Uma nova metodologia para a síntese de modelos de lignina a partir de reações de inserção O-H entre fenóis de α-aril diazocetonas

A biomassa lignicelulósica tem sua estrutura composta por celulose, hemicelulose e lignina. Dentre essas, a lignina tem se mostrado interessante por ser uma fonte precursora sustentável de fragmentos aromáticos antes obtidos apenas de combustíveis fósseis. Sua estrutura é composta por resíduos de fenilpropanóides p-hidroxibenzeno (H), guaiacil (G) e siringil (S) unidas por ligações C–C e C–O–C em que a ligação β–O–4 é a predominante (mais de 50%). Devido à sua complexidade estrutural e conformacional, a clivagem de suas ligações é pouco seletiva e a caracterização dos fragmentos resultantes é complexa. Uma estratégia comumente empregada para evitar esses desafios é o uso de modelos mais simples. Entretanto, poucas metodologias são reportadas na literatura para a sua síntese e a maioria delas envolve o emprego de halocetonas. O presente trabalho desenvolveu duas novas metodologias promissoras para síntese desses oligômeros, contendo ligação β–O–4 por meio da química de diazo: (a) reação de inserção O–H entre fenol e α–aril diazocetonas, e (b) compostos α–diazo β-cetoéster. Ademais, a utilização de monômeros contendo a função fenol e diazocetona no mesmo anel permitiria a síntese de cadeias de diversos tamanhos em uma única etapa. Como ponto de partida para o estudo, limitou-se à síntese de dímeros, visando entender a reação de inserção O–H. Os produtos desejados foram obtidos em rendimentos de 27–51% após catálise com Cu(hfac)2. Por fim, os modelos de lignina propriamente ditos foram sintetizados após simples adição aldólica e redução em rendimentos globais de 51–78%. Os estudos envolvendo a inserção de fenol em α–diazo β-cetoéster mostraram resultados promissores, corroborando para uma nova estratégia sintética para a obtenção de modelos de lignina. Novos estudos em nosso laboratório estão sendo desenvolvidos para se obter resultados mais conclusivos.

Hydrothermal Carbons from Hemicellulose-Derived Aqueous Hydrolysis Products as Electrode Materials for Supercapacitors

Acid pretreatment of lignocellulosic biomass, required for bioethanol production, generates large amounts of by-products, such as lignin and hydrolyzed hemicellulose fractions, which have found so far very limited applications. In this work, we demonstrate how the recovered hemicellulose hydrolysis products can be effectively utilized as a precursor for the synthesis of functional carbon materials through hydrothermal carbonization (HTC). The morphology and chemical structure of the synthesized HTC carbons are thoroughly characterized to highlight their similarities with glucose-derived HTC carbons. Furthermore, two routes for introducing porosity within the HTC carbon structure are presented: i) silica nanoparticle hard-templating, which is shown to be a viable method for the synthesis of carbonaceous hollow spheres; and ii) KOH chemical activation. The synthesized activated carbons (ACs) show an extremely high porosity (pore volume≈1.0 cm3 g−1) mostly composed of micropores (90 % of total pore volume). Because of their favorable textural properties, the ACs are further tested as electrodes for supercapacitors, yielding very promising results (300 F g−1 at 250 mA g−1) and confirming the high suitability of KOH-activated HTC carbons derived from spruce and corncob hydrolysis products as materials for electric double layer supercapacitors.

Physical and chemical evaluation of furniture waste briquettes

Furniture waste is mainly composed of wood and upholstery foam (mostly polyurethane foam). Both of these have a high calorific value, therefore, energy recovery would be an appropriate process to manage these wastes. Nevertheless, the drawback is that the energy content of these wastes is limited due to their low density mainly that of upholstery foam. Densification of separate foam presents difficulties due to its elastic character. The significance of this work lies in obtaining densified material by co-densification of furniture wood waste and polyurethane foam waste. Densification of furniture wood and the co-densification of furniture wood waste with polyurethane foam have been studied. On the one hand, the parameters that have an effect on the quality of the furniture waste briquettes have been analysed, i.e., moisture content, compaction pressure, presence of lignin, etc. The maximum weight percentage of polyurethane foam that can be added with furniture wood waste to obtain durable briquettes and the optimal moisture were determined. On the other hand, some parameters were analysed in order to evaluate the possible effect on the combustion. The chemical composition of waste wood was compared with untreated wood biomass; the higher nitrogen content and the concentration of some metals were the most important differences, with a significant difference of Ti content.

