Raman mapping for determination of TiO2 in different solid food samples by multivariate curve resolution with alternating least squares.

Titanium dioxide is a food additive commonly used as a white food coloring (E171). Its wide use by the food industry associated with the nanometric size distribution of the particles of this pigment has shown high genotoxicity associated with recurrent exposure by ingestion. Therefore, the use of E171 in food products has already been banned by some industries and in the European Union. Such banishment should soon be extended to other countries around the world, making it important to establish techniques for the efficient determination of TiO2 in different food products. The association between hyperspectral images and chemometric tools can be useful in this sense, aiming to enable the use of a single method for sample preparation and analysis of different types of food. Thus, the present work aims to evaluate the use of Raman mapping associated with the resolution of multivariate curves with alternating least squares (MCR-ALS) for the determination of titanium dioxide in solid food samples with different compositions, without the need to introduce specific sample preparation. The proposed method allowed for the first-time quantification of TiO2 in different food matrices without specific sample preparation, with a simple, rapid, accurate (93% of recovery), low detection limits (0.0111% m/m) and quantification (0.0370% m/m) and adequate linearity (r = 0.9990) and precise (standard deviation around 0.020-0.030% w/w) methodology. Such results highlight the potential use of Raman mapping associated with the MCR-ALS for quantification of the nano-TiO2 in commercial samples.

High-Resolution Magic Angle Spinning (HR-MAS) NMR-Based Fingerprints Determination in the Medicinal Plant Berberis laurina.

Berberis laurina (Berberidaceae) is a well-known medicinal plant used in traditional medicine since ancient times; however, it is scarcely studied to a large-scale fingerprint. This work presents a broad-range fingerprints determination through high-resolution magical angle spinning (HR-MAS) nuclear magnetic resonance (NMR) spectroscopy, a well-established flexible analytical method and one of most powerful "omics" platforms. It had been intended to describe a large range of chemical compositions in all plant parts. Beyond that, HR-MAS NMR allowed the direct investigation of botanical material (leaves, stems, and roots) in their natural, unaltered states, preventing molecular changes. The study revealed 17 metabolites, including caffeic acid, and berberine, a remarkable alkaloid from the genus Berberis L. The metabolic pattern changes of the leaves in the course of time were found to be seasonally dependent, probably due to the variability of seasonal and environmental trends. This metabolites overview is of great importance in understanding plant (bio)chemistry and mediating plant survival and is influenceable by interacting environmental means. Moreover, the study will be helpful in medicinal purposes, health sciences, crop evaluations, and genetic and biotechnological research.

Statistical analysis of wheat under different seed treatments: development of a discriminative model based on physicochemical and rheological properties.

BACKGROUND: Quality control in the wheat industry comprises numerous analyses that are time-consuming and demand numerous procedures and specific apparatus. The application of multivariate calibration techniques contributes to the interpretation of the data generated during these analyses. The present study aimed to correlate a representative number of wheat properties with the treatment applied to the wheat seeds using multivariate calibration techniques. RESULTS: In the present study, a wheat pilot planting experiment applying different fungicides combination as a seed treatment (carbendazim, carbendazim + thiram, carboxin + thiram, and triadimenol) was conducted. The resulting wheat grains were subjected to 33 analyses routinely performed in industry. A principal components analysis indicated all analyses were relevant for the different seed treatment discrimination. Afterwards, a k-nearest neighbors discriminative model was developed and was able to classify the seed treatments. In accordance with this model, the most relevant variables for the seed treatment discrimination were the rheological properties of the dough. CONCLUSION: It was possible to develop a discriminative model that directly correlated the wheat seed treatment with the properties of the resulting grains and flours. © 2017 Society of Chemical Industry.

Determination of fat, protein and moisture in ricotta cheese by near infrared spectroscopy and multivariate calibration.

