Biomarkers of exposure in urine of active smokers, non-smokers, and vapers.

The exposure to smoking related products has been evaluated through urine illness risk marker determination through the analysis of urine samples of smokers and vapers. Biomarkers and their metabolites such as N-acetyl-S-(2-cyanoethyl)-L-cysteine (CEMA), N-acetyl-S-(3,4-dihydroxybutyl)-L-cysteine (DHBMA), N-acetyl-S-[1-(hydroxymethyl)-2-propen-1-yl)-L-cysteine (MHBMA), N-acetyl-S-(3-hydroxypropyl)-L-cysteine (3HPMA), 2R-N-acetyl-S-(4-hydroxybutan-2-yl)-L-cysteine (HMPMA), and N-acetyl-S-(3-carboxy-2-propyl)-L-cysteine (CMEMA) together with nicotine and cotinine were identified and quantified by LC-HRMS and LC-MS/MS, and data found normalized to the creatinine level. One hundred two urine samples were collected from smokers, non-smokers, and vapers, spanning an age range from 16 to 79 years. Results obtained showed that CEMA was only detected in urine samples from smokers and MHBMA was in the same order of magnitude in all the urine samples analyzed. HMPMA was found in the urine of vapers at the same order of concentration as in non-smokers. 3HPMA in vapers was lower than in the urine of smokers, presenting an intermediate situation between smokers and non-smokers. On the other hand, DHBMA in vapers can reach similar values to those found for smokers, while CMEMA shows concentrations in the urine of vapers higher than in the case of non-smokers and traditional smokers, requiring new research to link this metabolite to the use of electronic cigarettes and possible alternative metabolomic routes. In general, this study seems to verify that traditional smoking practice constitutes a major source of carcinogenic chemicals compared with substitutive practices, although those practices are not free of potential harm.

Monolith-coated microcentrifuge tubes for the easy extraction of psychoactive substances from urine samples and liquid chromatography-tandem mass spectrometry determination.

BACKGROUND: Sample extraction is one of the most critical steps in most of the analytical processes. Nowadays, there is a demand for simple approaches that can effectively extract and concentrate target analytes from complex matrices, like biofluids, with accurate and reliable results. RESULTS: A porous monolith of poly(methacrylic acid-co-ethylene glycol dimethacrylate) has been immobilized on the inner wall of a 2 mL commercial polypropylene microcentrifuge tube through radical photopolymerization, using bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as radical initiator and 405 nm laser pointer activation. Photopolymerization parameters were adjusted to obtain a continuous and homogeneous polymer layer (0.16 mm wet polymer thickness and 31 mg dry polymer weight) in the inner tube surface. Extraction efficiency of twelve psychoactive substances was assessed by the evaluation of the effect of sample pH, extraction and desorption times, and desorption solvent volume. Moreover, matrix effect, reusability and stability of monolith-coated microcentrifuge tubes were studied. Sample extracts were measured by liquid chromatography-tandem mass spectrometry, providing limits of quantification (LOQ) from 0.2 to 2.7 µg L-1, recoveries from 80 to 118 %, relative standard deviations lower than 17 %, and a linear range from LOQ to 500 µg L-1. SIGNIFICANCE: The proposed device is suitable for the easy and simple extraction of psychoactive substances from urine samples with a high portability, reduced solvent consumption, low cost, and low environmental impact.

A green methodology for the determination of cocaine in camouflaged samples.

A methodology based on the ultrasound-assisted extraction with ethanol and the dry film attenuated total reflectance infrared spectroscopy (DF-ATR-FTIR) measurement of extracts has been developed for a fast evaluation of non-conventional ("exotic") solid-sized cocaine samples. The method provides quantitative results in less than three minutes with a limit of detection in the solid sample of 1.6 µg g-1 of cocaine with a variation coefficient lower than 7%. Results found for seized samples of different natures were compared with those obtained by a reference gas chromatography method and the greenness of the whole proposed procedure was evaluated and compared using the analytical eco-scale, green analytical procedure index (GAPI), and analytical greenness metric (AGREE). The green evaluation of the proposed methodology provided green scores by considering different evaluation criteria.

Protein determination in serum and whole blood by attenuated total reflectance infrared spectroscopy.