Potential Shifts in Canadian High Arctic Sedimentary Organic Matter Composition With Permafrost Active Layer Detachments

Increased temperature and precipitation in Arctic regions have led to deeper thawing and structural instability in permafrost soil. The resulting localized disturbances, referred to as active layer detachments (ALDs), may transport organic matter (OM) to more biogeochemically active zones. To examine this further, solid state cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS NMR) and biomarker analysis were used to evaluate potential shifts in riverine sediment OM composition due to nearby ALDs within the Cape Bounty Arctic Watershed Observatory, Nunavut, Canada. In sedimentary OM near ALDs, NMR analysis revealed signals indicative of unaltered plant-derived material, likely derived from permafrost. Long chain acyclic aliphatic lipids, steroids, cutin, suberin and lignin occurred in the sediments, consistent with a dominance of plant-derived compounds, some of which may have originated from permafrost-derived OM released by ALDs. OM degradation proxies for sediments near ALDs revealed less alteration in acyclic aliphatic lipids, while constituents such as steroids, cutin, suberin and lignin were found at a relatively advanced stage of degradation. Phospholipid fatty acid analysis indicated that microbial activity was higher near ALDs than downstream but microbial substrate limitation was prevalent within disturbed regions. Our study suggests that, as these systems recover from disturbance, ALDs likely provide permafrost-derived OM to sedimentary environments. This source of OM, which is enriched in labile OM, may alter biogeochemical patterns and enhance microbial respiration within these ecosystems.

Morphomechanical Innovation Drives Explosive Seed Dispersal

How mechanical and biological processes are coordinated across cells, tissues, and organs to produce complex traits is a key question in biology. Cardamine hirsuta, a relative of Arabidopsis thaliana, uses an explosive mechanism to disperse its seeds. We show that this trait evolved through morphomechanical innovations at different spatial scales. At the organ scale, tension within the fruit wall generates the elastic energy required for explosion. This tension is produced by differential contraction of fruit wall tissues through an active mechanism involving turgor pressure, cell geometry, and wall properties of the epidermis. Explosive release of this tension is controlled at the cellular scale by asymmetric lignin deposition within endocarp b cells-a striking pattern that is strictly associated with explosive pod shatter across the Brassicaceae plant family. By bridging these different scales, we present an integrated mechanism for explosive seed dispersal that links evolutionary novelty with complex trait innovation.

