Bionanocomposite Based on Cassava Waste Starch, Locust Bean Galactomannan, and Cassava Waste Cellulose Nanofibers.

Natural polysaccharides are among the renewable sources with great potential for replacing petroleum-derived chemicals as precursors to produce biodegradable films. This study aimed to prepare biopolymeric films using starch extracted from the periderm and cortex of cassava roots (waste from cassava root processing), locust bean galactomannan, and cellulose nanofibers also obtained from cassava waste. The films were prepared by casting, and their physicochemical, mechanical, and biodegradability properties were evaluated. The content of cellulose nanofibers varied from 0.5 to 2.5%. Although the addition of cellulose nanofibers did not alter the mechanical properties of the films, it significantly enhanced the vapor barrier of the films (0.055 g mm/m2 h kPa-2.5% nanofibers) and their respective stabilities in aqueous acidic and alkaline media. All prepared films were biodegradable, with complete degradation occurring within five days. The prepared films were deemed promising alternatives for minimizing environmental impacts caused by the disposal of petroleum-derived materials.

Improvement of Targeted Fungi Secondary Metabolite Production Using a Systematic Experimental Design and Chemometrics Analysis.

Fungi are well-known producers of chemically diverse and biologically active secondary metabolites. However, their production yields through fermentation may hamper structural analysis and biological activity downstream investigations. Herein, a systematic experimental design that varies multiple cultivation parameters, followed by chemometrics analysis on HPLC-UV-MS or UHPLC-HRMS/MS data, is presented to enhance the production yield of fungal natural products. The overall procedure typically requires 3-4 months of work when first developed, and up to 3 months as a routine procedure.

Development of Films from Spent Coffee Grounds' Polysaccharides Crosslinked with Calcium Ions and 1,4-Phenylenediboronic Acid: A Comparative Analysis of Film Properties and Biodegradability.

Most polymeric materials are synthetic and derived from petroleum, hence they accumulate in landfills or the ocean, and recent studies have focused on alternatives to replace them with biodegradable materials from renewable sources. Biodegradable wastes from food and agroindustry, such as spent coffee grounds (SCGs), are annually discarded on a large scale and are rich in organic compounds, such as polysaccharides, that could be used as precursors to produce films. Around 6.5 million tons of SCGs are discarded every year, generating an environmental problem around the world. Therefore, it was the aim of this work to develop films from the SCGs polysaccharide fraction, which is comprised of cellulose, galactomannans and arabinogalactans. Two types of crosslinking were performed: the first forming coordination bonds of calcium ions with polysaccharides; and the second through covalent bonds with 1,4-phenylenediboronic acid (PDBA). The films with Ca2+ ions exhibited a greater barrier to water vapor with a reduction of 44% of water permeability vapor and 26% greater tensile strength than the control film (without crosslinkers). Films crosslinked with PDBA presented 55-81% higher moisture contents, 85-125% greater permeability to water vapor and 67-150% larger elongations at break than the films with Ca2+ ions. Film biodegradability was demonstrated to be affected by the crosslinking density, with the higher the crosslinking density, the longer the time for the film to fully biodegrade. The results are promising and suggest that future research should focus on enhancing the properties of these films to expand the range of possible applications.

Polyphenols in Jabuticaba (Plinia spp.) Peel Flours: Extraction and Comparative Evaluation of FTIR and HPLC for Quantification of Individual Compounds.

