An approach to epistemic emotions in physics' teaching-learning. The case of pre-service teachers.

It is well established that emotions play a key role in the teaching-learning process and cognitive and affective factors should receive especial consideration. This fact becomes even more important when dealing with pre-service teachers, since their emotions towards science will be projected into their future practice as early-childhood teachers. It has been also stated the influence of the instructional approach in which the teaching-learning process is based on the emotions of students towards science. In this line, the current study aims to monitor and interpret the emotions of pre-service teachers when addressing physics content learning, namely forces, from two different instructional approaches with increasing experimentality degree and implication of students. The considered instructional approaches consisted on a theoretical problem solving one and a practical one designed in the form of inquiry-based hands-on activities. A sample size of 118 students was considered and a questionnaire was employed for in situ emotions monitorization. A decrease from 30% to 12% in negative emotions and an increase from 85% to 91% in positive emotions was detected when considering the transition from instructional approach 1 (classroom approach) to instructional approach 2 (inquiry-based hands-on approach). The whole dataset was analyzed by means of principal component analysis (PCA). PCA reveals the importance of emotions' valence, but also their activating/deactivating character. An approach to epistemic emotions is achieved from this perspective. It has been demonstrated that the implementation of inquiry-based hand-on activities results in increased occurrence of security and trust among the students, in comparison with occurring emotions after receiving more theoretical interventions.

Detailed Emotional Profile of Secondary Education Students Toward Learning Physics and Chemistry.

The present research arises from the need to identify the emotions that K-7 to K-10 students experience toward the learning of Physics and Chemistry, since it is a fact that there is a decrease in the number of students choosing itineraries related to Science. Different blocks of contents have been considered in each subject in order to identify emotions toward each one of them. The considered sample consisted of 149 K-8 students, 152 K-9 students and 130 K-10 students from several middle and high schools in Badajoz (Spain) during the 2014-2015 school year. Students experienced more positive emotions toward the content of Chemistry than toward those of Physics. A decrease was detected in the mean frequency of positive emotions such as joy, fun, and tranquility from K-8 to K-10, as well as an increase in negative emotions such as boredom, anxiety, disgust, fear, nervousness, worry, and sadness. It has also been found that positive emotions toward Chemistry contents are mainly related to teachers' methods and attitudes, while negative emotions toward Physics contents are related to the exclusive use of the textbook, solving Physics problems, or giving oral presentations of the topics in class.

Front-face fluorescence excitation-emission matrices in combination with three-way chemometrics for the discrimination and prediction of phenolic response to vineyard agronomic practices.

Phenolic extracts from cv Tempranillo grapes subjected to water stress and irrigation treatment, both of them with high and low crop load, were analyzed by front-face fluorescence. Excitation-emission matrices (EEMs) were analyzed by means of unsupervised parallel factor analysis (PARAFAC), PARAFAC supervised by linear discriminant analysis, and discriminant unfolded partial least-squares. All algorithms allowed to differentiate between water stress and irrigation grape samples when the fluorescence maxima region of catechin and epicatechin, and resveratrol was considered. A central composite design was employed for the calibration of catechin, epicatechin and resveratrol. Resveratrol was quantified by U-PLS in both, irrigated and water stressed samples, and levels between 3.46 ±â€¯0.22 and 4.67 ±â€¯0.08 µg mL-1 and 2.43 ±â€¯0.60 and 3.03 ±â€¯0.10 µg mL-1, respectively, were found. PARAFAC only allowed the determination of the sum of catechin plus epicatechin (R2 = 0.9397). The determination of total catechin plus epicatechin by means of PARAFAC was successfully validated by liquid chromatography.

Detection and quantification of extra virgin olive oil adulteration by means of autofluorescence excitation-emission profiles combined with multi-way classification.