Near-infrared reflectance spectroscopy (NIRS) with partial least squares regression (PLSR) was used to determine levels of fat, protein and moisture in ricotta cheese without complex sample preparation. Spectra of 19 conventional and low-fat ricotta samples from different manufacturers were collected in duplicate, with 33 of the 38 spectra used as a calibration set and the remaining 5 spectra used as an external validation set. The best results were obtained by processing the spectral region between 1,100 and 2,500 nm. Multivariate models with six latent variables (LVs) showed good prediction capability for fat and protein determinations, with average relative errors (Er) of 6.37 % and 5.95 %, respectively. For moisture, a more robust model was obtained with 4 LVs, showing better prevision capacity and Er of 1.91 %.

Evaluation of polypropylene microporous membranes as extraction devices for determination of carcinogenic aromatic amines in smoker urine by GC-MS/MS.

Exposure to tobacco smoke is highly correlated to the incidence of different types of cancer due to various carcinogenic compounds present in such smoke. Aromatic amines, such as 1-naphthylamine (1-NA) and 2-naphthylamine (2-NA), are produced in tobacco burning and are linked to bladder cancer. Miniaturized solid phase extraction techniques, such as microporous membrane solid phase extraction (MMSPE), have shown potential for the extraction of aromatic compounds. In this study, a bioanalytical method for the determination of 1-NA and 2-NA in human urine was developed using polypropylene microporous membranes as a sorptive phase for MMSPE. Urine samples were hydrolyzed with HCl for 1 h at 80 °C, after which pH was adjusted to 10. Ultrasound-assisted MMSPE procedure was optimized by factorial design as follows. To each sample, 750 µL of methanol was added, and ultrasound-assisted MMSPE was conducted for 1 h with four devices containing seven 2 mm polypropylene membrane segments. After extraction, the segments were transferred to 400 µL of hexane, and desorption was conducted for 30 min. Extracts were submitted to a simple and fast microwave-assisted derivatization procedure, by the addition of 10 µL of PFPA and heating at 480 W for 3 min, followed by clean-up with phosphate buffer pH 8.0 and GC-MS/MS analysis. Adequate linearity was obtained for both analytes in a range from 25 to 500 µg L-1, while the multiple reaction monitoring approach provided satisfactory selectivity and specificity. Intra-day (n = 6) and inter-day (n = 5) precision and accuracy were satisfactory, below 15 % and between 85 and 115 %, respectively. Recovery rates found were 91.9 and 58.4 % for 1-NA and 2-NA, respectively, with adequate precision. 1-NA was found in first-hand smokers' urine samples in a concentration range from 20.98 to 89.09 µg in 24 h, while it could be detected in second-hand smoker's urine samples, and 2-NA detected in all first and second-hand smokers' urine samples. The proposed method expands the applicability of low cost MMSPE devices to aromatic amines and biological fluids.

TiO2 and ZnO mediated photocatalytic degradation of E2 and EE2 estrogens.

In this work, the photocatalytic degradation of selected estrogens (E2 and EE2) was evaluated, using bench-scale and continuous treatment systems assisted by artificial UV-A and solar radiation. Processes based on the use of TiO2 permit an efficient degradation of E2 and EE2 estrogens, usually at reaction times lower than 15 min. Especially remarkable is the high degradation efficiency shown by sunlight-assisted processes, which are extremely favored by the high efficiency of compound parabolic collectors.

A green method for the authentication of sugarcane spirit and prediction of density and alcohol content based on near infrared spectroscopy and chemometric tools.

