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- Liquefaction optimization of peel of potato Solanum tuberosum L. var Monalisa.Publication . Dulyanska, Y.; Cruz-Lopes, Luísa; Esteves, Bruno; Guiné, Raquel P. F.; Ferreira, José; Domingos, IdalinaThe potato (Solanum tuberosum L.) is native to South America, in the Andes Mountains where it was consumed by native populations 1. According to the Food and Agriculture Organization of the United Nations (FAO), there has been a large increase in potato production in Latin America and Asia, especially China, that in 2018 was the largest producer followed by India. These two countries represented almost a third of the potatoes consumed in the world 1. In Portugal, the most widely planted potato is Solanum tuberosum L. var Monalisa, that is used by potatoes’ processing industry, generating tons of potato peel waste annually. The waste from the potato industry accounts for approximately 27% of total production. The objective of this work was to evaluate the potentiality of potato industrial residues to be liquefied by polyhydric alcohols and the chemical transformations observed in this process with subsequent use to produce polyurethane foams. Potato peel waste (PPW) was dried in an oven, crushed in the Retsch SMI mill and sifted in a vibratory sieve model Retsh 5657 HAAN 1 for 30 minutes. The fractions obtained were > 35 mesh, 35-40 mesh (0.500-0.425 mm); 40-60 mesh (0.425-0.250 mm); 60-80 mesh (0.250-0.180 mm) and 80 mesh (< 0.180 mm). The liquefactions were made in an oil-heated double-shirt reactor with a mixture of glycerol and ethylene glycol 1:1, catalyzed by 3% sulfuric acid. The effect of particle size (<80 mesh at >35 mesh) temperatures (140 oC - 180 oC), ratio material/solvent (1:5, 1:7, 1:10, 1:12) and times (15-60 min) were studied. The Fourier Transform Infrared Spectroscopy by Attenuated total reflection (FTIR-ATR) was used to evaluate the functional groups present in the original sample of PPW, in the liquefied sample and in the solid residue obtained. Liquefaction percentage with increased temperature, time, material/solvent ratio and granulometry is presented (Figure 1). Results show that liquefaction performed at 180 oC with a 1:10 material/solvent ratio, increases along time, reaching a maximum at 60 min. Similarly, liquefactions made during 60 min with a 1:10 material/solvent ratio show that there is an increase in liquefaction yield with the increase in temperature until 180 oC. A higher temperature could increase the liquefaction yield but would lead to a higher energy consumption in the process. There seems to be no significative advantage in increasing material/solvent ratio above 1:7, although the liquefaction yield increases for higher ratios. Granulometry testing shows that the smaller the particle the best is the liquefaction percentage. It was concluded that the best liquefaction yield, of approximately 90%, was obtained with a temperature of 180 oC, for 60 min and particle size <80 mesh for PPW. This material has good properties to be converted in a liquid mixture that can be used later, on the production of polyurethane foams (Figure 1). The PPW spectrum exhibits the common bands for agricultural materials (Figure 2). The main differences between the solid material and the liquefied material is the high OH band with a peak at around 3300 cm-1 for both the original material and the liquefied, while the peak for the solid residue is at higher wavenumbers. The liquefied sample has a considerable higher OH peak than the solid samples, which is probably due to the polyalcohols used for the liquefaction. The band at 1740 cm-1 (non-conjugated C=O bonds) is higher in the solid residue spectrum and smaller in the liquefied material. Similarly Jin et al. 2 observed the absence of C=O groups after the liquefaction of enzymatic hydrolysis lignin. The highest peak in the original and in the liquefied material spectra is the peak at 1100 cm-1 which has been attributed to C–O stretching vibrations in carbohydrates. This is in accordance with several chemical compositions reported for PPW 1. In the liquefied material a new peak appears at around 860 cm-1, which can be due to stretching in the pyranose ring as stated before 3.