Within olive oils, extra virgin olive oil is the highest quality and, in consequence, the most expensive one. Because of that, it is common that some merchants attempt to take economic advantage by mixing it up with other less expensive oils, like olive oil or olive pomace oil. In consequence, the characterization and authentication of extra virgin olive oils is a subject of great interest, both for industry and consumers. This paper reports the potential of front-face total fluorescence spectroscopy combined with second-order chemometric methods for the detection of extra virgin olive oils adulteration with other olive oils. Excitation-emission matrices (EEMs) of extra virgin olive oils and extra virgin olive oils adulterated with olive oils or with olive pomace oils were recorded using front-face fluorescence spectroscopy. The full information content in these fluorescence images was analyzed with the aid of unsupervised parallel factor analysis (PARAFAC), PARAFAC supervised by linear discriminant analysis (LDA-PARAFAC), and discriminant unfolded partial least-squares (DA-UPLS). The discriminant ability of LDA-PARAFAC was studied through the tridimensional plots of the canonical vectors, defining a surface separating the established categories. For DA-UPLS, the discriminant ability was established through the bidimensional plots of predicted values of calibration and validation samples, in order to assign each sample to a given class. The models demonstrated the possibility of detecting adulterations of extra virgin olive oils with percentages of around 15% and 3% of olive and olive pomace oils, respectively. Also, UPLS regression was used to quantify the adulteration level of extra virgin olive oils with olive oils or with olive pomace oils.

Rapid and Nondestructive Determination of Aleurone Content in Pearling Fractions of Barley by Near-Infrared (NIR) and Fluorescence Spectroscopies.

The aim of the present work was to develop and evaluate near-infrared (NIR) and fluorescence spectroscopies as rapid and potential online methods for determination of the amount of aleurone in pearling dust fractions of barley. Phytic acid was used as a marker for the aleurone layer. Different varieties of barley were pearled, and dust fractions were progressively taken out. Sample concentration of phytic acid varied in the range of 0.5-4.1 g/100 g, and highest concentrations were obtained in dust fractions for pearling degrees in the range of 15-25%. Regression models for phytic acid were developed with the same high correlations for NIR and fluorescence spectroscopies (R2 = 0.96) and prediction errors of ±0.16-0.18 g/100 g. The models performed well on a test set of pearling fractions from two other barley varieties. The techniques are rapid and nondestructive, which means that they can be used online in connection with industrial pearling systems.

Evaluation of the combination of micellar electrokinetic capillary chromatography with sweeping and cation selective exhaustive injection for the determination of 5-nitroimidazoles in egg samples.

A methodology is presented for the sensitive determination of nitromidazole residues in egg by means of micellar electrokinetic capillary chromatography in combination with cation selective exhaustive injection and ultraviolet detection. Six compounds have been considered and the separation has been achieved in less than 12min in a 61.5-cm effective length capillary with 50-µm internal diameter. Phosphate buffer 44mM pH 2.5, containing 8% tetrahydrofurane and 123mM sodium dodecyl sulfate was employed as running buffer. Solid phase extraction has been employed for sample clean-up. The methodology has been successfully validated in hen eggs, obtaining method detection limits in the range of 2.1-5.0ng/g. Precision was studied in terms of repeatability and intermediate precision, with relative standard deviations lower than 18.0%. Recoveries were calculated in quail eggs and a commercial pasteurized egg white product, reaching over 70% for most of the considered 5-nitroimidazoles.

Applications of capillary electrophoresis with chemiluminescence detection in clinical, environmental and food analysis. A review.

This paper reviews the latest developments and analytical applications of chemiluminescence detection coupled to capillary electrophoresis (CE-CL). Different sections considering the most common CL systems have been included, such as the tris(2,2'-bipyridine)ruthenium(II) system, the luminol and acridinium derivative reactions, the peroxyoxalate CL or direct oxidations. Improvements in instrumental designs, new strategies for improving both resolution and sensitivity, and applications in different fields such as clinical, pharmaceutical, environmental and food analysis have been included. This review covers the literature from 2010 to 2015.

Development of an ultrasensitive stacking technique for 5-nitroimidazole determination in untreated biological fluids by micellar electrokinetic chromatography.

Cation-selective exhaustive injection and sweeping followed by a MEKC separation is evaluated for the sensitive analysis of 5-nitroimidazoles in untreated human serum and urine. Deproteinized serum and urine samples were diluted 76 and 143 times, respectively, in a low-conductivity solvent (5.00 mM orthophosphoric acid containing 5.0% v/v methanol). Samples were electrokinetically injected at 9.8 kV for 632 s in a previously conditioned fused-silica capillary (65.0 cm × 50 µm id). Separation was performed at -30 kV and 20°C using 44 mM phosphate buffer (pH 2.5), 123 mM SDS, and 8% v/v tetrahydrofurane as BGE. Signals were monitored at 276 nm and peak area was selected as analytical response. Good linearity (R(2) ≥ 0.988) and LODs lower than 1.5 and 1.8 µg/mL were achieved in serum and urine, respectively.

