Industrial wood modification by heat treatments

216 p.El objetivo principal de este trabajo de tesis fue el de mejorar las propiedades naturales de la madera solida modificándola químicamente por medio de calor a altas temperaturas. La tecnología de termo-tratado ha despertado un gran interés a nivel industrial en países como Finlandia, Alemania y Holanda y a pequeña escala en España. El proceso se ha desarrollado en cámaras de secado bajo atmósfera inerte o bajo atmosfera saturada de vapor de agua, en donde se lleva a cabo un secado preliminar a 100 ºC para la a continuación incrementar la temperatura lentamente bajo atmósfera modificada hasta alcanzar la temperatura máxima de modificación o temperatura de termo-tratado, que por lo general se encuentra en un rango entre 170-210 ºC. Las especies que se han termo-tratan son especies de bajo valor comercial las cuales han mejorado su estabilidad dimensional, durabilidad biológica además de alterar su carácter hidrofóbico, incrementando así su valor comercial y el rango de aplicaciones. En la presente tesis doctoral se analizan muestras de diferentes especies forestales usadas en la industria española y de otros países, obteniendo un estudio completo de los cambios que ocurren en el material a nivel químico, físico, mecánico y biológico, además de las interacciones con factores abióticos y superficiales, analizando el ciclo de vida de sus productos y llegando a dar un posible uso para los residuos generados durante el proceso. En general, las propiedades naturales han sido mejoradas y el material es adecuado para su uso en exteriores sin contacto directo con el suelo, para uso interior y bajo condiciones de elevada humedad, además la modificación no repercute de forma negativa cuando se le aplican en la superficie productos de revestimiento, aumentando su vida útil con respecto a el material sin modificar

Industrial wood modification by heat treatments

216 p.El objetivo principal de este trabajo de tesis fue el de mejorar las propiedades naturales de la madera solida modificándola químicamente por medio de calor a altas temperaturas. La tecnología de termo-tratado ha despertado un gran interés a nivel industrial en países como Finlandia, Alemania y Holanda y a pequeña escala en España. El proceso se ha desarrollado en cámaras de secado bajo atmósfera inerte o bajo atmosfera saturada de vapor de agua, en donde se lleva a cabo un secado preliminar a 100 ºC para la a continuación incrementar la temperatura lentamente bajo atmósfera modificada hasta alcanzar la temperatura máxima de modificación o temperatura de termo-tratado, que por lo general se encuentra en un rango entre 170-210 ºC. Las especies que se han termo-tratan son especies de bajo valor comercial las cuales han mejorado su estabilidad dimensional, durabilidad biológica además de alterar su carácter hidrofóbico, incrementando así su valor comercial y el rango de aplicaciones. En la presente tesis doctoral se analizan muestras de diferentes especies forestales usadas en la industria española y de otros países, obteniendo un estudio completo de los cambios que ocurren en el material a nivel químico, físico, mecánico y biológico, además de las interacciones con factores abióticos y superficiales, analizando el ciclo de vida de sus productos y llegando a dar un posible uso para los residuos generados durante el proceso. En general, las propiedades naturales han sido mejoradas y el material es adecuado para su uso en exteriores sin contacto directo con el suelo, para uso interior y bajo condiciones de elevada humedad, además la modificación no repercute de forma negativa cuando se le aplican en la superficie productos de revestimiento, aumentando su vida útil con respecto a el material sin modificar

One-Step Lignin Refining Process: The Influence of the Solvent Nature on the Properties and Quality of Fractions

Heterogeneity of kraft lignin is one of the main limitations for the development of high-performance applications. Therefore, refining lignin using organic solvents is a promising strategy to obtain homogenous fractions with controlled quality in terms of structure and properties. In this work, one-step refining processes for hardwood kraft lignin using nine organic solvents of different chemical nature and polarity were carried out with the aim of investigating and understanding the effect of the type of organic solvent on the quality of resulting fractions. Structural features of both soluble and insoluble lignin fractions were assessed by GPC, Py-GC-MS, and FTIR linked to PCA analysis. Moreover, functional properties such as physical appearance, hygroscopicity, antioxidant capacity, and thermal properties were evaluated. The results evidenced the relationship between the nature and polarity of the solvents and the properties of the obtained soluble and insoluble fractions.This research was funded by the European Commission’s funding of the InnoRenew project (Grant Agreement #739574 under the Horizon 2020 WIDESPREAD-2-Teaming program) and the Republic of Slovenia (investment funding from the Republic of Slovenia and the European Regional Development Fund). O.G. is grateful for the financial support received from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Action for development of the BIO4CARE project (Grant Number #101023389). R.H. received funding from the Spanish Ministry of Science and Innovation and the University of the Basque Country UPV/EHU (POSTDOC: IJC2020-043740-I)