Jabuticabas are wild fruits native to Brazil, and their peels, the main residue from jabuticaba processing, contain significant amounts of bioactive compounds, which are mostly phenolics. Conventional methods based on the estimation of total extractable phenolics (TEP-Folin-Ciocalteau) or total monomeric anthocyanins (TMA) have limitations and may not reflect the actual antioxidant potential of these peels. Analytical methods, such as high-performance liquid chromatography (HPLC), are more appropriate for the quantification of specific phenolics, and can be used as a reference for the construction of mathematical models in order to predict the amount of compounds using simple spectroscopic analysis, such as Fourier Transform Infrared Spectroscopy (FTIR). Therefore, the objectives of this study were (i) to evaluate the composition of specific polyphenols in flours prepared from jabuticaba peels and verify their correlation with TEP and TMA results from a previous study, and (ii) to employ FTIR coupled with chemometrics to predict the concentrations of these polyphenols in jabuticaba peel flours (JPFs) using HPLC as a reference method. Cyanidin-3-glucoside (C3G), ellagic acid (EA) and delphinidin-3-glucoside (D3G) were the main polyphenols found in the samples. The C3G contents ranged from 352.33 mg/100 g (S10) to 1008.73 mg/100 g (S22), with a strong correlation to TMA (r = 0.97; p = 0.00) and a moderate correlation to TEP (r = 0.45; p = 0.02). EA contents ranged from 163.65 mg/100 g (S23) to 334.69 mg/100 g (S11), with a moderate to strong correlation to TEP (r = 0.69; p = 0.00). The D3G values ranged from 94.99 mg/100 g (S10) to 203.36 mg/100 g (S5), with strong correlations to TMA (r = 0.91; p = 0.00) and C3G levels (r = 0.92; p = 0.00). The developed partial least squares-PLS models based on FTIR data provided satisfactory predictions of C3G and EA levels, reasonably matching those of HPLC.

Adsorption of Phenylalanine from Aqueous Solutions Using Activated Carbon from Sunflower Meal Functionalized with Sulfonic Groups.

The present work proposes the use of an agro-industrial residue from the sunflower crop as a feedstock to produce a low-cost adsorbent with a chemically modified surface bearing sulfonic groups. This modified low-cost adsorbent can be used for the removal of phenylalanine, and can also be applied in the process of obtaining a source of protein supplementation for patients with phenylketonuria. The functionalization of the adsorbent with sulfonic groups was adapted and presented advantages in terms of execution time, energy expenditure, number of reagents used and adsorbed amino acids. The produced adsorbent presented a surface area of 317.31 m2 g-1 with a predominance of micro- and mesopores, that influenced an approximate 30-fold reduction in adsorption equilibrium time. The optimization results indicated a higher adsorption capacity (39.64 mg g-1) in pH = 4; temperature of 25 °C and adsorbent dosage of 10 g L-1. The FTIR analyzes and the qualitative analysis of the elements present in the samples by EDS confirmed the introduction of sulfonic groups in the MPS500 coal. This work contributed to the understanding behind the adsorption of L-phenylalanine on charcoal surfaces functionalized with sulfonic groups, showing that they can be more selective for the adsorption of phenylalanine in a competitive system.

Potential Uses of Spent Coffee Grounds in the Food Industry.

Current estimates place the amount of spent coffee grounds annually generated worldwide in the 6 million ton figure, with the sources of spent coffee grounds being classified as domestic (i.e., household), commercial (i.e., coffee houses, cafeterias and restaurants), and industrial (i.e., soluble and instant coffee industries). The majority of the produced spent coffee grounds are currently being inappropriately destined for landfills or to a form of energy recovery (e.g., incineration) as a refuse-derived fuel. The disposal of spent coffee in landfills allows for its anaerobic degradation with consequent generation and emission of aggressive greenhouse gases such as methane and CO2, and energy recovery processes must be considered an end-of-life stage in the lifecycle of spent coffee grounds, as a way of delaying CO2 emissions and of avoiding emissions of toxic organic volatile compounds generated during combustion of this type of waste. Aside from these environmental issues, an aspect that should be considered is the inappropriate disposal of a product (SCG) that presents unique thermo-mechanical properties and textural characteristics and that is rich in a diversity of classes of compounds, such as polysaccharides, proteins, phenolics, lipids and alkaloids, which could be recovered and used in a diversity of applications, including food-related ones. Therefore, researchers worldwide are invested in studying a variety of possible applications for spent coffee grounds and products thereof, including (but not limited to) biofuels, catalysts, cosmetics, composite materials, feed and food ingredients. Hence, the aim of this essay was to present a comprehensive review of the recent literature on the proposals for utilization of spent coffee grounds in food-related applications, with focus on chemical composition of spent coffee, recovery of bioactive compounds, use as food ingredients and as components in the manufacture of composite materials that can be used in food applications, such as packaging.