Attenuated total reflectance mid-infrared spectra of serum and blood samples were obtained from 4,000 to 600 cm(-1). Models for the determination of albumin, immunoglobulin, total globulin, and albumin/globulin coefficients were established for serum samples, using reference data obtained by capillary electrophoresis. Based on the use of the amide bands I and II regions, the relative root mean square error of prediction (RRMSEP) was 4.9, 14.9, 4.5, and 7.1% for albumin, immunoglobulin, total globulin, and albumin/globulin coefficients, respectively, determined in an independent validation set of 120 samples using 200 samples for calibration. Additionally, the use of Kennard-Stone method for the selection of a representative calibration subset of samples provided comparable results using only 60 samples. For whole blood analysis, hemoglobin was determined in 40 validation samples using models built from 40 calibration independent samples with RRMSEP of 8.3, 5.5, and 4.9% with models built from direct spectra in the first case and from sample spectra recorded after lysis by sodium dodecyl sulfate and freezing, respectively, for the last two ones. The developed methodologies offer green alternatives for patient diagnosis in a few minutes, minimizing the use of reagents and residues and being adaptable for its use as a point-of-care method.

Date-rape evidence through fast determination of γ-butyrolactone in adulterated beverages.

An infrared spectroscopy (IR) based methodology has been developed to determine γ-butyrolactone (GBL) in adulterated beverages. The proposed method permits the direct screening of GBL in beverages and involves a minimum sample treatment requiring less than 2 min for quantitative determination of GBL. Sensitivity of IR method was improved by using liquid-liquid extraction (LLE) providing detection limits of 0.023 mg g-1. Accuracy of the proposed methodology was evaluated through the analysis of soft beverages and alcoholic cocktails spiked with GBL at concentration levels ranging from 0.075 to 10 mg g-1 providing recovery values from 91 to 100%. GBL was determined in twelve blind-spiked beverages, including from mineral water to wine and cocktails. Results obtained were statistically comparable to those provided by a liquid chromatography (LC) reference methodology and consistent with the spiked values. Therefore, the use of LLE-FTIR allowed a simple, sensitive and quantitative determination of GBL in soft beverages and alcoholic cocktails, thus evidencing its use for sex submission intention.

The use of near-infrared spectrometry in the olive oil industry.

The enormous possibilities offered by near-infrared (NIR) spectroscopy for the (on/in/at-line) quality control process of olive fruits, pastes, and oils are summarized throughout this paper. Special attention has been paid to the combination of NIR and chemometric treatments for the on-line analysis of olive fruits and also for the quality parameters evaluation on olive oils and pastes which can enhance the production of a high quality olive oil and the selection of olive fruit with superior properties. The implementation of NIR sensors in olive mills with successful results has also been reviewed and the commercial olive fruit and oil analyzers highlighted.

Self-Administered Cognitive Testing by Older Adults At-Risk for Cognitive Decline.

Self-administered computerized cognitive testing could effectively monitor older individuals at-risk for cognitive decline at home. In this study, we tested the feasibility and reliability of 3 tablet-based executive functioning measures and an executive composite score in a sample of 30 older adults (age 80±6) with high multimorbidity. The tests were examiner-administered at baseline and then self-administered by the participants at home across 2 subsequent days. Eight of the participants reported no prior experience with touchscreen technology. Twenty-seven participants completed both self-administered assessments, and 28 completed at least one. Cronbach's alpha (individual tests: .87-.89, composite: .93) and correlations between examiner-administered and self-administered performances (individual tests: .72-.91, composite: .93) were high. The participants who had never used a smartphone or a tablet computer showed comparable consistency. Remote self-administered tablet-based testing in older adults at-risk for cognitive decline is feasible and reliable, even among participants without prior technology experience.

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 factor which maximizes the analyte signal minimizing the interferent contributions, being selected the detection wavenumbers of 1034 and 1138 cm(-1) for lecithin and soybean oil, respectively in the first order derivative ATR-FTIR spectra. The method provides limits of detection of 2 and 4 mg ml(-1) for lecithin and soybean oil and repeatability values, measured as relative standard deviation, of 2.5% and 3.4% being extended the linear range till 100 mg ml(-1) for lecithin and up to 50 mg ml(-1) for soybean oil. Accurate results were found for 10 synthetic samples and 7 commercial dietary supplement preparations.

Determination of glycolic acid in cosmetics by online liquid chromatography-Fourier transform infrared spectrometry.