Cachaça is a Brazilian beverage obtained from the fermentation of sugarcane juice (sugarcane spirit) and is considered one of the most consumed alcoholic beverages in the world with a strong economic impact on the northeastern Brazil, more specifically in the Brejo. This microregion produces sugarcane spirits with high quality associated to edaphoclimatic conditions. In this sense, analysis for sample authentication and quality control that uses solvent-free, environmentally friendly, rapid and non-destructive methods is advantageous for cachaça producers and production chain. Thus, in this work commercial cachaça samples using near-infrared spectroscopy (NIRS) were classified based on geographical origin using one-class classification Data-Driven in Soft Independent Modelling of Class Analogy (DD-SIMCA) and One-Class Partial Least Squares (OCPLS) and predicted quality parameters of alcohol content and density based on different chemometric algorithms. A total of 150 sugarcane spirits samples were purchased from the Brazilian retail market being 100 from Brejo and 50 from other regions of Brazil. The one-class chemometric classification model was obtained with DD-SIMCA using the Savitzky-Golay derivative with first derivative, 9-point window and 1st degree polynomial as preprocessing algorithm and sensibility was 96.70 % and specificity 100 % in the spectral range 7,290-11,726 cm-1. Satisfactory results were obtained in the model constructs for density and the chemometric model, iSPA-PLS algorithm with baseline offset as preprocessing, obtained root mean square errors of prediction (RMSEP) of 0.0011 mg/L and Relative Error of Prediction (REP) of 0.12 %. The chemometric model for alcohol content prediction used the iSPA-PLS algorithm with Savitzky-Golay derivative with first derivative, 9-point window and 1st degree polynomial as algorithm as preprocessing obtaining RMSEP and REP of 0.69 and 1.81 % (v/v), respectively. Both models used the spectral range from 7,290-11,726 cm-1. The results reflected the potential of vibrational spectroscopy coupled with chemometrics to build reliable models for identifying the geographical origin of cachaça samples for predicting quality parameters in cachaça samples.

1H NMR-based metabolic profile and chemometric analysis for the discrimination of Passiflora species genotypic variations.

The species of the genus Passiflora (Passifloraceae family) have been used as food, cosmetic and traditional herbal. As a result, the Passiflora species are widely cultivated and has an economic, medicinal and ornamental importance. The popular designation as "passion fruit" and chemical profile of several Passiflora species remains unknown. The lack of chemical information contributes to the erroneous classification and adulteration. In recent years, special attention has been paid to the bioactivity and phytochemical profiles of several Passiflora species extracts. In this research, 1H NMR-based metabolic profiling coupled with chemometric tools was used to characterize and distinguish extracts obtained from different wild Passiflora species (P. alata, P. cincinnata, and P. setacea) and genetic varieties (P. alata var. BRS Pérola do Cerrado, P. cincinnata var. BRS Sertão Forte, and P. setacea var. BRS Pérola do Cerrado). Fourteen metabolites were identified by 1D and 2D NMR experiments, highlighting the presence of fatty acids, carbohydrates, saponins, alkaloids, and mainly C-glycosidic flavones. Principal components analysis (PCA) allowed discrimination of Passiflora extracts, which the quadranguloside, oleanolic acid-3-sophoroside, α-glucose, ß-glucose, and vitexin-2-O"-rhamnoside were relevant in the differentiation of P. alata and P. alata var. BRS Pérola do Cerrado, while the flavones isovitexin and isovitexin-2-O"-xyloside were dominant in the grouping of P. setacea and P. setacea var. BRS Pérola do Cerrado, and finally P. cincinnata and P. cincinnata var. BRS Sertão Forte grouped by the influence of the fatty acids, sucrose, flavones (isoorientin and vitexin-2-O"-xyloside), and trigonelline. The varieties of P. setacea, and P. cincinnata are chemically equivalent to the original Passiflora species. However, the PCA analysis showed that the genetic variety of P. alata occupied a different position in the scores plot provoked mainly by the presence of oleanolic acid-3-sophoroside. The 1H NMR metabolic profile can be efficient for quality control evaluation, and can contribute to the investigation of new alternatives for official Passiflora herbal medicines.

1H HR-MAS NMR chemical profile and chemometric analysis as a tool for quality control of different cultivars of green tea (Camellia sinensis).

Green tea is a product obtained from the processing of fresh leaves of Camellia sinensis (L.) O. Kuntze species. In this study, the influence of climatic parameters on the chemical composition of green tea cultivars ('Yabukita' and 'Yutakamidori') over the harvest was evaluated using HR-MAS NMR. 'Yabukita' showed higher concentrations of epicatechin while higher amounts of theanine and caffeine were found in 'Yutakamidori'. The decline of theanine was associated with high average maximum temperature and solar radiation index, this latter also seemed to be responsible for relevant changes in epicatechin concentrations. It was not possible to associate any trend between climatic parameters and caffeine concentration. Fluctuations in linolenic acid concentration were monitored during the harvest period and were associated with the plant's defense mechanism. Monitoring of green tea over seasons and correlating the fluctuations of compounds to climatic parameters might become an efficient strategy for establishing quality standards for green teas.

