Cationization of eucalyptus kraft lignoboost lignin: preparation, properties, and potential applications

Current changes toward a more biobased economy have recently created tremendous renewed interest in using lignin as a valuable source for chemicals and materials. Here, we present a facile cationization approach aiming to impart kraft lignin water-solubility, with similar good features as lignosulfonates. Eucalyptus globulus kraft lignin obtained from a paper mill black liquor by applying the LignoBoost process was used as the substrate. Its reaction with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTAC) in an aqueous alkaline medium was studied to assess the impact of different reaction conditions (temperature, time, educt concentration, molar CHPTAC-to-lignin ratio) on the degree of cationization. It has been shown that at pH 13, 10 wt % lignin content, 70 °C, and 3 h reaction time, a CHPTAC-to-lignin minimum molar ratio of 1.3 is required to obtain fully water-soluble products. Elemental analysis (4.2% N), size-exclusion chromatography (M w 2180 Da), and quantitative 13C NMR spectroscopy of the product obtained at this limit reactant concentration suggest introduction of 1.2 quaternary ammonium groups per C9 unit and substitution of 75% of the initially available phenolic OH groups. The possible contribution of benzylic hydroxyls to the introduction of quaternary ammonium moieties through a quinone methide mechanism has been proposed. Since both molecular characteristics and degree of substitution, and hence solubility or count of surface charge, of colloidal particles can be adjusted within a wide range, cationic kraft lignins are promising materials for a wide range of applications, as exemplarily demonstrated for flocculation of anionic dyes.publishe

Valorization of lignin side-streams into polyols and rigid polyurethane foams—a contribution to the pulp and paper industry biorefinery

Valorization of industrial low-value side-streams are of great interest, contributing to boosts in the circular economy. In this context, lignin side-streams of the pulp and paper industry were oxypropylated to produce biobased polyols and tested in the synthesis of rigid polyurethane (RPU) foams. E. globulus lignins, namely a lignin isolated from an industrial Kraft black liquor and depolymerized lignins obtained as by-products of an oxidation process, were used. RPU foams, synthesized with 100% lignin-based polyols and using a 1.1 NCO/OH ratio, were characterized concerning apparent density, morphology, thermal conductivity, thermal stability, and heat release rate (HRR). Foams containing the lignin-based polyols presented densities varying from 44.7 to 112.2 kg/m3 and thermal conductivity in the range of 37.2–49.0 mW/mK. For the reference foam (sample produced with 100% wt. Daltofoam TP 32015 polyol), values of 70.9 kg/m3 and 41.1 mW/mK were obtained, respectively. The achieved results point out the viability of using the generated lignin-based polyols at 100% content in RPU foams, mainly when depolymerized lignins are used. Moreover, fire retardancy was favored when the lignin-based polyols were introduced. The proposed strategies can contribute to establishing the integrated pulp and paper biorefinery concept where material synthesis (polyols and RPU foams) can be combined with chemical production (vanillin and syringaldehyde).Foundation for Science and Technology (FCT, Portugal) and FEDER under Program PT2020 for financial support to CIMO (UIDB/00690/2020), and to UIDB/50020/2020 of the Associate Laboratory LSRE-LCM—funded by national funds through FCT/MCTES (PIDDAC); national funding by FCT, PI, through the institutional scientific employment program contract for Isabel P. Fernandes. This work was carried out under the Project No. 33969 Bioblocks—Design of biobased products from renewable lignocellulosic sources as precursors for the bioindustry of chemical synthesis and biomaterials—financed by FEDER through the Operational Program for Competitiveness Factors (POFC) and QREN. To COST Action LignoCOST (CA17128) supported by COST (European Cooperation in Science and Technology).info:eu-repo/semantics/publishedVersio

