The methods tested are based on the use of different features as the analytical UV signals: peak heights, perpendicular drop areas, first and second derivatives of the chromatograms, peak areas obtained by deconvolution of the overlapped peaks with data fitting optimization, and a multivariate model (principal component regression, PCR). The amphetamine-derivative drug pseudoephedrine was selected as a model compound. For chromatography, LiChrospher 100 RP 18 and a mobile-phase consisting of methanol and a solution of carboxymethyl-β-cyclodextrin (the chiral selector) were use…

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(+).

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 …

Evaluation and elimination of the “blank bias error” using the H-point standard addition method

Abstract The basis of the H-point standard addition method in the cases where the analyte determination requires the use of an absorbent reagent is considered. The method evaluates and eliminates the blank bias error present in such procedures by using the absorbance increment at two selected wavelengths as the analytical signal of the calibration graphs. Three different determinations were tested: the determination of proteins with the biuret method, thorium with thoron and of magnesium with Titan Yellow. These procedures are better described by the proposed method than by the traditional approach using absorbance values against reagent blank.

On-line in-tube solid phase microextraction coupled to capillary liquid chromatography-diode array detection for the analysis of caffeine and its metabolites in small amounts of biological samples.

Abstract In-tube solid phase microextraction (IT-SPME) coupled on-line to capillary liquid chromatography with diode array detection provides a simple and fast analytical methodology for the simultaneous quantitation of caffeine and its three primary metabolites (theobromine, paraxanthine and theophylline) in micro samples of serum, saliva and urine matrices. The sample amount required for one analysis was only 2.5 μL of saliva, 6.25 μL of serum or 40 μL of urine, a requirement for its implementation in a hospital laboratory for preterm newborns, where sample availability is a major problem. In standard conditions, 25 μL of diluted saliva or serum (or 100 μL of urine) were processed by IT-S…

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…

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…

Cotton swabs supported in-situ assay for quaternary ammonium compounds residues in effluents and surfaces

Abstract Cellulose paper and cotton swabs have been tested as sampling, reaction and measurement media for quaternary ammonium compounds (QACs) using the reagent Chromo Azurol S in the presence of aluminum cations (CAS-Al). On the basis of the results obtained a new method is proposed for the analysis of QACs in water samples which only entails the successive immersion of swabs into 1 mL of the samples, 1 mL of a solution of CAS-Al for the formation of a ternary blue complex, and 1 mL of water to remove the excess of reagent. The method can be used for the visual on site detection of QACs in effluents, as well as for their quantification within the 3.62–36.2 mg/L range through the direct me…

Innovations in Extractive Phases for In-Tube Solid-Phase Microextraction Coupled to Miniaturized Liquid Chromatography: A Critical Review

Over the past years, a great effort has been devoted to the development of new sorbents that can be used to pack or to coat extractive capillaries for in-tube solid-phase microextraction (IT-SPME). Many of those efforts have been focused on the preparation of capillaries for miniaturized liquid chromatography (LC) due to the reduced availability of capillary columns with appropriate dimensions for this kind of system. Moreover, many of the extractive capillaries that have been used for IT-SPME so far are segments of open columns from the gas chromatography (GC) field, but the phase nature and dimensions are very limited. In particular, polar compounds barely interact with stationary GC phas…

An evaluation of solid phase microextraction for aliphatic amines using derivatization with 9-fluorenylmethyl chloroformate and liquid chromatography

The reliability of SPME combined with a chemical reaction for the analysis of short-chain aliphatic amines by liquid chromatography has been investigated. Different options to couple SPME and derivatization have been tested and compared: (i) derivatization of the analytes in solution followed by the extraction of the derivatives, (ii) extraction of the analytes and subsequent derivatization by immersing the SPME fibre onto a solution of the reagent, and (iii) extraction/derivatization of the analytes using fibres previously coated with the reagent. Methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA) have been selected as a model of primary, secondary and tertiary amines, respecti…

Capillary Liquid Chromatography for the Determination of Terpenes in Botanical Dietary Supplements

Dietary supplements of botanical origin are increasingly consumed due to their content of plant constituents with potential benefits on health and wellness. Among those constituents, terpenes are gaining attention because of their diverse biological activities (anti-inflammatory, antibacterial, geroprotective, and others). While most of the existing analytical methods have focused on establishing the terpenic fingerprint of some plants, typically by gas chromatography, methods capable of quantifying representative terpenes in herbal preparations and dietary supplements with combined high sensitivity and precision, simplicity, and high throughput are still necessary. In this study, we have e…

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 …

New Calibration Model: Combining Integrated Calibration Method and H-point Standard Addition Method to Detect and Avoid Interference Effects

A new calibration methodology based on the combination of integrated calibration method (ICM) and the H-point standard addition method (HPSAM) is presented. It allows the diagnosis and correction o...