An isocratic online liquid chromatography Fourier transform infrared procedure has been developed for the determination of glycolic acid in cosmetics. The method involves the ultrasound-assisted extraction of glycolic acid from the samples with an acetonitrile:phosphate buffer (25 mM, pH 2.7) (3:97 v/v). The extracts were centrifuged and filtered before their injection into the chromatography system, which was equipped with a C18 column and used a flow rate of 150 microL min(-1). FTIR spectra were acquired using a time-resolved rapid scan mode. To calculate the chromatograms, the spectral area was integrated between 1288 and 1215 cm(-1), with baseline correction established between 1319 and 1150 cm(-1), after correcting for the eluent spectral background. Peak area values of the extracted sample chromatograms were interpolated from an external calibration curve. The method provided a limit of detection of 0.034 mg mL(-1) and a relative standard deviation of 6% for five measurements at the 0.174 mg mL(-1) concentration level. Recovery values obtained by spiking 400 mg of three commercially available samples with amounts of glycolic acid from 3.7 to 9.8 mg ranged between 99.6 and 101%. The results obtained for the commercial samples agree well with their declared concentrations. An attempt to directly determine glycolic acid by attenuated total reflectance measurements using partial least squares calibration showed that results were strongly influenced by compounds coextracted from the matrix.

Fast authentication of tea tree oil through spectroscopy.

Two new procedures, based on infrared spectroscopy in the near infrared (NIR) and mid infrared (MIR), have been developed for the authentication of tea tree oil (TTO) commercial samples. Infrared measurements were made on untreated samples by transmission NIR and attenuated total reflectance (ATR) followed by partial least square discriminant analysis (PLS-DA). These methods offer a fast and low cost alternative to enantiomeric two-dimensional gas chromatography coupled to mass detection usually employed to discriminate between authentic and non-authentic samples. In these studies, a set of 267 samples, including authentic and non-authentic labelled tea tree oil samples, were used to build the models based on the wavenumber range, data pre-processing and latent variables number selection. Infrared methods can be discriminant for authentic and non-authentic TTO samples with a 98% certainty for both ATR and NIR methodologies, employing 92 and 142 external samples respectively. Developed PLS-DA infrared based methodologies and the reference methodology have been evaluated and compared from a Green Analytical point of view.

Separation of motor oils, oily wastes and hydrocarbons from contaminated water by sorption on chrome shavings.

In this paper, the ability of chrome shavings to remove motor oils, oily wastes and hydrocarbons from water has been studied. To determine amount of hydrocarbons sorbed on tanned wastes, a FT-NIR methodology was used and a multivariate calibration based on partial least squares (PLS) was employed for data treatment. The light density, porous tanned waste granules float on the surface of water and remove hydrocarbons and oil films. Wastes fibers from tannery industry have high sorption capacity. These tanned solid wastes are capable of absorbing many times their weight in oil or hydrocarbons (6.5-7.6g of oil and 6.3g of hydrocarbons per gram of chrome shavings). The removal efficiency of the pollutants from water is complete. The sorption of pollutants is a quasi-instantaneous process.

Prediction of organic carbon and total nitrogen contents in organic wastes and their composts by Infrared spectroscopy and partial least square regression.

Middle and near infrared (MIR and NIR) were employed to determine organic carbon (OC) and total nitrogen (TN) in different soil organic amendments including wastes, composts and mixtures of composts and organic wastes. Prediction models based on partial least squares (PLS) regression from the spectra of untreated samples were built. Different spectra preprocessing strategies were adopted and the best number of latent variable was evaluated using leave-one-out cross-validation. Attenuated total reflectance (PLS-ATR-MIR) and diffuse reflectance (PLS-DR-NIR) models were built and evaluated from root mean square error of cross validation and prediction (RMSECV and RMSEP), coefficients of determination for prediction (R2 pred) and residual predictive deviation (RPD). ATR-MIR provided a better prediction capability than DR-NIR with RMSEP, R2pred and RPD values of 2.2%, 0.76 and 2.0 for OC and values of 0.2%, 0.82 and 2.4 for TN, respectively.

Determination of total phenolic compounds in compost by infrared spectroscopy.

Middle and near infrared (MIR and NIR) were applied to determine the total phenolic compounds (TPC) content in compost samples based on models built by using partial least squares (PLS) regression. The multiplicative scatter correction, standard normal variate and first derivative were employed as spectra pretreatment, and the number of latent variable were optimized by leave-one-out cross-validation. The performance of PLS-ATR-MIR and PLS-DR-NIR models was evaluated according to root mean square error of cross validation and prediction (RMSECV and RMSEP), the coefficient of determination for prediction (Rpred(2)) and residual predictive deviation (RPD) being obtained for this latter values of 5.83 and 8.26 for MIR and NIR, respectively.