Chemical Characterization of Coffee Husks, a By-Product of Coffea arabica Production.

Coffee husks are a major by-product of coffee production and are currently being underutilized. The aim of this work was to chemically characterize coffee husks to allow for an adequate evaluation of their potential for valorization. Blanched and non-blanched coffee husks were characterized for extractable and non-extractable phenolics, caffeine, trigonelline content, and for their polysaccharide and proximal composition. The total, soluble and insoluble fiber contents were determined, together with the husks' technological properties. Antioxidant activity and bioaccessibility of phenolic compounds of coffee husks were evaluated. Two types of husk were studied: one comprised mostly of outer skin and pulp (CH1); and other comprised mostly of parchment (CH2). Blanching had positive effects on non-extractable phenolics, chlorogenic acid and on the bioaccessibility of phenolics, promoting small reductions in extractable phenolics, protocathecuic acid, caffeine and trigonelline contents. Blanched CH1 presented more appropriate properties than CH2 for potential applications in food. It also presented better antioxidant, hydration, and oil holding properties than those of other agri-food by-products. Tentatively identified polysaccharides included galactomannans, arabinogalactans type II, pectin and cellulose.

Chemical Characterization and Bioaccessibility Assessment of Bioactive Compounds from Umbu (Spondias tuberosa A.) Fruit Peel and Pulp Flours.

Umbu, a common fruit from the northeastern region of Brazil, contains many bioactive compounds not yet exploited. Thus, this study evaluated the potential of pulps and peels of mature and semi-mature umbu as a source of bioactive compounds. Trigonelline contents ranged from 1.75 to 6.14 mg/100 g, values higher than those of many vegetables described in the literature, such as corn and barley. The contents of extractable and non-extractable phenolic compounds were also higher than those of other vegetables. Bioaccessibility of total extractable phenolics, flavonoids, and tannins was determined (15.67-37.73%, 31.87-39.10% and 18.81-114.27%, respectively). The constituent polysaccharides of the pulp and peel were tentatively chemically characterized as arabinoxylans, arabinogalactans, rhamnoarabinogalactans, xyloglucans, and pectin of the rhamnogalacturonan type. The technological potential of peel flours was evaluated. The maturation advancement showed no significant changes in the technological properties of the flours, except for color and water solubility index. Results indicated excellent prospects for future research on umbu pulps and peels as potential sources of natural bioactive compounds.

Profile of bioactive compounds in pequi (Caryocar brasilense Camb.) peel flours.

The bioactive compounds of pequi peel flours were characterized. Flavonoid contents ranged from 19.67 to 87.61 mg/100 g, high in comparison to many vegetables described in the literature. Gallic acid (11.52-418.67 mg/100 g), gallate ethyl (2026.75 - 5205.90 mg/100 g), ellagic acid (509.47 - 1630.66 mg/100 g), lutein (0.17-1.36 mg/100 g), ß-carotene (0.82 - 1.49 mg/100 g), and ß-cryptoxanthin (0.07 - 0.11 mg/100 g) were identified by HPLC, contributing to a greater valorization of the pequi peel flours. Phytochemical tests indicated the presence of hydrolyzable tannins and saponins. The detection of these compounds makes the product commercially attractive, in addition to generating value for an agro-industrial residue. The results obtained in this study confirm the multifunctional potential of pequi peel flour as a functional ingredient.

Polysaccharide-rich fraction of spent coffee grounds as promising biomaterial for films fabrication.