- Maritime pine land use environmental impact evolution in the context of life cycle assessmentPublication . Ferreira, José; Esteves, Bruno; Cruz-Lopes, Luísa; Domingos, IdalinaBetween 2005 and 2015, the forest area occupied by maritime pine trees in Continental Portugal decreased by about 10.6%, and the existing volume decreased by about 18.4%mainly due to fires and pests (e.g., nematode) that occurred during this period. The purpose of this study was to study the evolution of the land use environmental impact of 1m3 of maritime pine, standing in Portuguese forest, during that period using the model by Milà i Canals based on soil organic matter measured by soil organic carbon. Results show that the land use impact category increased from 16,812 kg C deficit in 2005 to 18,423kg C deficit in 2015. Land transformation to forest roads is the main contribution for land use impact representing 54%of the total value followed by land occupation as forest that represents about 40%.
- Extraction of Phenolic Compounds from Cherry Seeds: A Preliminary StudyPublication . Dulyanska, Yuliya; Cruz-Lopes, Luísa; Esteves, Bruno; Ferreira, José; Domingos, Idalina; Lima, Maria João; Correia, Paula; Ferreira, Manuela; Fragata, Anabela; Barroca, Maria João; Moreira da Silva, Aida; Guiné, Raquel P. F.Agri-food waste has proved to be a valuable bioresource that can be used to obtain a variety of valuable materials, ingredients and chemicals. The optimum conditions for extracting bioactive compounds from sweet cherry seeds (SCS) with different solvents and temperatures were tested in this work. The choice criteria were based on the most efficient extracting capacity while looking for cleaner techniques with lower health or environmental impacts. Some extracting solvents (methanol, ethanol and water) were tested in different combinations and temperatures. The obtained extracts were evaluated for total phenolic compounds and some families of phenolics as well, using spectrophotometric methods. The results obtained showed that the highest extraction of total phenolic compounds was at 70 °C with 60:40 ratio water:ethanol (2.65 mg GAE/g), while maximum flavonoids were obtained at 80 °C and 50% ethanolic aqueous solution (7.26 mg QE/g). The highest value for ortho-diphenols was 21.47 mg GAE/g for 50 °C and water:ethanol 50:50 solution. The highest proanthocyanidins and flavonols were obtained for 50:50 solution at 70 °C (6.43 mg CE/g and 3.88 mg QE/g, respectively), while the same solution at 80 °C allowed obtaining maximum phenolic acids (1.68 mg CAE/g). The extraction of anthocyanins was found to vary significantly with concentration and temperature, being highest in the range 35–40 °C, when using an 80:20 water:ethanol solution. Hierarchical clustering showed three clusters, while factor analysis resulted in two factors and four groups of samples. In conclusion, it was found that extracts obtained from sweet cherry seeds have relevant bioactive compounds with applications in the food, pharmaceutical or cosmetic industries.
- Chemical composition and study on liquefaction optimization of chestnut shellsPublication . Cruz-Lopes, Luísa; Domingos, Idalina; Ferreira, José; Esteves, BrunoChestnut shell (CS) is a by-product of some food sector companies. The aim of this study was to test the suitability of this material to be liquefied with polyalco- hols, optimizing the main liquefaction parameters in order to use the liquefied material for the production of high added value products. As the chemical composition of the fruit shell depends on the variation in the soil, cli- mate, and species, the chemical composition of CS was determined. Liquefaction was performed with 50:50 ethy- leneglycol:glycerol catalyzed by sulfuric acid. Different tests were carried out and several parameters were tested: par- ticle size, temperature 130–190°C, and time 15–120min. Chemical composition of CSs was determined. The main component found was lignin with 47.0%, which is higher than α-cellulose with around 20.5%, hemicelluloses 15.2%, and extractives in ethanol 8.8%. For the tested parameters, the best liquefaction yield was obtained at 190°C, 30 min, and a 40–60 particle size.