Determination of sulfonamides in serum by on-line solid-phase extraction coupled to liquid chromatography with photoinduced fluorescence detection.

An analytical method based on on-line solid-phase extraction coupled to liquid chromatography with photoinduced fluorescence detection has been developed to determine sulfonamides in serum. A home-made setup was used to percolate 3 mL of sample through a solid-phase extraction column. Analytes were retained onto the sorbent by an anion exchange mechanism which ensures an optimum compatibility with the subsequent chromatographic separation using a C-18 column and an on-line photoreactor in order to derivatize sulfonamides, which do not present native fluorescence. The method allowed the determination of 7 sulfonamides in serum samples previously deproteinized in less than 18 min and with limits of detection ranging between 1.8 and 3.6 mg/L. Relative recoveries between 91.5% and 102.1% were obtained with satisfactory precision since relative standard deviations were always below 10.5%.

Ultrasensitive analysis of lysergic acid diethylamide and its C-8 isomer in hair by capillary zone electrophoresis in combination with a stacking technique and laser induced fluorescence detection.

This article deals with the development and validation of a novel capillary zone electrophoresis (CZE) with laser induced fluorescence detection method for the analysis of lysergic acid diethylamide (LSD) and its isomer iso-LSD in hair samples. The separation of both analytes has been achieved in less than 13 min in a 72-cm effective length capillary with 75-µm internal diameter. As running buffer 25 mM citrate, pH 6.0 has been employed and separation temperature and voltage of 20 °C and 13 kV respectively, were applied. Field amplified sample injection (FASI) has been employed for on-line sample preconcentration, using ultrapure water containing 117 µM H3PO4 as optimum injection medium. Injection voltage and time have been optimized by means of experimental design, obtaining values of 7 kV and 15s, respectively. Methylergonovine has been employed as internal standard in order to compensate irreproducibility from electrokinetic injection. The analytical method has been applied to hair samples, previous extraction of the target analytes by ultrasound assisted solid-liquid extraction at 40 °C for 2.5 h, employing acetonitrile as extracting solvent. Linear responses were found for LSD and iso-LSD in matrix-matched calibrations from around 0.400 up to 50.0 pg mg(-1). LODs (3 S/N) in the order of 0.100 pg mg(-1) were calculated for both analytes, obtaining satisfactory recovery percentages for this kind of sample.

Novel cation selective exhaustive injection-sweeping procedure for 5-nitroimidazole determination in waters by micellar electrokinetic chromatography using dispersive liquid-liquid microextraction.

A novel method consisting of cation-selective exhaustive injection and sweeping (CSEI-sweeping) as on-line preconcentration followed by a micellar electrokinetic chromatography (MEKC) separation has been developed for the determination of 5-nitroimidazoles (5-NDZ) in environmental waters. Moreover, dispersive liquid-liquid microextraction (DLLME) has been proposed for first time as sample treatment technique prior to CSEI-sweeping-MEKC. DLLME was applied to 5mL of sample. Dibromomethane (1156µL) and 2-butanol (1363µL) were employed as extractant and dispersive solvents, respectively. Salting-out effect was achieved by the addition of 16% (w/v) NaCl to the samples. After DLLME and organic solvent evaporation, the residue was redissolved in a low conductivity solvent (5mM phosphoric acid with 5% of methanol) and electrokinetically injected at 9.8kV for 632s in a bare fused-silica capillary (57.2cm, 50µm I.D.). Prior to the injection, the capillary was rinsed with 50mM phosphate buffer pH 2.5, followed by a plug of a higher conductivity buffer (100mM phosphate pH 2.5, 50mbar, 264s) and a plug of water (50mbar, 2s). Separation was carried out applying -30kV at 20°C in 44mM phosphate buffer pH 2.5, containing 8% tetrahydrofuran and 123mM sodium dodecyl sulfate. Analytical signals were monitored at 276nm. Validation was performed in river and well waters, obtaining satisfactory results in terms of linearity, precision (% RSD generally lower than 10%) and trueness (recoveries higher than 70% in almost all cases). LODs ranged from 0.61 to 2.44ng/mL. The combination of this microextraction technique with the proposed capillary electrophoresis methodology supposes a simple, sensitive and cheap alternative for 5-NDZ analyses, in accordance with the aims of green chemistry.