Spent coffee grounds are wastes generated annually worldwide in significantly large amounts in the soluble coffee industry and in household and commercial beverage preparation. Although spent coffee grounds are rich in several classes of compounds, predominantly polysaccharides, profitable applications have not yet been effectively implemented for such wastes. Thus, it was the aim of this study to verify the feasibility of producing biopolymeric films from the polysaccharide-rich fraction of spent coffee grounds, obtained by alkaline hydrogen peroxide treatment of the coffee waste. Produced films were characterized for their physicochemical, barrier and mechanical properties and these properties were comparable to those of similar polysaccharides films from the literature.

Attenuated Total Reflectance Fourier Transform Spectroscopy (ATR-FTIR) and chemometrics for discrimination of espresso coffees with different sensory characteristics.

Coffee cup quality, determined by the sensory attributes evaluated by professional tasters, is a decisive factor for evaluating coffee, with the "Specialty Coffee Association of America" (SCAA) classification being nowadays considered the most suitable. Panels of trained coffee tasters are used by the industry to describe and evaluate beverage quality, but those evaluations can be subjective and time demanding. Recent studies have demonstrated the potential of spectroscopy-based methods for establishing parameters of quality in the analysis of food products, including coffee. Thus, the aim of this study was to evaluate the potential of ATR-FTIR and chemometrics to discriminate espresso coffees with different sensory characteristics reported by a panel of coffee tasters. The results showed good consistency among coffee tasters. PLS-DA models based on spectroscopic data were able to classify samples according to sensory attributes, confirming the potential of FTIR and chemometrics in coffee quality evaluation.

Buriti (Mauritia flexuosa L. f.) fruit by-products flours: Evaluation as source of dietary fibers and natural antioxidants.

Buriti by-products flours were evaluated as sources of dietary fibers and natural antioxidants. All flours presented chemical characteristics that allowed classification as high dietary fiber powders. Presence of pectic polysaccharides, arabinoxylans and xyloglucans was inferred by the neutral monosaccharides profile. Peels and defatted pulp flours are highlighted as those with higher antioxidant potential (total extractable polyphenols and antioxidant activities by DPPH and FRAP) compared to endocarp and manually-produced bran flours. Carotenoids content were also higher in the peels flours. All produced flours showed expressive amounts of total non-extractable proanthocyanidins (NEPA). Buriti peels flours NEPA levels are among the highest values previously described in the literature. Blanching preserved the extractable polyphenols but not carotenoids or NEPA. Technological properties were influenced mainly by the size of the particles. Buriti by-products flours have potential to be used as sources of dietary fiber and natural antioxidants in food.

Mid infrared spectroscopy and chemometrics as tools for the classification of roasted coffees by cup quality.

Sensory (cup) analysis is a reliable methodology for green coffee quality evaluation, but faces barriers when applied to commercial roasted coffees due to lack of information on roasting conditions. The aim of this study was to examine the potential of mid-infrared spectroscopy for predicting cup quality of arabica coffees of different roasting degrees. PCA analysis showed separation of arabica and robusta. A two-level PLS-DA Hierarchical strategy was employed, with coffee being classified as high or low quality in the first level and then separated according to cup quality in the second level. Validation results showed that the second level models exhibited 100% sensitivity and specificity in the training sets. For the test set, sensitivity ranged from 67% (rio zona) to 100% (soft) while specificity ranged from 71% (rio) to 100% (rioysh, hard). Thus, the proposed method can be used for the quality evaluation of arabica coffees regardless of roasting conditions.

Mini-incubators improve the adventitious rooting performance of Corymbia and Eucalyptus microcuttings according to the environment in which they are conditioned.

