Espectroscopia no infravermelho e método quimiométrico para a pesquisa de antimicrobianos em leite da microrregião de Pato Branco - PR

Considering the social and economic importance that the milk has, the objective of this study was to evaluate the incidence and quantifying antimicrobial residues in the food. The samples were collected in dairy industry of southwestern Paraná state and thus they were able to cover all ten municipalities in the region of Pato Branco. The work focused on the development of appropriate models for the identification and quantification of analytes: tetracycline, sulfamethazine, sulfadimethoxine, chloramphenicol and ampicillin, all antimicrobials with health interest. For the calibration procedure and validation of the models was used the Infrared Spectroscopy Fourier Transform associated with chemometric method based on Partial Least Squares regression (PLS - Partial Least Squares). To prepare a work solution antimicrobials, the five analytes of interest were used in increasing doses, namely tetracycline from 0 to 0.60 ppm, sulfamethazine 0 to 0.12 ppm, sulfadimethoxine 0 to 2.40 ppm chloramphenicol 0 1.20 ppm and ampicillin 0 to 1.80 ppm to perform the work with the interest in multiresidues analysis. The performance of the models constructed was evaluated through the figures of merit: mean square error of calibration and cross-validation, correlation coefficients and offset performance ratio. For the purposes of applicability in this work, it is considered that the models generated for Tetracycline, Sulfadimethoxine and Chloramphenicol were considered viable, with the greatest predictive power and efficiency, then were employed to evaluate the quality of raw milk from the region of Pato Branco . Among the analyzed samples by NIR, 70% were in conformity with sanitary legislation, and 5% of these samples had concentrations below the Maximum Residue permitted, and is also satisfactory. However 30% of the sample set showed unsatisfactory results when evaluating the contamination with antimicrobials residues, which is non conformity related to the presence of antimicrobial unauthorized use or concentrations above the permitted limits. With the development of this work can be said that laboratory tests in the food area, using infrared spectroscopy with multivariate calibration was also good, fast in analysis, reduced costs and with minimum generation of laboratory waste. Thus, the alternative method proposed meets the quality concerns and desired efficiency by industrial sectors and society in general.

Desenvolvimento e aplicação de modelo de calibração multivariada para determinação de açúcares e ácidos orgânicos em bebidas comerciais utilizando espectroscopia no infravermelho

The routine analysis for quantization of organic acids and sugars are generally slow methods that involve the use and preparation of several reagents, require trained professional, the availability of special equipment and is expensive. In this context, it has been increasing investment in research whose purpose is the development of substitutive methods to reference, which are faster, cheap and simple, and infrared spectroscopy have been highlighted in this regard. The present study developed multivariate calibration models for the simultaneous and quantitative determination of ascorbic acid, citric, malic and tartaric and sugars sucrose, glucose and fructose, and soluble solids in juices and fruit nectars and classification models for ACP. We used methods of spectroscopy in the near infrared (Near Infrared, NIR) in association with the method regression of partial least squares (PLS). Were used 42 samples between juices and fruit nectars commercially available in local shops. For the construction of the models were performed with reference analysis using high-performance liquid chromatography (HPLC) and refractometry for the analysis of soluble solids. Subsequently, the acquisition of the spectra was done in triplicate, in the spectral range 12500 to 4000 cm-1. The best models were applied to the quantification of analytes in study on natural juices and juice samples produced in the Paraná Southwest Region. The juices used in the application of the models also underwent physical and chemical analysis. Validation of chromatographic methodology has shown satisfactory results, since the external calibration curve obtained R-square value (R2) above 0.98 and coefficient of variation (%CV) for intermediate precision and repeatability below 8.83%. Through the Principal Component Analysis (PCA) was possible to separate samples of juices into two major groups, grape and apple and tangerine and orange, while for nectars groups separated guava and grape, and pineapple and apple. Different validation methods, and pre-processes that were used separately and in combination, were obtained with multivariate calibration models with average forecast square error (RMSEP) and cross validation (RMSECV) errors below 1.33 and 1.53 g.100 mL-1, respectively and R2 above 0.771, except for malic acid. The physicochemical analysis enabled the characterization of drinks, including the pH working range (variation of 2.83 to 5.79) and acidity within the parameters Regulation for each flavor. Regression models have demonstrated the possibility of determining both ascorbic acids, citric, malic and tartaric with successfully, besides sucrose, glucose and fructose by means of only a spectrum, suggesting that the models are economically viable for quality control and product standardization in the fruit juice and nectars processing industry.