Radiofrequency catheter ablation of common atrial flutter in 80 patients.

OBJECTIVES: The purpose of this study was to evaluate the efficacy and safety of radiofrequency catheter ablation of common atrial flutter and to determine the optimal target sites in a large series of patients. BACKGROUND: Recent studies report the efficacy of radiofrequency current application in the low right atrial region to interrupt and prevent recurrences of common atrial flutter. However, larger groups of patients are required to confirm the efficacy of this technique and to specify the target sites. METHODS: Two different approaches were used to target the ablation site in 80 consecutive patients. In the first 50 patients, target sites were localized using both anatomic landmarks and electrophysiologic variables. Three anatomic landmarks were used: area 1 = between the tricuspid valve and inferior vena cava orifice; area 2 = between the tricuspid valve and coronary sinus ostium; area 3 = between the inferior vena cava and coronary sinus. The electrophysiologic criterion was to ablate when there was a stable atrial electrogram during the plateau phase. In the next 30 patients we assessed the effect of application of radiofrequency energy in a single line in area 1, 2 or 3 in groups of 10 patients. RESULTS: Overall atrial flutter was interrupted and rendered noninducible after a single session in 72 patients (90%) and could not be interrupted in 8 (10%). The mean (+/- SD) number of radiofrequency applications was 12 +/- 8. After a mean (+/- SD) follow-up of 20 +/- 8 months, recurrences occurred in 14 patients (17%). The location of the final successful site in the first group of 50 patients was in area 1 in 39%, area 2 in 36% and area 3 in 25%. In the next 30 patients, when lines of radiofrequency lesions were placed at several sites, they produced success rates of 70%, 40% and 10% at areas 1, 2 and 3, respectively. CONCLUSIONS: Radiofrequency catheter ablation of atrial flutter can be performed with a high success rate and is safe. The highest success rate is achieved with radiofrequency energy applied in the isthmus between the inferior vena cava orifice and tricuspid valve.

FIA-FT-IR determination of ibuprofen in pharmaceuticals.

A method has been developed for the determination of Ibuprofen (2-[4-isobutylphenyl]-propionic acid) in pharmaceuticals by FT-IR, using the carbonyl band which this compound presents at 1710 cm(-1) in carbon tetrachloride solutions. Samples are dissolved in carbon tetrachloride. In this solvent the excipients are not soluble and so the drug can be directly determined without any additional treatment. The use of a simple FIA manifold permits one to carry out this analysis with a low consumption of reagent and the FT-IR provides a continuous monitoring of the spectral base-line which permits an accurate determination of the maximum in the absorbance band. Also, the FIA system permits easy and fast sampling and cleaning of the measurement cell. The method has a dynamic range between 0.5 and 20 mg/ml with a sensitivity of 0.366 +/- 0.004 au . mg(-1) . ml . mm(-1) and a variation coefficient of 0.8% for 5 independent measurements of a real sample containing 200 mg of Ibuprofen per capsule. The developed procedure provides concentration values comparable with those found by UV spectrophotometry in the analysis of real samples but is free from matrix interferences.

Simultaneous determination of acetylsalicylic acid and caffeine in pharmaceuticals by flow injection with fourier transform infrared detection.

A fast quality control methodology has been developed for the simultaneous determination of acetylsalicylic acid (ASA) and caffeine in pharmaceuticals by flow injection-Fourier Transform Infrared Spectrometry. The method is based on the solubilization of ASA and caffeine in CH(2)Cl(2) and the use of a flow system to introduce samples and standards in the spectrometer. Two solutions, containing 90 and 110% of the reported concentration of the two active principles in the sample, were employed in order to control the extreme tolerance levels accepted by the International Pharmacopeia for the composition of formulations. A 300 mul volume of each solution was injected in turn, into a carrier stream of the sample, and their absorbances were measured at wavenumbers of 1770 and 1661/cm for ASA and caffeine, respectively. The absorbance values obtained for the carrier, at the same wavenumbers, were interpolated between those obtained for the standards. This rapid methodology provides a simultaneous quantitative evaluation of the concentration of ASA and caffeine in pharmaceuticals. The method permits us to carry out 53 injections/hr and provides a sensitivity of 0.231 absorbance units/mg ml/mm for ASA and 1.065 for calteine. Accurate results were obtained for the analysis of different samples containing one or both compounds in the presence of excipients which are insoluble in CH(2)Cl(2) and also in the presence of other active principles, such as acetaminophen or ergotamine tartrate.

