Atmospheric Solids Analysis Probe (ASAP) and Atmospheric Pressure Gas Chromatography (APGC) coupled to Quadrupole Time of Flight Mass Spectrometry (QTOF-MS) as alternative techniques to trace aromatic markers of mineral oils in food packaging.

The aim of this work was to select and identify the best markers of aromatic hydrocarbon mineral oil (MOAH) in food packaging. For this purpose, a series of mineral oils was initially analysed. Polycyclic Aromatic Hydrocarbons (PAHs) and the alkylated isomers of Methylnaphthalene (MNS), Diisopropylnaphtalene (DIPNs), Dibenzothiophenes (DBTS), Methyldibenzothiophene (MDBTs), Dimethyldibenzothiophenes (DMDBTs) and Benzonaphthiophenes (BNTS) were then explored. Their presence was confirmed by direct analysis of several mineral oils by Atmospheric Solids Analysis Probe Quadrupole-Time of Flight Mass Spectrometry (ASAP-QTOF-MS). Atmospheric Pressure Gas Chromatography Quadrupole-Time of Flight Mass Spectrometry (APGC-QTOF-MS) was used to confirm the markers in different samples of oils, recycled PET (rPET), recycled cardboard and packaging of couscous and semolina to confirm the contamination. 27 markers were found in the mineral oil samples, 22 of them in rPET, 8 in recycled board and no MOAH were found in packaging of couscous and semolina.

Migration of oligomers from a food contact biopolymer based on polylactic acid (PLA) and polyester.

Polylactic acid (PLA) is a biopolymer commonly used in food packaging due to its good characteristics, similar to PET. To evaluate the safety of this material, the analysis of the non-intentionally added substances (NIAS) is required. Oligomers are NIAS and their behavior needs a deep study, especially if they migrate to the food. In this work, the analysis of the polymer and the migration to food simulants was carried out. A total dissolution/precipitation procedure was applied to PLA pellets and films, using dichloromethane and ethanol as solvent and antisolvent system respectively. The migration tests were carried out in three liquid simulants to mimic any kind of food. Since oligomers are not present in the positive list of the Directive 10/2011/EC, their concentration must be below the 0.01 mg/kg of food. UPLC-QTOF-MS, with and without ion mobility (IM), was used for the analysis. Thirty-nine different PLA oligomers made of repeated monomer units of [LA] (C3H4O2) and with different structures were identified. They corresponded to cyclic oligomers with [LA]n structure and two groups of linear oligomers, one with an hydroxyl group, OH-[LA]n-H, and the other one with an ethoxy group, CH3-CH2-O-[LA]n-H. Cyclic oligomers only appeared in the material and were not present in migration solutions. Linear oligomers HO-[LA]n-H were already present in the pellets/film and they migrated in a higher extension to aqueous food simulants (EtOH 10% and AcH 3%). However, linear oligomers CH3-CH2-O-[LA]n-H were not present initially in the pellets/film, but were detected in migration to simulants with ethanol content, EtOH 95% and EtOH 10%. Furthermore, 5 cyclic polyester oligomers were identified in migration. Ethanol 95% and ethanol 10% migration solutions were also analyzed by scanning electron microscopy (SEM), and the presence of microstructures that could be attributed to the oligomers migration was found. They could be seen as microplastics.

Simultaneous extraction and analysis of preservatives and artificial sweeteners in juices by salting out liquid-liquid extraction method prior to ultra-high performance liquid chromatography.

A novel and fast salting out liquid-liquid extraction method was developed for simultaneous determination of food additives with different polarities in juices. Chromatographic separation was achieved in less than 6 min using Acquity UPLC BEH C 18 (100 mm × 2.1 mm d.i. × 1.7 µm) column with ammonium acetate with 0.01% of trifluoroacetic acid as eluent A and acetonitrile as eluent B at a flow rate of 0.2 mL min-1. The main factors affecting the extraction efficiency were optimized. The method was validated applying accuracy profile based on total error. The extraction recoveries ranged from 84.97 to 122%. Relative standard deviation ranged from 1.24 to 7.99% for intraday assay and from 1.69 to 9.16% for intermediate precision. The limits of detection for five food additives were from 0.3 to 1.42 µg mL-1. The method was successfully applied to 47 samples of juices from nine brands.

Progress in mass spectrometry for the analysis of set-off phenomena in plastic food packaging materials.