Simultaneous multi-residue pesticide analysis in southern Brazilian soil based on chemometric tools and QuEChERS-LC-DAD/FLD method.

A simple and straightforward QuEChERS extraction method was proposed for the simultaneous determination of atrazine (ATZ), desethylatrazine (DEA), desisopropylatrazine (DIA), carbaryl (CBL), carbendazim (CBD), and diuron (DIU) in soil with high agricultural activity from southeastern Brazil, using high-performance liquid chromatography-diode-array detection/fluorescence detection. Screening studies carried out by 24 factorial design indicate better recoveries when less sample (1.0 g) and the volume of solvent (2.0 mL of ACN) were applied, compared to the original QuEChERS method. Furthermore, interactions between factors were not negligible in the experimental set, except for ATZ and DIU, in which only water volume influenced their recovery. The influence of the type (primary secondary amine (PSA), C18, and Florisil) and the sorbent amount ratio to the compounds' concentration were also considered. PSA (25 mg) was selected as the best sorbent without losing analytical response. The limits of quantification (LOQ) were estimated to be 5.0 to 15 µg kg-1 in the soil matrix. Analytical performances were consistent with linearity (R2 ≥ 0.998), recovery from 74.7 to 108%, and relative standard deviations (RSD) between 2.6 and 20.2%. Robustness was assessed by fractional factorial Plackett-Burman design. The method is recommended for chemicals that are soluble in water, and it was successfully applied in the analysis of real soil samples containing the analytes in the range of µg kg-1, proving to be suitable for the study of soils strongly impacted by agricultural activity.

1H HR-MAS NMR and chemometric methods for discrimination and classification of Baccharis (Asteraceae): A proposal for quality control of Baccharis trimera.

Baccharis trimera is a species recognized by health agencies and recommended by the Brazilian Pharmacopoeia by having medicinal properties. In this work, HR-MAS NMR spectroscopy combined with chemometric tools, such as Principal Components Analysis (PCA), Partial Least Squares Discriminant Analysis (PLS-DA) and Soft Independent Modeling by Class Analogy (SIMCA), were used to evaluate the quality control and authenticity of commercial samples of Baccharis, as well as to discriminate B. trimera samples from other species of the Caulopterae section (B. articulata, B. trimera, B. junciformis, B. milleflora, and B. myriocephala). The high morphological similarity of these species makes it difficult for their identifications and discriminations, even by taxonomists. Different PCA pre-processing (autoscaling, Pareto scaling, and mean centering) allowed to discriminate B. trimera and B. myriocephala from the other species, mainly due to the presence of carquejyl acetate, indicated their chemical similarity. The 1H HR-MAS NMR spectral profile offers the possibility of tracking not only the chemical markers, such as the presence of carquejyl acetate, which can also be helpful in the B. trimera authentication/identification. The application of classification methods in standard samples revealed that PLS-DA models showed better performance on the calibration and validation sets than SIMCA model. However, PLS-DA and SIMCA applied to commercial samples showed that none of the commercial samples were classified as B. trimera, which suggested the lack of strict quality control regarding these products. The methodology developed in the present work might contribute to chemotaxonomy of the genus Baccharis.

Olfactory response of Mahanarva spectabilis (Hemiptera: Cercopidae) to volatile organic compounds from forage grasses.