- The impact of extraction temperature and solution concentration on the antioxidant activity of sweet cherry seeds’ extractsPublication . Dulyanska, Y.; Cunha, Margarida; Lima, M. J.; Correia, Paula; Ferreira, Manuela; Fragata, Anabela; Cardoso, Ana Paula; Barroca, Maria João; Silva, A.; Cruz-Lopes, Luísa; Esteves, Bruno; Ferreira, José; Domingos, Idalina; Guiné, Raquel P. F.Sweet cherry seeds, a valuable lignin-cellulose raw material for the production of polyurethane foams 1, are also a significant source of different phenolic compounds 2 and can be a good source of natural antioxidants, which can play an important role in preventing the formation of free radicals and protection against degenerative diseases. Considering sustainability, the main objective of this project was the use of cherry by-products (seeds) to produce extracts rich in antioxidant compounds. In this work, the seed extracts were obtained with the addition of different combinations of ethanolic solution (water:ethanol ratios - 50:50; 60:40; 80:20; 100:0 v:v) and at different temperatures (35, 50, 70 and 80 °C), all under magnetic stirring for 40 minutes. Then, the antioxidant activity of the extracts was evaluated through spectrophotometric methods, using the DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2′-azino-di-(3-ethylbenzthiazoline sulfonic acid)) radicals, and also the Ferric Reducing Antioxidant Power Assay (FRAP). All measurements were replicated at least in triplicates and were expressed as mg Trolox equivalents per gram (mg TE/g). Statistical analysis was performed using the JAVA software. ANOVA tests show that there is a statistically significant effect of temperature, water percentage and temperature on the antioxidant activity evaluated by the three methods used (p> 0.001 in all tests). The percentage of water is the variable that most contributes to this effect. Individual Post Hoc comparisons show, for all tests, that in general the temperatures induce differences in antioxidant activity, except 70 °C and 80 °C in DPPH and FRAP, and 80 °C and 50 °C in ABTS. Regarding the percentage of water, it was found that all samples are different from each other, except the FRAP, in which no significant differences between 50 and 60% of water were found. In conclusion, no major differences between the ABTS, DPPH and FRAP methods were found. Temperature and percentage of water have a significant effect on the concentration of antioxidant activity in all methods. In that way, the cherry pit is a good by-product to produce extracts with high content of antioxidant activity, being that the 70° C with 50:50 and 60:40 water:ethanol solutions are the most favorable conditions to potentiate the antioxidant activity.
- Effect of heat treatment on shore-D hardness of some wood speciesPublication . Esteves, Bruno; Sahin, Sirri; Ayata, Ümit; Domingos, Idalina; Ferreira, José; Gürleyen, LeventHardness is an important wood property for several applications. Typically, it is necessary to use traditional methods, such as a universal test machine, to determine a wood’s hardness value. This work reports the hardness of some wood species before and after heat treatment (ThermoWood method) using the Shore-D hardness method. The Shore- D hardness value of untreated wood ranged between 35.3 for Limba wood and 77.2 for Santos wood. With heat treatment, hardness decreased, and the decrease was greater for samples that underwent harsher treatment (2 h at 212 °C). The decrease of hardness was highest for Sipo wood (14%) and the lowest for Afrormosia wood (2.5%). Analysis of variance tests showed that there was a significant difference between wood species, heat treatment, and the interaction between both variables at the chosen level of significance (P ≤ 0.05). Results showed that Shore-D hardness could be used to measure hardness directly in a production line or in small wood companies without using a universal test machine.