In most cases, food packaging materials contain inks whose components can migrate to food by diffusion through the material as well as by set-off phenomena. In this work, different mass spectrometry approaches had been used in order to identify and confirm the presence of ink components in ethanol (95%) and Tenax(®) as food simulants. Three different sets of materials, manufactured with different printing technologies and with different structures, were analyzed. Sample analysis by ultra performance liquid chromatography mass spectrometry (UPLC-MS), using a quadrupole-time of flight (Q-TOF) as a mass analyser proved to be an excellent tool for identification purposes while ion mobility mass spectrometry (IM-MS) shown to be very useful for the confirmation of the candidates proposed. The results showed the presence of different non-volatile ink components in migration such as colorants (Solvent Red 49), plasticizers (dimethyl sebacate, tributyl o-acetyl citrate) or surfactants (SchercodineM, triethylene glycol caprilate). An oxidation product of an ink additive (triphenyl phosphine oxide) was also detected. In addition, a surface analysis technique, desorption electrospray mass spectrometry (DESI-MS), was used for analyzing the distribution of some ink components (tributyl o-acetyl citrate Schercodine L, phthalates) in the material. The detection of some of these compounds in the back-printed side confirmed the transference of this compound from the non-food to the food contact side. The results also showed that concentration of ink migrants decreased when an aluminum or polypropylene layer covered the ink. When aluminum was used, concentration of most of ink migrants decreased, and for 5 out of the 9 even disappeared.

Enfermeria basada en la evidencia. Protocolo para la movilización temprana y segura del paciente en UCI / Evidence based nursin: early and safe protocol for ICU patients´s mobilization

El paciente ingresado en la UCI tiene riesgo de inmovilidad y de un deterioro temprano e importante de su función física. Objetivo. Desarrollar e implementar un protocolo para la movilización temprana y segura del paciente en UCI. Metodología. Se utilizó el Evidence Based Practice Model for Staff Nurses que engloba: Valoración, Identificación del problema, Planificación, Implementación y evaluación e Integración y mantenimiento en la práctica. Resultados. El equipo investigador (la enfermera de práctica avanzada y enfermeras asistenciales expertas), junto con el equipo médico y el servicio de rehabilitación, detectó la necesidad de elaborar este protocolo. Para ello, se realizó una búsqueda bibliográfica en las bases de datos PubMed, CINAHL y Cochrane Library, se administró un cuestionario y se llevaron a cabo observaciones estructuradas. Para la implementación se impartieron sesiones de formación al personal de enfermería, se colocaron pósteres en la unidad y se incluyó el protocolo en el programa informático. Por último, se realizará una evaluación de los conocimientos, percepciones y prácticas de las enfermeras de la unidad y un registro de los eventos adversos relacionados con la movilización. Conclusiones. El desarrollo e implementación de un protocolo para la movilización temprana del paciente en UCI ha facilitado la integración de este cuidado en la práctica diaria. Este modelo de práctica basada en la evidencia permite que el personal de enfermería forme parte activa en el cambio de cultura en cuanto a la integración de la investigación en la práctica (AU)

Patients admitted to the ICU are at risk of immobility and an early and important physical deconditioning. Objective. To develop and to implement an early and safe protocol for ICU patients’ mobilization. Methodology. The Evidence Based Practice Model for Staff Nurses was used. It encompasses Assessment, Problem Identification, Planning, Implementation and Evaluation, Integration and Maintenance in Practice. Results. The research team (Advanced Practice Nurse and expert clinical nurses), along with the medical team and rehabilitation service, identified the need to develop the protocol. For its elaboration, a literature search on the data bases PubMed, CINAHL and Cochrane Library was performed; a questionnaire was administered and structured observations were conducted. For the implementation training sessions were offered to nurses, posters were placed in the unit and protocol was included in the computer program. Finally, an assessment of the knowledge, perceptions and practices of nurses in the unit and a recording of adverse events related to the mobilization will take place. Conclusions. The development and implementation of a protocol for early mobilization of ICU patients has facilitated the integration of this care in daily practice. This model of evidence-based practice allows nurses an active part in changing the culture in terms of the integration of research into practice (AU)

Direct screening of tobacco indicators in urine and saliva by Atmospheric Pressure Solid Analysis Probe coupled to quadrupole-time of flight mass spectrometry (ASAP-MS-Q-TOF-).