Avaliação da boatividade de frações fenólicas de Eucalyptus globulus labill

No contexto industrial, Eucalyptus globulus Labill é uma das espécies mais importantes para a obtenção de pasta de papel. Deste processo resulta um resíduo, a casca, cuja valorização por extração dos polifenóis tem sido estudada no LSRE [1-3]. Neste âmbito, o extrato obtido utilizando condições otimizadas, foi fracionado por ultra- e/ ou nano-filtração e purificado por adsorção/dessorção. O extrato inicial (Fração I) foi diafiltrado (Fração II) e submetido a um processo de adsorção/desorção. Daqui resultaram 2 frações: a fração recolhida à saída da coluna (Fração III) e a fração purificada obtida por dessorção com etanol (Fração IV). As propriedades antioxidantes das quatro frações (Fração I-IV) foram avaliadas através de ensaios in vitro (atividade captadora de radicais livres, poder redutor e inibição da peroxidação lipídica). Na determinação das propriedades citotóxicas aplicou-se o método da sulforrodamina B a linhas celulares tumorais humanas designadamente, MCF-7 (carcinoma de mama), NCI-H460 (carcinoma pulmão), HCT-15 (carcinoma de cólon), HeLa (carcinoma cervical) e HepG2 (carcinoma hepatocelular). A citotoxicidade das frações foi também avaliada utilizando culturas primárias de células de fígado de porco (células não-tumorais, PLP2). A fração purificada (Fração IV) mostrou ter melhor atividade antioxidante (valores de EC50 inferiores a 841-lg/mL) e antitumoral, (valores de GI50 inferiores a 921-lg/mL) com exceção da linha celular MCF-7 em que a fração à saída da coluna (Fração III) originou melhores resultados (GI50=23 11g/mL). Nenhuma amostra apresentou toxicidade contra células não tumorais (Gl50>400 11g/mL). A maior bioatividade demonstrada pela fração purificada está certamente relacionada com o seu teor superior em compostos fenólicos totais (67%) e proantocianidinas (55 o/o)

Espectro de gotas de pulverização e controle da ferrugem-asiática-da-soja em cultivares com diferentes arquiteturas de planta

O objetivo deste trabalho foi determinar o espectro de gotas de pulverização ideal para o controle da ferrugem-asiática-da-soja (Phakopsora pachyrhizi), em cultivares com diferentes arquiteturas de planta. O experimento foi conduzido na safra de 2009/2010. A aplicação de fungicida (piraclostrobina + epoxiconazol, com óleo mineral) foi avaliada com quatro espectros de gotas de pulverização - muito fino, <119 μm; fino, 119 a 216 μm; médio, 217 a 352 μm; e grosso, 353 a 464 μm -, em quatro cultivares de soja (BMX Apollo RR, NA 7636 RR, Fcep 53 RR e TMG 4001 RR) contrastantes quanto a índice de área foliar, estatura de plantas e número de ramos por planta. Foram quantificadas as variáveis: número de gotas por cm², diâmetro mediano volumétrico das gotas, área abaixo da curva de progresso da ferrugem-asiática e produtividade da soja. A definição do espectro de gotas a ser utilizado deve considerar a cultivar e as condições ambientais em que a pulverização será realizada. A magnitude da proteção exercida pelo fungicida varia de acordo com a cobertura de plantas e a penetração de gotas no dossel, proporcionada pelos diferentes espectros de gota. O espectro de gotas fino proporciona boa deposição de gotas, controle da doença e produtividade, independentemente da cultivar avaliada

NEOTROPICAL XENARTHRANS: a data set of occurrence of xenarthran species in the Neotropics

Xenarthrans – anteaters, sloths, and armadillos – have essential functions for ecosystem maintenance, such as insect control and nutrient cycling, playing key roles as ecosystem engineers. Because of habitat loss and fragmentation, hunting pressure, and conflicts with 24 domestic dogs, these species have been threatened locally, regionally, or even across their full distribution ranges. The Neotropics harbor 21 species of armadillos, ten anteaters, and six sloths. Our dataset includes the families Chlamyphoridae (13), Dasypodidae (7), Myrmecophagidae (3), Bradypodidae (4), and Megalonychidae (2). We have no occurrence data on Dasypus pilosus (Dasypodidae). Regarding Cyclopedidae, until recently, only one species was recognized, but new genetic studies have revealed that the group is represented by seven species. In this data-paper, we compiled a total of 42,528 records of 31 species, represented by occurrence and quantitative data, totaling 24,847 unique georeferenced records. The geographic range is from the south of the USA, Mexico, and Caribbean countries at the northern portion of the Neotropics, to its austral distribution in Argentina, Paraguay, Chile, and Uruguay. Regarding anteaters, Myrmecophaga tridactyla has the most records (n=5,941), and Cyclopes sp. has the fewest (n=240). The armadillo species with the most data is Dasypus novemcinctus (n=11,588), and the least recorded for Calyptophractus retusus (n=33). With regards to sloth species, Bradypus variegatus has the most records (n=962), and Bradypus pygmaeus has the fewest (n=12). Our main objective with Neotropical Xenarthrans is to make occurrence and quantitative data available to facilitate more ecological research, particularly if we integrate the xenarthran data with other datasets of Neotropical Series which will become available very soon (i.e. Neotropical Carnivores, Neotropical Invasive Mammals, and Neotropical Hunters and Dogs). Therefore, studies on trophic cascades, hunting pressure, habitat loss, fragmentation effects, species invasion, and climate change effects will be possible with the Neotropical Xenarthrans dataset

Polyols and rigid polyurethane foams derived from lignin side-streams of the pulp and paper industry