Organic geochemistry on sediment profiles from the Arctic Ocean

During the ARCTIC '91-Expedition with RV 'Polarstern', several Multicorer and Kastenlot-cores were recovered along a profile crossing the eastern part of the Arctic Ocean. The investigated cores consist mainly of clayey-silty sediments, and some units with a higher sand content. In this thesis, detailed sedimentological and organic-geochemical investigations were performed. In part, the near surface sediments were AMS-14C dated making it possible to Interpret the results of the organic-geochemical investigations in terms of climatic changes (isotopic stage 2 to the Holocene). The more or less absence of foraminifers within the long cores prevented the development of an oxygen isotope stratigraphy. Only the results of core PS2174-5 from the Amundsen-Basin could be discussed in terms of the climatic change that could be dated back to oxygen isotope stage 7. Detailed organic-geochemical investigations in the central Arctic Ocean are rare. Therefore, several different organic-geochemical methods were used to obtain a wide range of data for the Interpretation of the organic matter. The high organic carbon content of the surface sediments is derived from a high input of terrigenous organic matter. The terrigenous organic material is most likely entrained within the sea-ice On the Siberian shelves and released during ice-drift over the Arctic Ocean. Other factors such as iceberg-transport and turbidites are also responsible for the high input of terrigenous organic matter. Due to the more or less closed sea-ice Cover, the Arctic Ocean is known as a low productivity system. A model shows, that only 2 % of the organic matter in central Arctic Ocean sediments is of a marine origin. The influence of the West-Spitsbergen current increases the marine organic matter content to 16 %. Short chain n-alkanes (C17 and C19) can be used as a marker of marine productivity in the Arctic Ocean. Higher contents of short chain n-alkanes exist in surface sediments of the Lomonosov-Ridge and the Makarov-Basin, indicating a higher marine productivity caused by a reduced sea-ice Cover. The Beaufort-Gyre and Transpolar-Drift drift Patterns could be responsible for the lower sea-ice distribution in this region. The sediments of Stage 2 and Stage 3 in this region are also dominated by a higher content of short chain-nalkanes indicating a comparable ice-drift Pattern during that time. The content and composition of organic carbon in the sediments of core PS2174-5 reflect glaciallinterglacial changes. Interglacial stages 7 and 5e show a low organic carbon content (C 0,5 %) and, as indicated by high hydrogen-indices, low CIN-ratios, higher content of n-alkanes (C17 and C19) and a higher opal content, a higher marine productivity. In the Holocene, a high content of foraminifers, coccoliths, ostracodes, and sponge spicules indicate higher surface-water productivity. Nevertheless, the low hydrogenindices reveal a high content of terrigenous organic matter. Therefore, the Holocene seems to be different from interglacials 7 and 5e. During the glacial periods (stages 6, upper 5, and 4), TOC-values are significantly higher (0.7 to 1.3 %). In addition, low hydrogen-indices, high CIN-ratios, low short chain n-alkanes and opal contents provide evidence for a higher input of terrigenous organic matter and reduced marine productivity. The high lignin content in core sections with high TOC-contents, substantiates the high input of terrigenous organic matter. Changes in the content and composition of the organic carbon is believed to vary with the fluctuations in sea-level and sea-ice coverage.

Biogeochemical parameters of sea water and bottom sediments near the Curieuse Island (Seychelles Islands)

Biogeochemical reef studies carried out in 1981 and 1984 found low concentration of total natural and anthropogenic hydrocarbons in inshore waters. Detection of lignin in marine and bottom sediments indicates that the land has major effect on makeup of organic matter there. Comparison of compositions of organic matter in sea water, suspended matter and bottom sediments indicated that it was altered rapidly by the reef community. Thus, in the inshore zone of the island, runoff from the land is important in supplying nutrients to the reef ecosystem alongside with transport of nutrients by deep waters. Concentrations of nutri¬ents (N, P) in the inshore zone are higher than in waters of the tropical part of the ocean. Nitrogen is the limiting element in development of phytoplankton in the inshore zone.

Concentration of phenols in bottom sediments from the Kandalaksha Bay, White Sea

Data on distribution of organic carbon and phenols near the top of Kandalaksha Gulf, one of the largest gulfs of the White Sea, are presented. Investigations carried out the port city of Kandalasksha indicate that bottom sediments of the area adjoining the port contain synthetic phenols and have elevated concentrations of organic carbon. But in general sediments of this part of the gulf have near-normal concentration and composition of both phenols and organic carbon. This indicates that ecological situation in this area remains near-optimal.

Organic petrology of Neogene sediment from ODP Leg 117

Neogene sediments from three areas of the Northern Indian Ocean (Indus Fan, Owen Ridge, Oman Margin, ODP Leg 117) were studied in order to determine the amount, type, and preservation of organic matter as functions of the environments encountered. The work consisted of geochemical analyses on whole sediment (Total Organic Content and Rock Eval pyrolysis) and of petrographic studies on isolated organic matter by optical and scanning electron microscopy. In Indus Fan sediments, organic matter is present in low amounts, mainly as lignaceous fragments. A contrasting situation exists in Oman Margin sediments which are generally rich in amorphous autochtonous organic matter. Owen Ridge, located between Indus fan and Oman Margin areas, shows two phases of organic sedimentation as a consequence of the uplift of the ridge. The older phase (Oligocene to early or middle Miocene) is strongly influenced by detrital supply from the Indus, while the younger phase (middle Miocene to Pleistocene) is characterized by relatively high amounts of autochtonous organic matter. From a general point of view it appears that high amounts of organic matter are mainly due to good preservation of marine amorphous organic matter, such as in Oman Margin sediments and in upper pelagic levels of Indus Fan and Owen Ridge deposits. Low total organic carbon contents are correlated with low proportions of amorphous material in the total organic matter due to oxidizing conditions. This leads to a relative enrichment in components derived from resistant materials (lignin, chitin, or other resistant biopolymers) such as lignaceous fragments (Indus Fan) and/or fragments from benthic organisms and alveolate microplankton (Oman Margin).