Comparative study of different approaches for the flow injection-fourier transform infrared determination of toluene in gasolines.

A single channel flow injection manifold has been employed to carry out the direct determination of toluene in gasolines by FT-IR without any sample pretreatment and by using different strategies. Toluene can be directly determined by measuring the absorbance at 728 cm(-1), using a base line established between 835 and 575 cm(-1); and in this case a limit of detection of 0.01% (v/v) can be obtained with a dynamic range up to 2% (v/v). In some cases it could be convenient to determine toluene by derivative flow-injection FT-IR in order to avoid matrix interferences in the analysis of some types of gasolines. Carrying out the first order derivative FI-FT-IR measurements on the 728 cm(-1) band between the peak at 731 and the valley at 725 cm(-1) toluene can be determined without problems in establishing the base line and with a limit of detection of 0.01% (v/v). On the other hand, the use of the quotient between the first order derivative absorbance values of toluene, at the 728 cm(-1) band, and benzene, at the 675 cm(-1) band, can be applied for the determination of toluene in gasolines in which benzene has been previously analyzed, avoiding problems related to the determination of the base line and making measurements independent of the spacer employed.

[Value of protocol using standardised activities of daily living for the programming of rate responsive pacing]. / Intérêt d'un protocole comportant des exercices de la vie courante standardisés pour la programmation des stimulations à fréquence asservie.

To optimise the regulation of rate responsive pacemakers, the authors propose standardized tests of everyday activities. Seven tests were selected with monitoring of the heart rate (HR) by telemetry every 30 seconds: two reference tests--cycloergometry: 2 steps of 3 minutes at 30 then 60 watts and a symptoms-limited Bruce protocol on the treadmill--and 5 everyday activities, walking, going upstairs, going downstairs, squats and hyperventilation. Fifteen normal subjects (65 +/- 10 years) were used to establish normal values and 10 patients implanted with a Telelctronics Meta DDDR 1250 rate responsive pacemaker with minute ventilation sensing, were studied after choice of minimal and maximal HR on clinical criteria (age, pathology). The rate response frequency (RRF) was adjusted so that the pacemaker HR was within normal values. At the beginning of each test, the sensor was hypokinetic (p = 0.01). Hyperventilation caused hyperkinesia of the sensor (p = 0.01). A good correlation was obtained between PM patients and normal subjects on walking, going up down stairs and for squats (p = NS). On cycle ergometry and treadmill, the PM remained slightly hypokinetic (p = 0.02). The study of "ideal" RRF measured at "peak exercise" as proposed by the manufacturer was only satisfactory in 1 of the 10 cases. This study confirms the value of using everyday activities for programming rate responsive pacemakers, the limitations of automatic adjustment and the need for personalized programming.

Science based calibration for the extraction of 'analyte-specific' HPLC-DAD chromatograms in environmental analysis.

Multivariate science based calibration (SBC) has been applied to the resolution of overlapped peaks in liquid chromatography with diode array detection (LC-DAD). Complex river water samples spiked with 11 pharmaceutical substances resulted in poorly resolved chromatograms containing additional peaks from interfering matrix compounds and a change in the background absorbance due to the mobile phase gradient. Applying the present multivariate approach it was possible to resolve all 11 analytes from overlapping peaks, obtaining linear calibration lines (R(2)>0.96). Recovery percentages on spiked samples ranged between 74.6 and 113.5%, which are quite satisfactory taking into account the low concentration ranges considered to 1-7 µg L(-1).

Application of point-to-point matching algorithms for background correction in on-line liquid chromatography-Fourier transform infrared spectrometry (LC-FTIR).

A new background correction method for the on-line coupling of gradient liquid chromatography and Fourier transform infrared spectrometry has been developed. It is based on the use of a point-to-point matching algorithm that compares the absorption spectra of the sample data set with those of a previously recorded reference data set in order to select an appropriate reference spectrum. The spectral range used for the point-to-point comparison is selected with minimal user-interaction, thus facilitating considerably the application of the whole method. The background correction method has been successfully tested on a chromatographic separation of four nitrophenols running acetonitrile (0.08%, v/v TFA):water (0.08%, v/v TFA) gradients with compositions ranging from 35 to 85% (v/v) acetonitrile, giving accurate results for both, baseline resolved and overlapped peaks.