Quantitative Analysis of Terpenic Compounds in Microsamples of Resins by Capillary Liquid Chromatography

A method has been developed for the separation and quantification of terpenic compounds typically used as markers in the chemical characterization of resins based on capillary liquid chromatography coupled to UV detection. The sample treatment, separation and detection conditions have been optimized in order to analyze compounds of different polarities and volatilities in a single chromatographic run. The monoterpene limonene and the triterpenes lupeol, lupenone, &beta

Analysis of Contact Traces of Cannabis by In-Tube Solid-Phase Microextraction Coupled to Nanoliquid Chromatography

Because of its inherent qualities, in-tube solid-phase microextraction (IT-SPME) coupled on-line to nanoliquid chromatography (nanoLC) can be a very powerful tool to address the new challenges of analytical laboratories such as the analysis of traces of complex samples. This is the case of the detection of contact traces of drugs, especially cannabis. The main difficulties encountered in the analysis of traces of cannabis plants on surfaces are the low amount of sample available (typically &lt

Trends in Online Intube Solid Phase Microextraction

Cleaning sorbents used in matrix solid-phase dispersion with sonication: Application to the estimation of polycyclic aromatic hydrocarbons at ng/g levels in marine sediments

This study shows that ultrasonic assisted extraction is a good practise for removing impurities from sorbents used for matrix-solid phase dispersion (MSPD). A previous washing of the sorbent with an organic solvent or mixture of solvents eliminates part of the interferences, but this treatment is not enough for the quantification of PAHs at ng/g levels. It is demonstrated that the determination of traces of polycyclic aromatic hydrocarbons (PAHs) in solid samples processed by matrix-solid phase dispersion (MSPD) may be severely affected by the presence of sorbent impurities. Different extraction solvents and sonication conditions have been tested, and on the basis of the results obtained a …

Improving the On-Line Extraction of Polar Compounds by IT-SPME with Silica Nanoparticles Modified Phases

In the present work the extraction efficiency of in-tube solid-phase microextraction (IT-SPME) for polar herbicides has been evaluated using extractive capillaries coated with different polymeric sorbents. For this purpose, aqueous solutions of herbicides with a wide range of polarities, including some highly polar compounds (log Kow < 1), have been directly processed by IT-SPME coupled on-line to capillary liquid chromatography with UV-diode array detection. For extraction, commercially available capillary columns coated with polydimethylsiloxane (PDMS) and polyetilenglicol (PEG)-based phases have been used, and the results have been compared with those obtained with a synthesized tetra…

Evaluation and elimination of the blank bias error using the H-point standard additions method (HPSAM) in the simultaneous spectrophotometric determination of two analytes

Abstract The aim of this report is to demonstrate the usefulness of the HPSAM in all instances where the determination of two analytes requires the use of an absorbent reagent, particularly when it does not present a constant analytical signal because of its consumption. This problem can be treated as a ternary mixture by the HPSAM method and then, the fundamentals of the method for resolving these kind of mixtures can be applied. The method can calculate the concentration of one species from spectral data at two wavelengths where the two other species present the same absorbance relationship. These wavelength pairs are easily found, and can be selected to give the most precise results. The…

Liquid chromatographic determination of aliphatic amines in water using solid support assisted derivatization with 9-fluorenylmethyl chloroformate

A simple and sensitive method has been developed for the liquid chromatographic determination of short-chain aliphatic amines in water. Analytes are retained in solid-phase extraction (SPE) cartridges, and then derivatized by drawing an aliquot of the fluorogeneic reagent 9-fluorenylmethyl chloroformate (FMOC) through the cartridges. After a certain reaction time the derivatives formed are desorbed with acetonitrile. The collected extracts are then chromatographed on a LiChrospher 100 RP18 125 mm×4 mm i.d., 5 μm, column using an acetonitrile-water gradient. The influence of experimental conditions (SPE material, volume of sample, concentration of FMOC, time of reaction and pH) has been inve…

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…

Establishing the occurrence and profile of polycyclic aromatic hydrocarbons in marine sediments: The eastern Mediterranean coast of Spain as a case study.