- Chemical Composition and Optimization of Liquefaction Parameters of Cytisus scoparius (Broom)Publication . Cruz-Lopes, Luísa; Almeida, Daniela; Dulyanska, Yuliya; Domingos, Idalina; Ferreira, José; Fragata, Anabela; Esteves, BrunoInvasive plants spread in such a way that they are threats to native species and to biodiversity. In this context, this work aims to determine possible valorizations of Scotch Broom Cytisus scoparius (L.) Link. This species harvested in the Viseu region was used in the present study. The eco-valorization of these renewable resources was made by conversion into liquid mixtures that can later be used in the manufacture of valuable products. For a better understanding of the results obtained, a chemical characterization of the Cytisus scoparius branches (CsB) was made. The ash content, extractives in dichloromethane, ethanol and water, lignin, cellulose and hemicellulose of the initial material were determined. Liquefaction was made in a reactor with different granulometry, temperatures and time. Results show that Broom is mainly composed of cellulose (36.1%), hemicelluloses (18.6%) and lignin (14.6%) with extractives mainly soluble in ethanol, followed by water and a small amount in dichloromethane. Ashes were around 0.69%, mainly composed of potassium and calcium. Generally, smaller size, higher solvent ratio, higher temperature and higher time of liquefaction lead to higher liquefaction. The highest percentage of liquefaction was 95% which is better than most of the lignocellulosic materials tested before.
- Changes in the content and composition of the extractives in thermally modified tropical hardwoodsPublication . Esteves, Bruno; Ayata, Umit; Cruz-Lopes, Luísa; Brás, Isabel; Ferreira, José; Domingos, IdalinaChemical composition of wood is known to change during thermal treatments. Two species grown in Turkey, afrormosia (Pericopsis elata) and duka (Tapirira guianensis) were heat treated according to Thermowood® method. Lignin, cellulose, hemicelluloses and extractives in dichloromethane, ethanol and water were determined. Wood extracts were analysed by gas chromatography with mass detection and existing compounds were identified by NIST17 database. Results show that hemicelluloses and cellulose content decreased for both heat-treated woods along the treatment while lignin percentage increased. The analysis of extractives has shown several compounds normally associated to lignin thermal degradation that increased along the treatment. At the same time several compounds associated to carbohydrate thermal degradation were found in all the extracts for both heat-treated woods. These founding have allowed the understanding of the degradation pattern of wood during thermal modification. There was not much difference between afrormosia and duka woods structural compounds behaviour along thermal modification. However, the variation of the amount of extractives along the treatment depended on the species.
- Particleboard Production from Paulownia tomentosa (Thunb.) Steud. Grown in Portugal.Publication . Esteves, Bruno; Aires, Pedro; Sen, U; Gomes, Maria da Glória; Guiné, Raquel; Domingos, Idalina; Ferreira, José; Viana, Helder Filipe dos Santos; Lopes, Luísa P. Cruz
- Effects of artificial weathering on the surface properties of coated radiata pinePublication . Sahin, Sirri; Esteves, Bruno; Can, Ahmet; Sivrikaya, Hüseyin; Domingos, Idalina; Ferreira, José; Ayata, ÜmitRadiata pine boards were coated with two different methods A and B both beginning with a hydro primer and finishing with a mat oil but method A using an acrylic high gloss coating and method B three layers of an acrylic sealer in between. The samples were subjected to aging processes for 144 h, 288 h, and 432 h by using UV-A 340 nm lamps. The CIE L*a*b* and CIE L*C*H* coordinates were determined (L*, a*, b*, C*, ho *, ΔE*), gloss (perpendicular ( ) and parallel (//) to the grain at 20°, 60°, and 85° angles) and surface adhesion strength via the pull-off method were tested before and after weathering. Results have shown that lightness (L*), decreases with weathering for both varnish applications with a higher decrease for the B coating system. Redness increased for both applications with no significant differences. At the same time there was a yellowing of the samples along the weathering period. Parallel and perpendicular gloss decreased for 20º and 60º angles while it increased for 85º angle. The adhesion strength of method A was higher and its decrease with weathering was smaller than for method B. Both varnish applications have proven to confer some protection against wood discoloration, but method A showed the best results and is therefore the best method to be used by radiata pine.