Fractionation of lignin using organic solvents: A combined experimental and theoretical study

Refining of industrial lignin to produce homogeneous fractions is essential for high-value applications. However, the understanding of key interactions between a variety of solvents with lignin polymer is still uncertain. In this work, single-step fractionation of industrial hardwood kraft lignin (HKL) using organic solvents of different polarities - ethanol, acetone, diethyl ether and hexane - was investigated by combining an experimental and theoretical approach. Experimental results revealed that higher polarity solvents (ethanol and acetone) exhibited higher solubility yield compared to moderate and low polarity solvents. The chemical differences between lignin fractions were proven by pyrolysis gas chromatography mass spectrometry and near infrared spectroscopy. Density functional theory (DFT) results indicated that ethanol presented higher interaction energy followed by acetone, diethyl ether and hexane, which was consistent with experimental findings. Hydrogen bond and non-covalent interaction results from DFT demonstrated that the predominant interaction was found for high polarity of ethanol over other solvents and gamma-OH in the lignin model is the key site.The authors gratefully acknowledge the European Commission for funding the InnoRenew project [Grant Agreement #739574] under the Horizon2020 Widespread-Teaming program, the Republic of Slovenia (investment funding from the Republic of Slovenia and the European Union European Regional Development Funds) and infrastructural ARRS program IO-0035. Additionally, O.G. is grateful for the financial support received from the University of the Basque Country (post-doctoral grant DOCREC18/29) and R.H. acknowledges to the Department of Education of the Basque Government (post-doctoral grant INGVTCL4-D00112-7)

Characterization of the Compounds Released in the Gaseous Waste Stream during the Slow Pyrolysis of Hemp (Cannabis sativa L.)

This study aims to characterize and valorize hemp residual biomass by a slow pyrolysis process. The volatile by-products of hemp carbonization were characterized by several methods (TGA, UV-VIS, TLC, Flash Prep-LC, UHPLC, QTOF-MS) to understand the pyrolysis reaction mechanisms and to identify the chemical products produced during the process. The obtained carbon yield was 29%, generating a gaseous stream composed of phenols and furans which was collected in four temperature ranges (F1 at 20–150 °C, F2 at 150–250 °C, F3 at 250–400 °C and F4 at 400–1000 °C). The obtained liquid fractions were separated into subfractions by flash chromatography. The total phenolic content (TPC) varied depending on the fraction but did not correlate with an increase in temperature or with a decrease in pH value. Compounds present in fractions F1, F3 and F4, being mainly phenolic molecules such as guaiacyl or syringyl derivatives issued from the lignin degradation, exhibit antioxidant capacity. The temperature of the pyrolysis process was positively correlated with detectable phenolic content, which can be explained by the decomposition order of the hemp chemical constituents. A detailed understanding of the chemical composition of pyrolysis products of hemp residuals allows for an assessment of their potential valorization routes and the future economic potential of underutilized biomass.This research was funded by the European Commission for funding the InnoRenew project (Grant agreement #739574 under the Horizon 2020 WIDESPREAD-2-Teaming program) and the Republic of Slovenia (investment funding from the Republic of Slovenia and the European Regional Development Fund), the European Union’s Horizon 2020 research and innovation programme under the H2020 Marie Skłodowska-Curie Actions (Grant Number 898179). Kristine Meile received funding from the ERDF Project No. 1.1.1.2/VIAA/3/19/388 “A biorefinery approach to the separation and application of the products of lignocellulose pyrolysis”. Rene Herrera received funding from Spanish Ministry of Science and Innovation and the University of the Basque Country UPV/EHU (POSTDOC: IJC2020-043740-I)

Recovery of Bioactive Compounds from Hazelnuts and Walnuts Shells: Quantitative–Qualitative Analysis and Chromatographic Purification