Sampling, cost-effective analysis, diagnosis of sources of pollution and assessment of potential toxicological effects were included in the case study. Marine sediments collected from 24 points along the eastern Mediterranean coast of Spain (Comunitat Valenciana region) in 2010, 2011, 2012 and 2015 have been analysed for polycyclic aromatic hydrocarbons. Fluoranthene, pyrene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene were the most found. An analysis of the relative abundance of selected PAHs revealed that petrogenic and mixed petrogenic/pyrogenic sources are predominant in the area. The total concentrations of the target compounds ranged from 14.7 to 615.3 ng/g dry weight. The effec…

Development of the H-point standard additions method for analyte determinations in unknown matrix

Abstract The development of the H-point standard additions method is proposed in order to obtain the unbiased analyte concentration when the matrix of the sample is completely unknown. A spectral region where the interferent behaviour can be considered linear at three wavelengths must be chosen. The method uses the analytical signal data at these three wavelengths, usually situated in the maxima region of the analyte. Two procedures are proposed in order to know and to locate this behaviour for the unknown interferent. Several binary and ternary mixtures of phenol, 4-chlorophenol and 4-chloro-3-methylphenol as representative examples have been assayed, with accurate (less than 3% relative e…

Sensitive determination of methylenedioxylated amphetamines by liquid chromatography.

Different strategies for the liquid chromatographic determination of methylenedioxylated amphetamines were evaluated: separation and detection of underivatized analytes by (i) UV or (ii) fluorescence, (iii) derivatization with 3,5-dinitrobenzoyl chloride followed by separation and UV detection of the derivatives formed and (iv) derivatization with 9-fluorenylmethyl chloroformate (FMOC) and subsequent separation and fluorimetric detection of the derivatives. The compounds tested were 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDE). On the basis of these studies, a new procedure for the chromatographic determination of…

Separation of the enantiomers of primary and secondary amphetamines by liquid chromatography after derivatization with (−)-1-(9-fluorenyl)ethyl chloroformate

The chiral reagent (−)-1-(9-fluorenyl)ethyl chloroformate (FLEC) has been evaluated for the enantioselective analysis of amphetamines by liquid chromatography. For separation of the FLEC diastereomers conventional reversed-phase conditions were used. The conditions affording the best enantiomeric resolution and sensitivity were determined for amphetamine, methamphetamine, ephedrine, pseudoephedrine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), and 3,4-methylenedioxyethylamphetamine (MDE). All the amphetamines assayed could be separated with resolution factors ranging from 0.91 to 1.92. Although FLEC is typically used as a fluorogenic reagent, it was shown t…

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…

Exploring hand-portable nano-liquid chromatography for in place water analysis: Determination of trimethylxanthines as a use case.

Abstract Analytical performance and optimization of figures of merit of a portable nano liquid chromatograph (NanoLC) with UV detection at 255 nm have been established for in place analysis. Methylxanthines: caffeine, theophylline and theobromine were selected as target analytes. A fast lab method based on IT-SPME coupled on line with capillary liquid chromatograph (CapLC) with diode array detection (DAD) was employed for comparative studies. IT-SPME and solid phase extraction were coupled off-line to NanoLC for improving instrumental parameters, mainly detection capacity and selectivity. IT-SPME or SPE/portable NanoLC based methods were superior in terms of chromatographic resolution and o…

Analyte estimation using the generalized H-point standard additions method and a new methodology for locating linear spectral intervals for unknown interferents

An improvement in the way to locate linear spectral intervals for unknown interferents which overlap the analyte signal in UV–visible spectrophotometry is offered as an alternative to the method previously described by Campins-Falco et al. (Anal. Chim. Acta, 302, 323 (1995)). In that report, quotients of the second-derivative spectra of the sample and analyte were used. The new method improves on the old one by using first- instead of second-derivative data, thus eliminating the possible divisions by zero (inflection points for the analyte) obtained in the previous procedure. The linear intervals are now obtained by plotting for each wavelength the differences in first-derivative data betwe…

A cost-effective method for estimating di(2-ethylhexyl)phthalate in coastal sediments.