Correlação entre o sinal mecanomiográfico e a escala modificada de Ashworth durante avaliação clínica da espasticidade

Spasticity is a common disorder in people who have upper motor neuron injury. The involvement may occur at different levels. The Modified Ashworth Scale (MAS) is the most used method to measure involvement levels. But it corresponds to a subjective evaluation. Mechanomyography (MMG) is an objective technique that quantifies the muscle vibration during the contraction and stretching events. So, it may assess the level of spasticity accurately. This study aimed to investigate the correlation between spasticity levels determined by MAS with MMG signal in spastic and not spastic muscles. In the experimental protocol, we evaluated 34 members of 22 volunteers, of both genders, with a mean age of 39.91 ± 13.77 years. We evaluated the levels of spasticity by MAS in flexor and extensor muscle groups of the knee and/or elbow, where one muscle group was the agonist and one antagonist. Simultaneously the assessment by the MAS, caught up the MMG signals. We used a custom MMG equipment to register and record the signals, configured in LabView platform. Using the MatLab computer program, it was processed the MMG signals in the time domain (median energy) and spectral domain (median frequency) for the three motion axes: X (transversal), Y (longitudinal) and Z (perpendicular). For bandwidth delimitation, we used a 3rd order Butterworth filter, acting in the range of 5-50 Hz. Statistical tests as Spearman's correlation coefficient, Kruskal-Wallis test and linear correlation test were applied. As results in the time domain, the Kruskal-Wallis test showed differences in median energy (MMGME) between MAS groups. The linear correlation test showed high linear correlation between MAS and MMGME for the agonist muscle as well as for the antagonist group. The largest linear correlation occurred between the MAS and MMG ME for the Z axis of the agonist muscle group (R2 = 0.9557) and the lowest correlation occurred in the X axis, for the antagonist muscle group (R2 = 0.8862). The Spearman correlation test also confirmed high correlation for all axes in the time domain analysis. In the spectral domain, the analysis showed an increase in the median frequency (MMGMF) in MAS’ greater levels. The highest correlation coefficient between MAS and MMGMF signal occurred in the Z axis for the agonist muscle group (R2 = 0.4883), and the lowest value occurred on the Y axis for the antagonist group (R2 = 0.1657). By means of the Spearman correlation test, the highest correlation occurred between the Y axis of the agonist group (0.6951; p <0.001) and the lowest value on the X axis of the antagonist group (0.3592; p <0.001). We conclude that there was a significantly high correlation between the MMGME and MAS in both muscle groups. Also between MMG and MAS occurred a significant correlation, however moderate for the agonist group, and low for the antagonist group. So, the MMGME proved to be more an appropriate descriptor to correlate with the degree of spasticity defined by the MAS.

Adsorção de corantes têxteis aniônicos e catiônicos em resíduos do processamento de fios de algodão modificados quimicamente

The textile industry generates a large volume of high organic effluent loading whoseintense color arises from residual dyes. Due to the environmental implications caused by this category of contaminant there is a permanent search for methods to remove these compounds from industrial waste waters. The adsorption alternative is one of the most efficient ways for such a purpose of sequestering/remediation and the use of inexpensive materials such as agricultural residues (e.g., sugarcane bagasse) and cotton dust waste (CDW) from weaving in their natural or chemically modified forms. The inclusion of quaternary amino groups (DEAE+) and methylcarboxylic (CM-) in the CDW cellulosic structure generates an ion exchange capacity in these formerly inert matrix and, consequently, consolidates its ability for electrovalent adsorption of residual textile dyes. The obtained ionic matrices were evaluated for pHpcz, the retention efficiency for various textile dyes in different experimental conditions, such as initial concentration , temperature, contact time in order to determine the kinetic and thermodynamic parameters of adsorption in batch, turning comprehensive how does occur the process, then understood from the respective isotherms. It was observed a change in the pHpcz for CM--CDW (6.07) and DEAE+-CDW (9.66) as compared to the native CDW (6.46), confirming changes in the total surface charge. The ionized matrices were effective for removing all evaluated pure or residual textile dyes under various tested experimental conditions. The kinetics of the adsorption process data had best fitted to the model a pseudosecond order and an intraparticle diffusion model suggested that the process takes place in more than one step. The time required for the system to reach equilibrium varied according to the initial concentration of dye, being faster in diluted solutions. The isotherm model of Langmuir was the best fit to the experimental data. The maximum adsorption capacity varied differently for each tested dye and it is closely related to the interaction adsorbent/adsorbate and dye chemical structure. Few dyes obtained a linear variation of the balance ka constant due to the inversion of temperature and might have influence form their thermodynamic behavior. Dyes that could be evaluated such as BR 18: 1 and AzL, showed features of an endothermic adsorption process (ΔH° positive) and the dye VmL presented exothermic process characteristics (ΔH° negative). ΔG° values suggested that adsorption occurred spontaneously, except for the BY 28 dye, and the values of ΔH° indicated that adsorption occurred by a chemisorption process. The reduction of 31 to 51% in the biodegradability of the matrix after the dye adsorption means that they must go through a cleaning process before being discarded or recycled, and the regeneration test indicates that matrices can be reused up to five times without loss of performance. The DEAE+-CDW matrix was efficient for the removal of color from a real textile effluent reaching an UV-Visible spectral area decrease of 93% when applied in a proportion of 15 g ion exchanger matrix L-1 of colored wastewater, even in the case of the parallel presence of 50 g L-1 of mordant salts in the waste water. The wide range of colored matter removal by the synthesized matrices varied from 40.27 to 98.65 mg g-1 of ionized matrix, obviously depending in each particular chemical structure of the dye upon adsorption.