Humic acids in bottom sediments of the Western Pacific

Elemental composition, functional groups, and molecular mass distribution were determined in humic acids from the Western Pacific abyssal and coastal bottom sediments. Humic acid structure was studied by oxidative degradation with alkaline nitrobenzene and potassium permanganate, p-coumaric, guaiacilic, and syringilic structural units typical for lignin of terrestrial plants were identified in humic acids by chromatographic analysis of oxidation products. Polysubstituted and polycondensed aromatic systems with minor proportion of aliphatic structures were basic structural units of humic acids in abyssal sediments.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

Soil solidification research, Cornell University, 1946 to 1951; final report.

v. 1. Summarization, fundamental and applied research.--v. 2. Fundamental properties, clay - water systems.--v. 3. Applied research, chrome-lignin process and soil briquetting.

Piggery pond sludge as a nitrogen source for crops. 1. Mineral N supply estimated from laboratory incubations and field application of stockpiled and wet sludge

Piggery pond sludge (PPS) was applied, as-collected (Wet PPS) and following stockpiling for 12 months ( Stockpiled PPS), to a sandy Sodosol and clay Vertosol at sites on the Darling Downs of Queensland. Laboratory measures of N availability were carried out on unamended and PPS-amended soils to investigate their value in estimating supplementary N needs of crops in Australia's northern grains region. Cumulative net N mineralised from the long-term ( 30 weeks) leached aerobic incubation was described by a first-order single exponential model. The mineralisation rate constant (0.057/week) was not significantly different between Control and PPS treatments or across soil types, when the amounts of initial mineral N applied in PPS treatments were excluded. Potentially mineralisable N (N-o) was significantly increased by the application of Wet PPS, and increased with increasing rate of application. Application of Wet PPS significantly increased the total amount of inorganic N leached compared with the Control treatments. Mineral N applied in Wet PPS contributed as much to the total mineral N status of the soil as did that which mineralised over time from organic N. Rates of CO2 evolution during 30 weeks of aerobic leached incubation indicated that the Stockpiled PPS was more stabilised (19-28% of applied organic C mineralised) than the Wet PPS (35-58% of applied organic C mineralised), due to higher lignin content in the former. Net nitrate-N produced following 12 weeks of aerobic non-leached incubation was highly correlated with net nitrate-N leached during 12 weeks of aerobic incubation (R-2 = 0.96), although it was

Comparison of the particulate organic carbon and permanganate oxidation methods for estimating labile soil organic carbon

Forty-four soils from under native vegetation and a range of management practices following clearing were analysed for ‘labile’ organic carbon (OC) using both the particulate organic carbon (POC) and the 333 mm KmnO4 (MnoxC) methods. Although there was some correlation between the 2 methods, the POC method was more sensitive by about a factor of 2 to rapid loss in OC as a result of management or land-use change. Unlike the POC method, the MnoxC method was insensitive to rapid gains in TOC following establishment of pasture on degraded soil. The MnoxC method was shown to be particularly sensitive to the presence of lignin or lignin-like compounds and therefore is likely to be very sensitive to the nature of the vegetation present at or near the time of sampling and explains the insensitivity of this method to OC gain under pasture. The presence of charcoal is an issue with both techniques, but whereas the charcoal contribution to the POC fraction can be assessed, the MnoxC method cannot distinguish between charcoal and most biomolecules found in soil. Because of these limitations, the MnoxC method should not be applied indiscriminately across different soil types and management practices.