This study describes the development of a new method for the analysis of di(2-ethylhexyl)phthalate (DEHP) using 0.1-0.3 g of sediment sample, based on matrix solid phase dispersion (MSPD) using C18 as dispersant phase (0.4 g) and acetonitrile-water as eluting solvent (3.4 mL 1:3.25, v/v). No evaporation step is required. 3 mL of extracts were processed on-line by in-tube solid phase microextraction (IT-SPME) coupled to capillary liquid chromatography (CapLC) and diode array detector (DAD). A short analytical column Zorbax SB C18 (35×0.5 mm, 5 μm) provided suitable results. FTIR-ATR was employed for characterizing sediment samples and MSPD procedure. The total analysis time was less than 20 …

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 …

Determination of aliphatic amines in water by liquid chromatography using solid-phase extraction cartridges for preconcentration and derivatization

Bond Elut C18 solid-phase extraction cartridges were used for preconcentration and pre-column derivatization with 3,5-dinitrobenzoyl chloride (DNB) of aliphatic amines in water. Conditions for analyte preconcentration and derivatization (including the volume of sample, concentration of reagent, time of reaction and pH) were investigated, using ethylamine, isopropylamine and dimethylamine as model compounds. On the basis of these studies, a rapid and sensitive method for the determination of aliphatic amines in water is presented. The analytes are retained and purified on the cartridges and then derivatized and desorbed by drawing in succession the DNB solution and acetonitrile. The collecte…

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…

Systematic Study of Several Causes and Effects Due to Absorbent Blanks in Determinations of One Analyte

A systematic study is performed about several factors involved in the measurements when a absorbent blank is used, as molar absorption coefficient of the formed complex, absorbance of the blank at the measured wavelength, and kind of spectrophotometer used (conventional double-beam or diode-array). It is proved that the usual methodology, measuring against reagent blank, produces less accurate measurements than those obtained against solvent blank. On the other hand, use of the H-Point standard additions method provides always equal or better results than the best ones obtained at single wavelengths by using measurements against solvent bank, at the maximum of the formed complex. To test th…

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…

A new tool for direct non-invasive evaluation of chlorophyll a content from diffuse reflectance measurements

Abstract Chlorophyll is a key biochemical component that is responsible for photosynthesis and is an indicator of plant health. The effect of stressors can be determined by measuring the amount of chlorophyll a , which is the most abundant chlorophyll, in vegetation in general. Nowadays, invasive methods and vegetation indices are used for establishing chlorophyll amount or an approximation to this value, respectively. This paper demonstrates that H-point curve isolation method (HPCIM) is useful for isolating the signal of chlorophyll a from non-invasive diffuse reflectance measurements of leaves. Spinach plants have been chosen as an example. For applying the HPCIM only the registers of bo…

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…

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…

Determination of amphetamines in hair by integrating sample disruption, clean-up and solid phase derivatization

The utility of matrix solid phase dispersion (MSPD) for the direct analysis of amphetamines in hair samples has been evaluated, using liquid chromatography (LC) with fluorescence detection and precolumn derivatization. The proposed approach is based on the employment of MSPD for matrix disruption and clean-up, followed by the derivatization of the analytes onto the dispersant-sample blend. The fluorogenic reagent 9-fluorenylmethyl chloroformate (FMOC) has been used for derivatization. Different conditions for MSPD, analyte purification and solid phase derivatization have been tested, using amphetamine (AMP), methamphetamine (MET), ephedrine (EPE) and 3,4-methylenedioxymethamphetamine (MDMA)…

H-Point standard additions method for resolution of binary mixtures with simultaneous addition of both analytes

Abstract The basis of the H-point standard additions method, HPSAM, with simultaneous addition of both analytes is proposed for the resolution of binary mixtures. It is a modification of the previously described H-point standard additions method that permits the resolution of both species from a unique calibration set by making the simultaneous addition of the two analytes. The method uses as analytical signals the absorbances at pairs of wavelengths where each species shows the same absorbance. The required data to apply the method are the absorbance values at the previously selected wavelengths for the sample alone and spiked with both species at known concentrations. Linear relations bet…

Disinfection by-products effect on swimmers oxidative stress and respiratory damage.