From multispectral imaging of autofluorescence to chemical and sensory images of lipid oxidation in cod caviar paste.

The potential of multispectral imaging of autofluorescence to map sensory flavour properties and fluorophore concentrations in cod caviar paste has been investigated. Cod caviar paste was used as a case product and it was stored over time, under different headspace gas composition and light exposure conditions, to obtain a relevant span in lipid oxidation and sensory properties. Samples were divided in two sets, calibration and test sets, with 16 and 7 samples, respectively. A third set of samples was prepared with induced gradients in lipid oxidation and sensory properties by light exposure of certain parts of the sample surface. Front-face fluorescence emission images were obtained for excitation wavelength 382 nm at 11 different channels ranging from 400 to 700 nm. The analysis of the obtained sets of images was divided in two parts: First, in an effort to compress and extract relevant information, multivariate curve resolution was applied on the calibration set and three spectral components and their relative concentrations in each sample were obtained. The obtained profiles were employed to estimate the concentrations of each component in the images of the heterogeneous samples, giving chemical images of the distribution of fluorescent oxidation products, protoporphyrin IX and photoprotoporphyrin. Second, regression models for sensory attributes related to lipid oxidation were constructed based on the spectra of homogeneous samples from the calibration set. These models were successfully validated with the test set. The models were then applied for pixel-wise estimation of sensory flavours in the heterogeneous images, giving rise to sensory images. As far as we know this is the first time that sensory images of odour and flavour are obtained based on multispectral imaging.

Dispersive liquid-liquid microextraction prior to field-amplified sample injection for the sensitive analysis of 3,4-methylenedioxymethamphetamine, phencyclidine and lysergic acid diethylamide by capillary electrophoresis in human urine.

A novel capillary zone electrophoresis (CZE) with ultraviolet detection method has been developed and validated for the analysis of 3,4-methylenedioxymethamphetamine (MDMA), lysergic acid diethylamide (LSD) and phencyclidine (PCP) in human urine. The separation of these three analytes has been achieved in less than 8 min in a 72-cm effective length capillary with 50-µm internal diameter. 100 mM NaH(2)PO(4)/Na(2)HPO(4), pH 6.0 has been employed as running buffer, and the separation has been carried out at temperature and voltage of 20°C, and 25kV, respectively. The three drugs have been detected at 205 nm. Field amplified sample injection (FASI) has been employed for on-line sample preconcentration. FASI basically consists in a mismatch between the electric conductivity of the sample and that of the running buffer and it is achieved by electrokinetically injecting the sample diluted in a solvent of lower conductivity than that of the carrier electrolyte. Ultrapure water resulted to be the better sample solvent to reach the greatest enhancement factor. Injection voltage and time have been optimized to 5 kV and 20s, respectively. The irreproducibility associated to electrokinetic injection has been correcting by using tetracaine as internal standard. Dispersive liquid-liquid microextraction (DLLME) has been employed as sample treatment using experimental design and response surface methodology for the optimization of critical variables. Linear responses were found for MDMA, PCP and LSD in presence of urine matrix between 10.0 and 100 ng/mL approximately, and LODs of 1.00, 4.50, and 4.40 ng/mL were calculated for MDMA, PCP and LSD, respectively. The method has been successfully applied to the analysis of the three drugs of interest in human urine with satisfactory recovery percentages.

Cereal ß-glucan quantification with calcofluor-application to cell culture supernatants.