A new screening method has been explored for direct analysis of tobacco smoke biomarkers in biological matrices (i.e., saliva and urine). Single run analysis using Atmospheric pressure Solid Analysis Probe (ASAP) and high resolution mass spectrometry with quadrupole and time of flight detector has been applied directly to some biological samples (i.e., urine and saliva), providing a fast, efficient and sensitive method of identification. The method has been applied to saliva and urine samples from heavy tobacco smokers for exposure studies. Nicotine itself, nicotine metabolites (i.e., cotinine, trans-3'-hydroxycotinine, nicotine-N-glucuronide) and other related tobacco smoke toxic compounds (i.e., NNK 4-[methyl(nitroso)amino]-1-(3-pyridinyl)-1-butanone, anatabine) were found in the analyzed samples. The identification of compounds was confirmed by ultrahigh performance liquid chromatography with MS-triple quadrupole detector after sample treatment. Different temporal trends and biomarkers behavior have been found in time series related samples. Both methods are compared for screening of these biological matrices.

Atmospheric pressure solid analysis probe coupled to quadrupole-time of flight mass spectrometry as a tool for screening and semi-quantitative approach of polycyclic aromatic hydrocarbons, nitro-polycyclic aromatic hydrocarbons and oxo-polycyclic aromatic hydrocarbons in complex matrices.

A new screening and semi-quantitative approach has been developed for direct analysis of polycyclic aromatic hydrocarbons (PAHs) and their nitro and oxo derivatives in environmental and biological matrices using atmospheric pressure solid analysis probe (ASAP) quadrupole-time of flight mass spectrometry (Q-TOF-MS). The instrumental parameters were optimized for the analysis of all these compounds, without previous sample treatment, in soil, motor oil, atmospheric particles (ashes) and biological samples such as urine and saliva of smokers and non-smokers. Ion source parameters in the MS were found to be the key parameters, with little variation within PAHs families. The optimized corona current was 4 µA, sample cone voltage 80 V for PAHs, nitro-PAHs and oxo-PAHs, while the desolvation temperatures varied from 300°C to 500°C. The analytical method performance was checked using a certified reference material. Two deuterated compounds were used as internal standards for semi-quantitative purposes together with the pure individual standard for each compound and the corresponding calibration plot. The compounds nitro PAH 9-nitroanthracene and oxo-PAH 1,4-naphthalenedione, were found in saliva and urine in a range below 1 µg/g while the range of PAHs in these samples was below 2 µg/g. Environmental samples provided higher concentration of all pollutants than urine and saliva.

Atmospheric pressure gas chromatography with quadrupole time of flight mass spectrometry for simultaneous detection and quantification of polycyclic aromatic hydrocarbons and nitro-polycyclic aromatic hydrocarbons in mosses.

Within the family of polycyclic aromatic hydrocarbons (PAHs), nitrated derivatives are of particular interest in environmental science because they have well-known carcinogenic and mutagenic effects. They are in fact more toxic than their parent PAHs. One valuable diagnosis of atmospheric pollution can be obtained using biomonitors such as mosses. These biomonitors can provide information about air pollution over long periods of time in wilderness areas. Thus, they can serve as monitors of the atmospheric transport of pollutants. In this study, atmospheric pressure gas chromatography coupled to a quadrupole hyphenated to a time of flight mass spectrometer (APGC-MS/Q-TOF) has been examined for the identification of target analytes (15 PAHs and 8 NPAHs) for subsequent use in the analysis of mosses. Working ranges in low µg g(-1) concentration levels were obtained with most correlation coefficients higher than 0.999. All LODs were in the 0.007-0.035µg g(-1) range and higher LODs (0.035µg g(-1)) were obtained for the less volatile PAHs with higher mass and retention times: benzo(g,h,i)perylene, dibenz(a,h)anthracene and indeno(1,2,3-c,d)pyrene. These LODs are of importance for the intended use, biomonitoring, especially taking into account that NPAHs are commonly found at very low concentration levels. Recoveries from mosses ranged from 75 to 98%. Intraday and interday precision ranged from 1.8 to 11.1% RSD and from 2.4 to 16.7% RSD, respectively. Very low concentrations of NPAHs were found in mosses compared to those of PAHs. All these data were used for pattern recognition of the pollutant source. The results are shown and discussed.

Development of new antioxidant active packaging films based on ethylene vinyl alcohol copolymer (EVOH) and green tea extract.