Disinfection by-products (DBPs) are generated through the reaction of chlorine with organic and inorganic matter in indoor swimming pools. Different DBPs are present in indoor swimming pools. This study evaluated the effects of different chlorinated formations in oxidative stress and lung damage in 20 swimmers after 40 min of aerobic swimming in 3 indoor pools with different characteristics. Biological samples were collected to measure lung damage (serum-surfactant-associated proteins A and B), oxidative stress parameters (plasma protein carbonylation and malondialdehyde, and whole-blood glutathione oxidation), and swimming exertion values (blood lactate) before and after exercise. Free chl…

Elimination of the unknown irrelevant matrix absorbance by using the H-Point Standard Additions Method (HPSAM)

It is demonstrated how the H-Point Standard Additions Method (HPSAM) using DeltaA as analytical signal (from data at three previously selected wavelengths) is only related with analyte concentration when unknown irrelevant matrix absorbance is present. The method is compared with the most common previously reported methods, such as derivative spectroscopy or the compensation method. The obtained results show that the proposed HPSAM leads to the same found concentration of analyte as the other reported methods, except detection limits and standard deviation for six replicates which are lower, because of the use of absorbance data (instead of first derivative data as usual). In addition, the …

H-point standard additions method for resolution of overlapped chromatographic peaks with a conventional fluorescence detector. Determination of phenol and cresols in waters

The H-Point Standard Additions Method (HPSAM) is proposed in order to resolve overlapping peaks in liquid chromatography by using a conventional fluorescence detector. The method uses as analytical signals the heights or the areas obtained at two previously selected emission wavelengths, and good results are obtained for highly overlapping peaks with highly overlapping fluorescence spectra. The principal benefits of the method are the ease of finding the required wavelengths, its insensitivity to changes in the retention time of the peak from one injection to another, and the possibility of using it in highly or only partially overlapping peaks. We have applied the method to the determinati…

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, …

Multivariate versus univariate calibration for nonlinear chemiluminescence data

Abstract Multivariate calibration is tested as an alternative to model chromium(III) concentration versus chemiluminescence registers obtained from luminol-hydrogen peroxide reaction. The multivariate calibration approaches included have been: conventional linear methods (principal component regression (PCR) and partial least squares (PLS)), nonlinear methods (nonlinear variants and variants of locally weighted regression) and linear methods combined with variable selection performed in the original or in the transformed data (stepwise multiple linear regression procedure). Both the direct and inverse univariate approaches have been also tested. The use of a double logarithmic transformatio…

Strategies for the enantiomeric determination of amphetamine and related compounds by liquid chromatography.

This paper summarizes recent research on the stereospecific analysis of amphetamine, its analogs and metabolites, by liquid chromatography. The different methods proposed have been evaluated and compared in terms of resolution power, time of analysis, sensitivity, or potential for automation. Chiral derivatization, followed by separation of the diastereomers formed in achiral chromatographic systems, is still the method preferred for the analysis of amphetamines at trace levels, as derivatization also improves analyte detectability. This is the method of choice for the enantiomeric analysis of amphetamines at the low concentrations typically encountered in biological samples. In recent year…

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…

Enantiomeric separation of amphetamine and related compounds by liquid chromatography using precolumn derivatization witho-phthaldialdehyde

The utility of the derivatization reagento-phthaldialdehyde (OPA) in combination with the chiral thiol N-acetyl-L-cysteine (NAC) for the enantioselective analysis of primary amphetamines and structurally related substances has been investigated. The diastereomers obtained have been chromatographed on an achiral, reversed phase C18 column (125 mm×4 mm i.d., 5 μm), and detected fluorimetrically. The influence of parameters affecting the chromatographic separation as well as the derivatization reaction has been optimized, using amphetamine, norephedrine, norepinephrine and 3,4-methylenedioxyamphetamine (MDA) as model compounds. On the basis of the results obtained, possible conditions for the …

Application of the H-point standard additions method by using absorbance increment values as analytical signals

Abstract This paper demonstrates how the absorbance increment (ΔA) between two wavelengths selected according to the fundamental criteria for application of the H-Point standard additions method (HPSAM) are only related to the analyte concentration. A procedure for calculation of the unknown analyte concentration with no bias error by applying HPSAM to ΔA values in much the same way as the method of standard additions (MOSA), is reported. The method was also applied to a calibration with a single standard. The results obtained on 6 samples with maximal separations between 65 and 0 nm are reported. Finally, the proposed method was applied to the resolution of different phenol-o-cresol mixtur…