The specific binding of the fluorescent dye calcofluor to cereal ß-glucan results in increased fluorescence intensity of the formed complex and is in use for the quantification of ß-glucan above a critical molecular weight (MW) by flow injection analysis. In this study, this method was applied in a fast and easy batch mode. In order to emphasize the spectral information of the emission spectra of the calcofluor/ß-glucan complexes, derivative signals were calculated. A linear relationship was found between the amplitude of the second derivative signals and the ß-glucan concentration between 0.1 and 0.4 µg/mL. The low detection limit of this new method (0.045 µg/mL) enabled its use to study the transport of cereal ß-glucans over differentiated Caco-2 cell monolayers. Additionally, the method was applied to quantify ß-glucan in arabinoxylan samples, which correlated well with data by an enzyme based method.

Effect of naturally occurring tetrapyrroles on photooxidation in cow's milk.

The objective of this work was to better understand the photosensitizing effect of riboflavin versus naturally occurring tetrapyrroles in cow's milk. This was done by exposure of milk samples to blue light (400-500 nm), which is absorbed by riboflavin and tetrapyrroles, orange light (575-750 nm), which is absorbed by tetrapyrroles but not riboflavin, and white light, which contains the entire visible region. The milk was exposed to about 1.6 W/m(2) in 20 h, and two different light sources were tested: HMI lamp and fluorescent light tubes used for commercial display. Sensory analysis showed that wavelengths longer than 575 nm induced significantly more off-flavors than wavelengths shorter than 500 nm. By fluorescence spectroscopy it was observed that tetrapyrroles, in particular, chlorophyllic compounds, were degraded more by orange light than by blue and that the degree of degradation correlated closely with the formation of sensory off-flavors. The fluorescent agent Singlet Oxygen Sensor Green (SOSG) was used to monitor the formation of singlet oxygen under the different light exposure conditions, and the method verified that singlet oxygen was formed in large proportions in milk exposed to wavelengths longer than 575 nm, presumably with minor or no involvement of riboflavin. The results suggest that cholorophyllic compounds are responsible for a major part of photooxidation in milk. It is also suggested that ß-carotene protects against photooxidation under blue light because it absorbs a major portion of the light below 500 nm and thereby reduces reactions with photosensitizers.

Sensitized synchronous fluorimetric determination of trans-resveratrol and trans-piceid in red wine based on their immobilization on nylon membranes.

It has been carried out the determination of trans-resveratrol and trans-piceid in red wine samples by using room temperature synchronous fluorescence, sensitized through their retention on nylon membranes, in front-face mode. These compounds are weakly fluorescent in solution but their retention allows using the native fluorescence of these compounds as analytical signal, due to the increase in the medium rigidity. To determine these compounds in red wine, a previous liquid-liquid extraction is necessary and in the case of trans-resveratrol it is also necessary a previous cleanup stage using C18 cartridges. Diethylether and ethyl acetate are the selected extractant solvents for trans-resvertarol and trans-piceid, respectively. The retention on nylon membranes was carried out by immersion of the membranes in solutions of these compounds. Variables involved in the retention and measurement processes were optimized, and the analytical figures of merit were obtained under optimal conditions. Ethanol:water 10:90 v:v and ethyl acetate were the solvents used for the retention of trans-resveratrol and trans-piceid, respectively and, for each case a immersion time of 300 and 600s was selected. Satisfactory linear relation between fluorescence intensity and concentration was found in the intervals 0.040 and 0.242mgL(-1) of trans-resvertarol and 0.009 and 0.288mgL(-1) of trans-piceid. Concentration of 1.08±0.21mgL(-1) for trans-resveratrol and 1.49±0.36mgL(-1) for trans-piceid were found in a wine sample obtained from a pool of commercial red wines.

Assessment of the quality attributes of cod caviar paste by means of front-face fluorescence spectroscopy.

This paper describes the fluorescent behavior of cod caviar paste, stored under different conditions, in terms of light exposure and concentration of oxygen in the headspace. Multivariate curve resolution was employed to decompose the overall fluorescence spectra into pure fluorescent components and calculate the relative concentrations of these components in the different samples. Profiles corresponding to protoporphyrin IX, photoprotoporphyrin, and fluorescent oxidation products were identified. Sensory evaluation, TBARS, and analysis of volatiles are typical methods employed in the routine analysis and quality control of such food. Successful calibration models were established between fluorescence and those routine methods. Correlation coefficients higher than 0.80 were found for 79% and higher than 0.90 for 50% of the assessed odors and flavors. For instance, R values of 0.94, and 0.96 were obtained for fresh and rancid flavors respectively, and 0.89 for TBARS. On the basis of these data, it can be argued that front-face fluorescence spectroscopy can substitute all of these expensive and tedious methodologies.