We addressed a major challenge in the in vitro clonal propagation of Corymbia citriodora, Eucalyptus urophylla and E. benthamii by using an ex vitro adventitious rooting strategy in a mini-incubator. Mini-incubators were placed in four environments for rooting. A shade house with no fogging system and a greenhouse with no ventilation but with a fogging environment had the best performance in terms of rooting, root growth and survival of microcuttings. Daily recording of the temperature within each mini-incubator in each environment allowed the verification of negative correlations between the maximum average temperature and the survival, adventitious rooting and root growth. The ideal maximum air temperature for the efficient production of clonal plants was 28.4°C (± 5.5°C), and the minimum was 20.3°C (± 6.2°C). E. benthamii was more sensitive to higher temperatures than C. citriodora and E. urophylla. Nevertheless, placing mini-incubators in the shade house with no fogging system resulted in a stable and uniform performance among the three species, with 100.0% survival and 81.4% rooting. Histological sections of the adventitious roots revealed connection with the stem vascular cambium. Therefore, our experimental system demonstrated the potential of mini-incubators coupled with the proper environment to optimize the adventitious rooting performance of microcuttings.

Physicochemical characterization, antioxidant capacity, total phenolic and proanthocyanidin content of flours prepared from pequi (Caryocar brasilense Camb.) fruit by-products.

The potential of pequi by-products as substrates for the production of flours rich in antioxidant dietary fibers was evaluated. Dietary fiber contents ranged from 39.8 to 43.3g/100g with pectic polysaccharide fraction constituted of rhamnogalacturonans and hemicellulose fraction consisted of arabinogalactans, xylans and glucomannans. Total polyphenols, non-extractable proanthocyanidins (NEPA) and carotenoid contents of the flours were determined (respectively, 15.5-17.4g GAE/100g, 215.54-346.84mg/100g and 2116.52-3499.03µg/100g). The antioxidant capacities of pequi by-product flours (986.94-1154.42µM TE/g ABTS; 44.43-48.02g/g DPPH; and 3027.31-3216.27µmol Fe2SO4/g FRAP) were found to be exceptionally higher than those of fruits and fruits by-products reported in the literature. Exocarp removal promoted no significant changes in the technological properties of the flour, except for color. Results showed promising prospects for future exploitation of pequi peel as a potential source of dietary fiber and natural antioxidants.

Melanoidin Removal Mechanism in An Aqueous Adsorption System: An Equilibrium, Kinetic and Thermodynamic Study.

Melanoidins are colored products that can be found in food and drinks, formed by Maillard reactions. Sometimes these compounds are considered undesirable in certain food products, because they impart a brownish color and must be removed. An overview of recent patents related to melanoidin removal indicates that it can be performed by chemical/biological degradation or by adsorption processes. Therefore, in the present study, the adsorption mechanism for synthetic melanoidin removal from aqueous solutions was studied using different Raphanus sativus press-cake sorbents, with the precursor material being carbonized in a microwave oven, either with direct heating or after a chemical activation process with phosphoric acid, nitric acid or potassium hydroxide. Physical and chemical modifications were evaluated by FTIR, pHPZC, thermogravimetry and BET. The adsorption kinetics was better described by a pseudo-second order model for all activated carbons (ACs). Evaluation of the diffusion process showed dependence on the initial melanoidin concentration due to the wide range of sizes of the adsorbed molecules. The equilibrium data were best fitted by the Langmuir model for the acid-treated AC and by the Freundlich model for the base-treated and non-chemically treated ACs. Melanoidin adsorption was characterized as a spontaneous, favorable and endothermic process involving hydrogen bonds and π-π interactions between the adsorbents surfaces and the adsorbed molecules.

Development and analytical validation of a screening method for simultaneous detection of five adulterants in raw milk using mid-infrared spectroscopy and PLS-DA.

This paper proposed a new screening method for the simultaneous detection of five common adulterants in raw cow milk by using attenuated total reflectance (ATR) mid infrared spectroscopy and multivariate supervised classification (partial least squares discrimination analysis - PLSDA). The method was able to detect the presence of the adulterants water, starch, sodium citrate, formaldehyde and sucrose in milk samples containing from one up to five of these analytes, in the range of 0.5-10% w/v. A multivariate qualitative validation was performed, estimating specific figures of merit, such as false positive and false negative rates, selectivity, specificity and efficiency rates, accordance and concordance. The proposed method does not need any sample pretreatment, requires a small amount of sample (30 µL), is fast and simple, being suitable for the control of raw milk in a dairy industry or for the quality inspection of commercialized milk.