Lignin is one of the major components of the side-streams of the pulp and paper industries and of the emerging lignocellulosic biore neries. Find new strategies for lignin valorisation, apart from e vironmental issues, will contribute to close the lignocellulosic value-chain. In this context, this work will focus on the synthesis of polyols through oxypropylation and their subsequent incorporation into rigid polyurethane (RPU) foam formulations. Two E. globulus lignin streams were tested: (i) lignin isolated from industrial kraft liquor and (ii) depolymerized lignin resulting from an oxidation process developed at the LA LSRE-LCM to produce vanillin and syringaldehyde. This work is therefore part of the LA LSRE-LCM global strategy towards the consolidation of the integrated process to valorise lignin from the kraft pulp industry, which accounts with more than 25 years of experience.info:eu-repo/semantics/publishedVersio

An electrospray ionization mass spectrometry study of azidoacetic acid/transition metal complexes: Complexation of azidoacetic acid with transition metals

RationaleThe complexation behavior of transition metals with organic azides by electrospray ionization (ESI) tandem mass spectrometry (MS/MS) is not completely understood. In this study, fragmentation patterns of complex ions having azidoacetic acid coordinated to Ni/Co/Fe were elucidated. The role of transition metals in the mediation of ligand rearrangements in gas phase is experimentally supported.MethodsThe complexation of some transition metals, nickel, cobalt and iron, by azidoacetic acid was studied by means of ESI and MS/MS. Fragmentation patterns were discerned via consecutive MS/MS experiments on an ion trap mass spectrometer and confirmed by high‐resolution (HR) Fourier transform ion cyclotron resonance MS. Density functional theory (DFT) calculations were used to characterize the major ions observed in MS.ResultsOnly singly positively charged complex ions were detected presenting various stoichiometries. MS/MS and theoretical calculations allowed us to confirm assignments and coordination sites. Structural evidence suggested that the azidoacetic acid can behave as monodentate and/or bidentate and coordination through the oxygen and nitrogen atoms are both possible. Experimental evidence strongly points to a role of Ni/Co/Fe, in oxidative state (I), in mediating C–C bond activation in the gas phase.ConclusionsMS/MS and HRMS experiments were able to elucidate azidoacetic acid complexation with Ni/Co/Fe and several gas‐phase processes involving metal reduction and rearrangements. The definition of the coordination pattern dictated by the competition between the nitrogen and the oxygen atoms is also dependent on the metal centre in a very dynamic process.<br/

Experimental lamellar keratoplasty in rabbits using microfibrilar cellulose membrane: clinical, morphological and immunohistochemical findings Ceratoplastia lamelar experimental em coelhos usando membrana microfibrilar de celulose: achados clínicos, morfológicos e imunoistoquímicos

The clinical, histopathological and immunohistochemical features of the cornea were investigated in adult male New Zealand rabbits submitted to lamellar keratoplasty with microfibrillar cellulose membrane. Thirty animals were divided into five groups (n=6) and evaluated up to 60 days after surgery. Clinical examination revealed moderate manifestations of edema, blepharospasm and photophobia on the second day, which became mild or disappeared after the seventh day. This period was characterized clinically by repair of the corneal defect. Histopathological analysis showed the presence of a thin layer of squamous cells covering the damaged area as early as 7th day, accompanied by a mild infiltrate of polymorphonuclear cells. Blood vessels were observed in the epithelium after the 15th day, which had regressed by day 48. Ki67 antibody labeling showed an increase of proliferating cells in the epithelium by the 15th day and in the stroma by day 30. Remodeling and epithelial adhesion were observed during this period. Microfibrillar cellulose membrane (Bionext®) used for lamellar keratoplasty was found to yield good results considering the good integration of the implant.<br>Avaliaram-se aspectos clínicos, histopatógicos e imunoistoquímicos da córnes de coelhos da raça Nova Zelândia adultos e machos em ceratoplastias lamelares com membrana de celulose microfibrilar. Trinta animais distribuídos em cinco grupos (n=6) foram estudados por até 60 dias de pós-operatório. A avaliação clínica revelou manifestações moderadas de edema, blefaroespasmo e fotofobia ao segundo dia, evoluindo para formas discretas ou ausentes a partir do sétimo dia, período em que se observou, clinicamente, reparo do defeito corneal. A histopatologia revelou uma fina camada de células escamosas, recobrindo a área lesada já aos sete dias, com discreto infiltrado de células polimorfonucleares. Observaram-se vasos no epitélio a partir do 15o dia, com regressão ao 48o dia. A marcação com o anticorpo Ki67 mostrou aumento de células em proliferação aos 15 dias no epitélio e aos 30 dias no estroma. Nesse período, ocorreram remodelamento e adesão epitealial. Considerando a boa integração do implante, admite-se a membrana de celulose como um bom material a ser utilizado em ceratoplastia lamellar