Ethylene vinyl alcohol copolymer (EVOH) films containing green tea extract were successfully produced by extrusion. The films were brown and translucent, and the addition of the extract increased the water and oxygen barrier at low relative humidity but increased the water sensitivity, the glass transition temperature, and the crystallinity of the films and improved their thermal resistance. An analysis by HPLC revealed that the antioxidant components of the extract suffered partial degradation during extrusion, reducing the content of catechin gallates and increasing the concentration of free gallic acid. Exposure of the films to various food simulants showed that the liquid simulants increased their capacity to reduce DPPH(•) and ABTS(•+) radicals. The release of green tea extract components into the simulant monitored by HPLC showed that all compounds present in the green tea extract were partially released, although the extent and kinetics of release were dependent on the type of food. In aqueous food simulants, gallic acid was the main antioxidant component released with partition coefficient values ca. 200. In 95% ethanol (fatty food simulant) the K value for gallic acid decreased to 8 and there was a substantial contribution of catechins (K in the 1000 range) to a greatly increased antioxidant efficiency. Kinetically, gallic acid was released more quickly than catechins, owing to its faster diffusivity in the polymer matrix as a consequence of its smaller molecular size, although the most relevant effect is the plasticization of the matrix by alcohol, increasing the diffusion coefficient >10-fold. Therefore, the materials here developed with the combination of antioxidant substances that constitute the green tea extract could be used in the design of antioxidant active packaging for all type of foods, from aqueous to fatty products, the compounds responsible for the protection being those with the higher compatibility with the packaged product.

Clinical applicability of B-type natriuretic peptide in patients with suspected heart failure in primary care in Spain: the PANAMA study.

AIM: To assess the predictive value of B-type natriuretic peptide (BNP) in the diagnosis of heart failure (HF) in a primary-care setting in Spain. METHODS: PANAMA was a multicenter and cross-sectional study. Patients ≥18 years of age with a clinical diagnosis of HF (Framingham criteria) were consecutively included in the study by primary-care investigators. BNP determination and an echocardiogram were performed in every patient. The cut-off point of BNP for the criterion of exclusion of HF was considered as <100 pg/ml, as suggested by European guidelines. Sensitivity, specificity, positive-predictive value and negative-predictive value were calculated. RESULTS: A total of 72 patients (mean age: 75.1 ± 8.7 years; 74.6% women) were included. The most frequent associated risk factors were hypertension (75.6%) and dyslipidemia (54.3%). The most common major and minor criteria of HF according to Framingham criteria were radiographic cardiomegaly (90.2%) and dyspnea on ordinary exertion (100%), respectively. BNP median was 49 pg/ml (33.3 pg/ml in those with a doubtful diagnosis of HF and 83.3 pg/ml in those with a likely diagnosis of HF). Approximately 60% of patients exhibited diastolic dysfunction. Concerning accuracy parameters comparing BNP >100 pg/ml with echocardiogram, sensitivity was 25%, the specificity 80.8%, and the positive- and negative-predictive values were 68.8 and 38.9%, respectively. CONCLUSION: In patients attended by general practitioners, BNP >100 pg/ml may be a useful diagnostic tool with a high specificity for the diagnosis of HF.

Pros and cons of analytical methods to quantify surrogate contaminants from the challenge test in recycled polyethylene terephthalate.

Different analytical methods were optimized and applied to quantify certain surrogate contaminants (toluene, chlorobenzene, phenol, limonene and benzophenone) in samples of contaminated and recycled flakes and virgin pellets of polyethylene terephthalate (PET) coming from the industrial challenge test. A screening analysis of the PET samples was carried out by direct solid-phase microextraction (SPME) in headspace mode (HS). The methods developed and used for quantitative analysis were a) total dissolution of PET samples in dichloroacetic acid and analysis by HS-SPME coupled to gas chromatography-mass spectrometry (GC-MS) and, b) dichloromethane extraction and analysis by GC-MS. The concentration of all surrogates in the contaminated PET flakes analyzed by HS-SPME method was lower than expected according to information provided by the supplier. Dichloroacetic acid interacted with the surrogates, resulting in a tremendous decrease of limonene concentration. The degradation compounds from limonene were identified. Dichloromethane extraction and GC-MS analysis evidenced the highest values of analytes in these PET samples. Based on the foregoing data, the efficiency of the recycling process was evaluated, whereby the removal of 99.9% of the surrogates proceeding from the contaminated flakes was confirmed.