Hazelnut (HS) and walnut (WS) shells, an abundant by-product of the processing industries of these edible nuts, are traditionally considered as a low-value waste. However, they are a source of valuable compounds with an interesting chemical profile for the chemical and pharmaceutical sectors. In this study, the lipophilic and hydrophilic extracts present in HS and WS were quantified and identified, then the polar fractions were chromatographically separated, and their antioxidant capacity was studied. The experimental work includes the isolation of crude lipophilic and hydrophilic extracts by an accelerated extraction process, chromatographic analysis (gas chromatography-flame ionization (GC-FID), GC-mass spectroscopy (GC-MS), high-performance size-exclusion chromatography (HPSEC), thin-layer chromatography (TLC)), and quantification of the components. In addition, a thorough compositional characterization of the subgroups obtained by flash chromatography and their antioxidant capacity was carried out. The gravimetric concentrations showed different lipophilic/hydrophilic ratios (0.70 for HS and 0.23 for WS), indicating a higher proportion of polar compounds in WS than in HS. Moreover, the lipophilic extracts were principally composed of short-chain fatty acids (stearic, palmitic, and oleic acid), triglycerides, and sterols. The polar fractions were screened by thin-layer chromatography and then separated by flash chromatography, obtaining fractions free of fatty acids and sugar derivatives (97:3 in HS and 95:5 in WS), and mixtures richer in phenolic compounds and flavonoids such as guaiacyl derivatives, quercetin, pinobanksin, and catechin. The most polar fractions presented a higher antioxidant capacity than that of the crude extracts.This work was supported by the Basque Government (Grupos Consolidados IT-1264-19). U.G.-G. was supported by Fundación Biofísica Bizkaia. A.B.-V. was supported by Programa de especialización de Personal Investigador Doctor en la UPV/EHU (2019) 2019–2020. S.J.-B. and A.L.-S. were supported by a grant PIF (2017–2018) and (2019–2020), Gobierno Vasco, respectively. A.L.-S. was partially supported by Fundación Biofísica Bizkaia

Nectandra grandiflora By-Products Obtained by Alternative Extraction Methods as a Source of Phytochemicals with Antioxidant and Antifungal Properties

Nectandra grandiflora Nees (Lauraceae) is a Brazilian native tree recognized by its durable wood and the antioxidant compounds of its leaves. Taking into account that the forest industry offers the opportunity to recover active compounds from its residues and by-products, this study identifies and underlines the potential of natural products from Nectandra grandiflora that can add value to the forest exploitation. This study shows the effect of three different extraction methods: conventional (CE), ultrasound-assisted (UAE) and microwave-assisted (MAE) on Nectandra grandiflora leaf extracts (NGLE) chemical yields, phenolic and flavonoid composition, physical characteristics as well as antioxidant and antifungal properties. Results indicate that CE achieves the highest extraction phytochemical yield (22.16%), but with similar chemical composition to that obtained by UAE and MAE. Moreover, CE also provided a superior thermal stability of NGLE. The phenolic composition of NGLE was confirmed firstly, by colorimetric assays and infrared spectra and then by chromatographic analysis, in which quercetin-3-O-rhamnoside was detected as the major compound (57.75–65.14%). Furthermore, the antioxidant capacity of the NGLE was not altered by the extraction methods, finding a high radical inhibition in all NGLE (>80% at 2 mg/mL). Regarding the antifungal activity, there was observed that NGLE possess effective bioactive compounds, which inhibit the Aspergillus niger growth.This research was financially supported by the Department of Education of Basque Government (IT1008-16) and by Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq process 454447/2014-0). Authors would like to thanks the CNPq for research grants received by Berta Maria Heinzmann, Ph.D. scholarship (process 203796/2014-4) granted to Daniela Thomas da Silva and the Basque Government for scholarship of young researchers training granted to Rene Herrera

Hydrophobization and Photo-Stabilization of Radiata Pinewood: The Effect of the Esterification on Thermal and Mechanical Properties