Fourier transform infrared spectroscopy and near infrared spectroscopy for the quantification of defects in roasted coffees.

The coffee strip-picking harvesting method, preferred in Brazil, results in high percentages of immature and overripe beans, as the fruits in a single tree branch do not reach ripeness at the same time. This practice, together with inappropriate processing and storage conditions, contribute to the production of high amounts of defective coffee beans in Brazil, which upon roasting will impart negative sensory aspects to the beverage. Therefore, the development of analytical methodologies that will enable the discrimination and quantification of defective and non-defective coffees after roasting is rather desirable. Given that infrared spectroscopy has been successfully applied to coffee analysis, the objective of this work was to evaluate and to compare the performances of Fourier transform infrared (FTIR) and near infrared (NIR) spectroscopies for the quantification of defective beans in roasted coffees. Defective and non-defective Arabica coffee beans were manually selected, roasted, ground and sieved. Mixtures of defective and non-defective roasted and ground coffees were produced and analyzed, with % defects ranging from 0% to 30%. FTIR and NIR spectra were recorded, respectively, within a range of 3100-800 cm(-1) and 1200-2400 nm and submitted to mathematical processing. Quantitative models were developed by partial least squares regression (PLSR). Excellent predictive results were obtained indicating that defective coffees could be satisfactorily quantified. The correlation coefficients and the root mean squared errors of validation for the FTIR and NIR models developed to quantify the amount of defective roasted coffees mixed with non-defective ones were, respectively, as high as 0.891 and as low as 0.032, and as high as 0.953 and as low as 0.026. A comparison between the two techniques indicated that NIR provided more robust models.

Application of elastic net and infrared spectroscopy in the discrimination between defective and non-defective roasted coffees.

The quality of the coffee beverage is negatively affected by the presence of defective coffee beans and its evaluation still relies on highly subjective sensory panels. To tackle the problem of subjectivity, sophisticated analytical techniques have been developed and have been shown capable of discriminating defective from non-defective coffees after roasting. However, these techniques are not adequate for routine analysis, for they are laborious (sample preparation) and time consuming, and reliable, simpler and faster techniques need to be developed for such purpose. Thus, it was the aim of this study to evaluate the performance of infrared spectroscopic methods, namely FTIR and NIR, for the discrimination of roasted defective and non-defective coffees, employing a novel statistical approach. The classification models based on Elastic Net exhibited high percentage of correct classification, and the discriminant infrared spectra variables extracted provided a good interpretation of the models. The discrimination of defective and non-defective beans was associated with main chemical descriptors of coffee, such as carbohydrates, proteins/amino acids, lipids, caffeine and chlorogenic acids.

Quantitative evaluation of multiple adulterants in roasted coffee by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and chemometrics.

The current study presents an application of Diffuse Reflectance Infrared Fourier Transform Spectroscopy for detection and quantification of fraudulent addition of commonly employed adulterants (spent coffee grounds, coffee husks, roasted corn and roasted barley) to roasted and ground coffee. Roasted coffee samples were intentionally blended with the adulterants (pure and mixed), with total adulteration levels ranging from 1% to 66% w/w. Partial Least Squares Regression (PLS) was used to relate the processed spectra to the mass fraction of adulterants and the model obtained provided reliable predictions of adulterations at levels as low as 1% w/w. A robust methodology was implemented that included the detection of outliers. High correlation coefficients (0.99 for calibration; 0.98 for validation) coupled with low degrees of error (1.23% for calibration; 2.67% for validation) confirmed that DRIFTS can be a valuable analytical tool for detection and quantification of adulteration in ground, roasted coffee.