Several herbivorous insects utilize plant chemical cues to identify hosts for feeding. The role of smell in host plant detection by Mahanarva spectabilis (Distant) remains largely unknown. In this study, assays were applied to assess M. spectabilis olfactory responses to forage grasses (Pennisetum purpureum cvs. Roxo Botucatu and Pioneiro; Panicum maximum cvs. Makueni and Tanzânia; Hyparrhenia rufa cv. Jaraguá; Melinis minutiflora; Cynodon dactylon cv. Tifton; Brachiaria brizantha cv. Marandú; and Brachiaria decumbens cv. Basilisk). Bioassays were performed using a Y-olfactometer to evaluate the behavior of adult M. spectabilis to forage damaged and undamaged by insects. M. spectabilis preferred volatiles of undamaged Basilisk and Pioneiro. Repellent behavior by M. spectabilis to cospecifics was recorded for plant volatiles from damaged Marandú. The mixture of volatiles from undamaged forage grasses differed from that of forage grasses damaged by insects. Forage grasses showed a greater diversity of compounds after damage, including menthone, eucalyptol and camphor, which are compounds likely to cause loss of attractiveness or repellence. Our results demonstrate that M. spectabilis employs plant chemical cues in its choice of hosts. This fact may contribute to strategies of integrated management against this pest.

Study of different environmental matrices to access the extension of metal contamination along highways.

Metals are indicators of contamination by anthropic activities, such as road traffic. To assess the extent of the metal contamination, more comprehensive studies analyzing different environmental matrices, such as soils, dust, and plants, collected in different sites that are potential sources of these pollutants along the highways, must be prioritized. Samples of soils, dust, and plants were collected alongside the highways of Brazil at 20 sites selected in strategic locations of metal accumulation (Cr, Pb, Zn, As, and Sb) or different situations of the high ways during two rain conditions (wet and dry weeks of sampling): nearby gutters and water supplies, tolls, petrol stations, a federal road police station, and areas associated with agriculture (yearly culture planting upstream of the highway). The geoaccumulation index (metal concentration in the sample of interest/background) varied from 0 to 6, and the decreasing order of contamination by metals during the wet and dry periods were, respectively: Zn > As > Pb = Sb > Cr and Zn > As > Pb > Cr > Sb. In the soils near the highways, the highest concentrations of metals were as follows (mg kg-1): As = 15.6, Cr = 81.9, Pb = 39.7, Sb = 5.0, and Zn = 379.3. The highest amounts of these elements in the most superficial layer in soils indicated their addition through atmospheric emissions. The most prominent metal was Sb, whose concentration was greater than the quality limits for soils. The concentration of Sb in soils was higher in the wet week than in the dry week. The emissions from road traffic promoted the increase in metals in the dust on the track, especially Zn and Pb. The highest metal concentrations in grasses (Brachiaria) were found in the roots, except for Sb and Zn, which suggests leaf absorption of atmospheric deposition. Metal contamination was widespread in all studied matrices along the highways.

1H HR-MAS NMR-based metabolomics study of different persimmon cultivars (Diospyros kaki) during fruit development.

1H HR-MAS NMR spectroscopy was used to track the metabolic changes throughout the whole development of astringent ('Giombo') and non-astringent ('Fuyu') cultivars of persimmon (Diospyros kaki). The NMR data revealed the low concentration of amino acids (threonine, alanine, citrulline and GABA) and organic acids (malic acid). In addition, the signals of carbohydrates (sucrose, glucose and fructose) seemed to play the most important role in the fruit development. In both cultivars, the growth was characterized by fluctuating sucrose concentration along with a constant increase in both glucose and fructose. In the initial growth stage, the polyphenol composition was quite different between the cultivars. Gallic acid was detected throughout the growth of 'Giombo', while for 'Fuyu', signals of polyphenols disappeared over time. Additional multivariate analysis suggested that these cultivars share many metabolic similarities during development. These findings might help the comprehension of fruit development, which in turn, impacts the quality of the fruits.

New insight into monitoring degradation products during the TiO2-photocatalysis process by multivariate molecular spectroscopy.

