New products from lignin.

214 p.La revalorización de la lignina se ve restringida por la heterogeneidad de su estructura, la cual varía en gran medida dependiendo de su origen lignocelulósico y el proceso de extracción del que se ha obtenido. Sin embargo, su gran disponibilidad, bajo precio y propiedades han atraído una gran atención, convirtiendo su valorización en un gran desafío. Además, la utilización de este producto natural renovable podría tener importantes beneficios económicos y ambientales. Por ello, en este trabajo, ligninas de diferentes orígenes han sido estructuralmente y térmicamente analizadas. Por otro lado, se han modificado químicamente a fin de cambiar sus propiedades y ampliar su rango de aplicación. Los nuevos productos sintetizados a partir de las diferentes ligninas han sido usados como aditivo para el poli(ácido láctico) y como agente protector en chapas de madera.CICnanoGUNE: nanoscience cooperative research cente

Características del cáncer de colon detectado en una segunda ronda de cribado tras una primera ronda negativa

85 p.El objetivo de esta tesis es determinar la incidencia y características del cáncer colorrectal en la segunda ronda de cribado mediante sangre oculta en las heces inmunológico (SOHi) tras una primera ronda negativa.Hipótesis: el cáncer de colon detectado en una segunda ronda de cribado tras un primer resultado negativo es muy poco frecuente y el estadio menos avanzado.Conclusión: en este trabajo se comprueba como la incidencia de CCR disminuye en una segunda ronda de cribado tras un primer resultado negativo. Los valores cuantificados del test son más bajos en la segunda ronda. No se observan diferencias en el estadio. Sí se observan diferencias en la localización, siendo con más frecuencia proximales los detectados en la segunda rond

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)

Surface chemistry and bioactivity of colloidal particles from industrial kraft lignins

The morphology control of lignin through particle size reduction to nanoscale seems to be a suitable conversion technology to overcome the intrinsic limitations of its native form to develop a wide range of biomaterials with high performance. Colloidal lignin particles (CLPs) in the range of 150–200 nm were synthesised from hardwood and softwood kraft lignins by the solvent shifting method. The initial molecular features of kraft lignins were evaluated in terms of purity, molecular weight distribution, and chemical functionalities. The impact of the lignin source and structure on the morphology, size distribution, and surface chemistry of CLPs was evaluated by particle size analyser, SEM, TEM and 1H NMR. The results evidenced the influence of the botanical origin on the morphology and surface chemistry of particles. Furthermore, the antioxidant properties and cytotoxicity of lignins and corresponding CLPs, towards lung fibroblast cells were compared. CLPs from hardwood kraft lignins exhibited higher antioxidant power against DPPH free radical and a higher cytotoxic effect (IC30 = 67–70 μg/mL) against lung fibroblast when compared to CLPs from softwood kraft lignin (IC30 = ~91 μg/mL). However, the cytotoxicity of these biomaterials was dose-dependent, suggesting their potential application as active ingredients in cosmetic and pharmaceutic products at low concentrations.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). The contribution of COST Action LignoCOST (CA17128), supported by COST (European Cooperation in Science and Technology, www.cost.eu), in promoting interaction, exchange of knowledge and collaboration in the field of lignin valorisation is gratefully acknowledged. O.S. is grateful to the Knut and Alice Wallenberg Foundation for financial support through the Wallenberg Wood Science Center at KTH Royal Institute of Technology. H.L. acknowledges The China Scholarship Council and Wood and Pulping Chemistry Research Network (WPCRN) at KTH for the financial support of her doctorate study

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

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

Effect of quenching strategy and Nb-Mo sdditions on phase transformations and quenchability of high-strength boron steels

The application of direct quenching after hot rolling of plates is being employed in the production of ultra-high-strength hot rolled plates. When heavy gauge plates are produced, the complexity involve in achieving high cooling rates in the plate core is increased and the formation of undesirable soft phases within martensite is common. In the current paper, both direct quenching and conventional quenching (DQ and CQ) processing routes were reproduced by dilatometry tests and continuous cooling transformation (CCT) diagrams were built for four different high-strength boron steels. The results indicate that the addition of Mo and Nb-Mo suppresses the ferritic region and considerably shifts the CCT diagram to lower transformation temperatures. The combination of DQ strategy and the Mo-alloying concept provides the best option to ensure hardenability and the formation of a fully martensitic microstructure, and to avoid the presence of soft phases in the center of thick plates

裁判員の刑事裁判への参加意識と法に関する認識 (2) : 予備的アンケート調査から

The growing concern about the environmental impact and human health risk related to the excessive use of synthetic ingredients in cosmetics and topical formulations calls for the exploration of safe and sustainable natural alternatives. Lignin-rich lignocellulosic industrial wastes such as hazelnut and walnut shells were used as a lignin polymer source. Agro-derived lignins were evaluated as a potential natural active ingredient for health care products. Aside from the structural characteristics of isolated lignins, which were identified by GPC, Py-GC–MS, and 2D HSQC NMR techniques, functional properties such as antioxidant power and UV absorption ability were investigated. The SPF values found for creams containing 5% of hazelnut and walnut lignin content were 6.9 and 4.5, respectively. Additionally, both lignin types presented appropriate protection against UVA radiation, highly interesting property to block the full ultraviolet spectrum. The biological activity of isolated lignins assessed at different concentrations (0.01–1 mg/mL) and different times (24, 48, and 72 h) on murine fibroblast cell line 3T3 suggested their suitability for cosmetic applications.The authors are grateful for the financial support received from the University of the Basque Country (post-doctoral grant of Ms. Gordobil DOCREC18/29) and from the Basque Government (doctoral grant of Ms. Olaizola PRE_2016_1_0269)

Uncovering the potentialities of protic ionic liquids based on alkanolammonium and carboxylate ions and their aqueous solutions as non-derivatizing solvents of Kraft lignin

The present study scrutinized in depth the ability of alkanolammonium-based Protic Ionic Liquids (PILs) with carboxylate anions to dissolve Kraft lignin at 323.15 K. A focus was put on understanding the role of both PIL ions and water on the dissolution process. The results demonstrated that the anion plays a more important role in lignin dissolution than the cation. Furthermore, lignin dissolution was favored by increasing the alkyl chain of the carboxylate anion, while a smaller cation with lower number of hydroxyalkyl groups performed better. Among the studied solvents, the 2-hydroxyethylammonium hexanoate (HEAH) displayed the highest lignin solubility (37 wt%). In general, the addition of water had a negative influence on lignin solubility with the tested PILs. A sharp decrease in lignin solubility curves of 2-hydroxyethylammonium formate (HEAF) and acetate (HEAA) was observed, while a more softly effect was observed for 2-hydroxyethylammonium propionate (HEAP) and HEAH with the addition of water. However, a distinct behavior was observed for 2-hydroxyethylammonium octanoate (HEAO) that acted as hydrotrope enhancing lignin solubility in aqueous solutions to a maximum value at 40 wt% water content. Furthermore, by increasing the temperature, the lignin solubility was favored due to endothermic behavior of lignin dissolution process. The dissolution of Kraft lignin was also performed at 393.15 K to unravel any lignin modification unleashed by PILs. GPC, FTIR-ATR and 2D NMR were employed for lignin characterization and the changes observed between native lignin and recovered lignin samples were negligible demonstrating the non-derivatizing char- acter of the PILs. Moreover, the recycle of 2-hydroxyethylammonium propionate (HEAP) was successfully de- monstrated for at least 3 cycles. In this way, PILs are herein revealed as promising solvents to apply in lignin valorization towards more efficient and eco-friendly processes.Suzano Papel & Celulosepublishe