Wood protection through chemical modification has received increasing interest over the last decades due to the environmental issues related to conventional biocides or protecting products. Consequently, a wide range of new treatments are developed in laboratories, which are later scaled up in the industrial environment. The main goal of modifying wood for indoor–outdoor application is to change its hydrophilic character, which in turn improves the intrinsic properties of the material and its durability against external factors. Wood can be esterified through its hydroxyl groups to obtain a hydrophobic and photo-stable material. Chemical modifications of Pinus radiata D. Don wood using hexanoyl chloride (P6), dodecanoyl chloride (P12), and stearoyl chloride (P18) were carried out at different concentrations. Esterification was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) technique combined with a discriminatory analysis. Weight percent gain was associated with the number of carbons of the aliphatic chain of the fatty acid (P6 > P12 > P18). Moreover, an increase of wood density as a consequence of modification treatments was observed. A substantial improvement of the hydrophobicity of wood was observed by dynamic contact angle measurements. In addition, the effect of ultraviolet (UV) radiation on color changes was reduced with the treatments. Furthermore, the P6 treatment presented acceptable values of modulus of elasticity (MOE) and modulus of rupture (MOR), being suitable for similar mechanical uses as non-treated pinewood. However, only treatments P12 and P18 enhanced thermal resistance of the pinewood in an oxidative atmosphere.This research was funded by the Basque Government, grant number IT1008-16 and the APC was funded by the Basque Government, grant number IT1008-16. The author gratefully acknowledges the European Commission for funding the InnoRenew project [Grant Agreement # 739574] under the Horizon2020 Widespread-Teaming program, the Republic of Slovenia (investment funding of the Republic of Slovenia and the European Union European Regional Development Fund) and infrastructural ARRS program IO-0035. Part of this work was conducted during the project Multi-spec (BI-IT/18-20-007) funded by ARRS. RH is grateful to the Department of Education of the Basque Government (post-doc INGVTCL4-D00112-7) and the University of the Basque Country UPV/EHU

Assessment of in vivo fetal growth and placental vascular function in a novel intrauterine growth restriction model of progressive uterine artery occlusion in guinea pigs

Intra-uterine growth restriction (IUGR) is associated with short and long-term metabolic and cardiovascular alterations. Mice and rats have been extensively used to study the effects of IUGR, but there are notable differences in fetal and placental physiology relative to those of humans that argue for alternative animal models. This study proposes that gradual occlusion of uterine arteries from mid-gestation in pregnant guinea pigs produces a novel model to better assess human IUGR. Fetal biometry and in vivo placental vascular function were followed by sonography and Doppler of control pregnant guinea pigs and sows submitted to surgical placement of ameroid constrictors in both uterine arteries (IUGR) at mid-gestation (35 days). The ameroid constrictors induced a reduction in the fetal abdominal circumference growth rate (0.205 cm day-1) compared to control (0.241 cm day-1, P \u3c 0.001) without affecting biparietal diameter growth. Umbilical artery pulsatility and resistance indexes at 10 and 20 days after surgery were significantly higher in IUGR animals than controls (P \u3c 0.01). These effects were associated with a decrease in the relative luminal area of placental chorionic arteries (21.3 ± 2.2% vs. 33.2 ± 2.7%, P \u3c 0.01) in IUGR sows at near term. Uterine artery intervention reduced fetal (∼30%), placental (∼20%) and liver (∼50%) weights (P \u3c 0.05), with an increased brain to liver ratio (P \u3c 0.001) relative to the control group. These data demonstrate that the ameroid constrictor implantations in uterine arteries in pregnant guinea pigs lead to placental vascular dysfunction and altered fetal growth that induces asymmetric IUGR

Assessment of in vivo fetal growth and placental vascular function in a novel intrauterine growth restriction model of progressive uterine artery occlusion in guinea pigs

Intra-uterine growth restriction (IUGR) is associated with short and long-term metabolic and cardiovascular alterations. Mice and rats have been extensively used to study the effects of IUGR, but there are notable differences in fetal and placental physiology relative to those of humans that argue for alternative animal models. This study proposes that gradual occlusion of uterine arteries from mid-gestation in pregnant guinea pigs produces a novel model to better assess human IUGR. Fetal biometry and in vivo placental vascular function were followed by sonography and Doppler of control pregnant guinea pigs and sows submitted to surgical placement of ameroid constrictors in both uterine arteries (IUGR) at mid-gestation (35 days). The ameroid constrictors induced a reduction in the fetal abdominal circumference growth rate (0.205 cm day-1) compared to control (0.241 cm day-1, P \u3c 0.001) without affecting biparietal diameter growth. Umbilical artery pulsatility and resistance indexes at 10 and 20 days after surgery were significantly higher in IUGR animals than controls (P \u3c 0.01). These effects were associated with a decrease in the relative luminal area of placental chorionic arteries (21.3 ± 2.2% vs. 33.2 ± 2.7%, P \u3c 0.01) in IUGR sows at near term. Uterine artery intervention reduced fetal (∼30%), placental (∼20%) and liver (∼50%) weights (P \u3c 0.05), with an increased brain to liver ratio (P \u3c 0.001) relative to the control group. These data demonstrate that the ameroid constrictor implantations in uterine arteries in pregnant guinea pigs lead to placental vascular dysfunction and altered fetal growth that induces asymmetric IUGR