This study focuses on the feasibility of a spectroscopic multivariate method for monitoring the concentration of phenol and its main degradation products during heterogeneous photocatalysis. Phenolic compounds were chosen as model to evaluate the degradation process due to their toxicity and persistence in the environment and also their well-known degradation pathway. The predictive capability of the multivariate method developed by partial least squares regression (PLSR) over the spectral range of 200-350 nm was satisfactory, allowing mean predicted errors below 5.0 % in the simultaneous determination of the target compounds using six latent variables and smoothing spectra. Suitable results were reported for the simultaneous determination of hydroquinone, resorcinol, pyrocatechol, and p-benzoquinone in accordance to the chromatographic method. Characteristics such as simplicity, low cost, and fast data acquisition are remarkable in this procedure, which makes it appropriate for this type of analytical control.

Avaliação da estabilidade foto-oxidativa dos óleos de canola e de milho em presença de antioxidantes sintéticos / Evaluation of stability photo-oxidative of canola oil and corn oilin the presence of synthetic antioxidants

A estabilidade dos óleos vegetais à oxidação depende do equilíbrio entre a composição e a presença de pró-oxidantes e antioxidantes. O objetivo deste estudo consistiu em avaliar o efeito da presença de antioxidantes sintéticos durante o processo de foto-oxidação dos óleos de canola e milho. As amostras dos óleos de canola e milho em presença e em ausência dos antioxidantes butil-hidroxitolueno (BHA), propil galato (PG) e terc butil-hidroquinona (TBHQ), foram submetidas ao estresse foto-oxidativo. A reação de foto-oxidação seguiu uma cinética de primeira ordem. A constante de velocidade no período de 20 dias de foto-oxidação evidenciou que o antioxidante PG apresentou maior efeito protetor para o óleo de canola e o TBHQ para o óleo de milho. A partir dos dados de UV e RMN de ¹H, no período de 60 dias, constatou-se que os três antioxidantes apresentaram um efeito protetor a foto-oxidação. Os dados de UV evidenciaram aumento de absorção da banda em 232 nm devido à foto-oxidação e formação de dienos conjugados. A redução da intensidade de absorção desta banda na foto-oxidação com o tempo de exposição revelou que a proteção, tanto para o óleo de canola como para o de milho, foi mais efetiva com o antioxidante PG. Os índices de oxidação Roa e fração residual de hidrogênios (H) dialílicos, alílicos e vinílicos também evidenciaram que o antioxidante PG apresentou o melhor desempenho na proteção dos dois tipos de óleo.

The stability of vegetable oils in relation to oxidation depends on the balance between the composition and the presence of antioxidants and pro-oxidants. The objective of this study was to evaluate the effect of the presence of antioxidants in vegetable oils in the protection of photo-oxidation. Samples of canola oil and corn oil in the presence and absence of the antioxidants, butylated hydroxytoluene (BHA), propyl gallate (PG) and tert-butylhydroquinone (TBHQ), were subjected to photo-oxidative stress at room temperature for 60 days. The photo-oxidation reaction followed a first order kinetics. The rate constant for the period of 20 days of photo-oxidation showed that the PG antioxidant showed greater protective effect for canola oil and TBHQ showed a greater protective effect for corn oil. The UV and ¹H NMR data at 60 days showed that the three antioxidants had a protective effect on photo-oxidation. The UV data showed increased absorption at the 232nm band due to photo-oxidation and the formation of conjugated dienes. The reduction in intensity of this absorption band in photo-oxidation with time of exposure revealed that the protection, both for the canola oil and for the corn oil, was more effective with the PG antioxidant. The rates of Roa oxidation and residual fraction of diallyl, allyl and vinyl hydrogens also showed that the PG antioxidant showed the best performance in protecting both oils.

Por que otimização multivariada? / Why multivariate optimization?

Normalmente, estudos que objetivam a otimização de variáveis experimentais são realizados através de procedimentos que avaliam o efeito de uma variável por vez, o que, de maneira geral, impede o estabelecimento de ótimos verdadeiros, em razão da freqüência com que as variáveis se apresentam altamente correlacionadas. Neste trabalho, algumas aplicações práticas são apresentadas, visando demonstrar a conveniência dos procedimentos multivariados de otimização, principalmente sistemas de planejamento fatorial de experimentos. A partir de três exemplos práticos relacionados com a otimização de processos de degradação, discutem-se aspectos relacionados com o desenho experimental e a interpretação de resultados.