Comprehensive two-dimensional liquid chromatography to quantify polyphenols in red wines.

A comprehensive two-dimensional liquid chromatography method has been applied for the quantification of polyphenols in red wines and compared to the most commonly employed conventional LC approach. Such methodology comprised the use of a microbore conventional HPLC column packed with totally porous particles in the first dimension and a partially porous column of conventional diameter in the second dimension. Even though a good number of applications in comprehensive LC have been reported, quantification experiments have been rarely described. To this regard, the advantages of comprehensive LC together with the employment of dedicated software capable of detecting and quantifying each peak from the 2D plot, have been taken into account for quantifying the most representative polyphenols in three different commercial Sicilian red wine samples. The optimized method has been validated in terms of linearity, sensitivity, detection and quantification limits. LODs as low as 0.02 ppm were obtained using the one-dimensional HPLC-DAD method, whereas values lower than 0.10 ppm were obtained by comprehensive LC. However, comprehensive LC allowed the quantification of a higher number of compounds with RSD lower than 10% thanks to its improved resolving power. The separation capabilities of comprehensive LC allowed the analysis of complex natural samples without any pre-treatment to effectively reduce the interferences coming from the matrix.

Usefulness of fluorescence excitation-emission matrices in combination with PARAFAC, as fingerprints of red wines.

The possibility of using front-face fluorescence spectroscopy to characterize red wines was investigated, and a tentative identification of their main fluorescent components was attempted. Fifty-seven red wine samples from different origins were included in the present study. Their fluorescence excitation-emission matrices (EEMs) were registered directly on 3-mL aliquots of untreated samples. The assayed excitation and emission ranges were 245-340 and 300-500 nm, respectively. The set of 57 EEMs was analyzed by means of parallel factor analysis (PARAFAC). Thus, the spectral excitation and emission profiles of possible "pure" fluorescence components (PARAFAC loadings) and the relative contribution of each component to the individual EEMs (PARAFAC scores) were obtained. The red wine system contained four main fluorescence components, and the excitation and emission loadings had maxima at the wavelength pairs 260/380, 275/323, 330/410, and 280/364 nm, respectively. A tentative identification of fluorophores was done by matching PARAFAC score values with HPLC measurements on the same 57 samples, as well as fluorescence measurements on pure compounds typically present in red wine. It was found that the third component was highly correlated with concentrations of catechin and epicatechin. When the PARAFAC score values were plotted against each other, they did to some extent discriminate the wines according to origin (country) and grape variety.

Post-column on-line photochemical derivatization for the direct isocratic-LC-FLD analysis of resveratrol and piceid isomers in wine.

Resveratrol is a stilbene produced by plants, e.g. grapes, in response to stress. Resveratrol is extracted during winemaking, being present in wine as 3-O-ß-d-gluocoside (piceid) and as aglycone. Both, resveratrol and piceid exist in two isomeric forms, trans and cis. Resveratrol and piceid are weakly fluorescent in both of their isomeric forms, but highly fluorescent compounds are obtained when the original molecules are UV-irradiated. A chromatographic method with post-column on-line photoderivatization, has been developed for the analysis of resveratrol and piceid isomers. The four analytes are firstly separated in a C18 column (150mm×3.9mm i.d., 4µm) by isocratic elution, at 15°C, with a mobile phase consisting of a mixture acetonitrile:o-phosphoric acid (0.04%), 18:82, v:v, at 0.9mLmin(-1), and secondly they are on-line phototransformed into their fluorescent photoproducts in a 3m PTFE tube coiled around a 4W xenon lamp. The elution conditions have been chemometrically optimized by means of the experimental design and the response surface methodology. Linearity ranges from 0.10 to 1.50 and from 0.10 to 1.00µgmL(-1) and LOD around 0.001 and 0.01µgmL(-1) have been calculated for trans- and cis-isomers, respectively. The method has been satisfactorily applied to red and white wine samples by standard addition and external calibration, respectively.