C. Pascoal Neto

Cork suberin as a new source of chemicals.: 1. Isolation and chemical characterization of its composition

Extractive-free cork from Quercus suber L. was submitted to a solvolysis treatment with methanolic NaOH which yielded 37% (o.d. cork) of suberin. This mixture of compounds was thoroughly characterized by FTIR, 1H- and 13C-NMR, gas chromatography coupled with mass spectrometric (GC-MS) analysis, vapour pressure osmometry (VPO), mass spectrography (MS) and gel permeation chromatography (GPC). After derivatization, the main components of the volatile fraction, representing less than half of the total, were found to be omega-hydroxymonocarboxylates, alpha, omega-dicarboxylates, simple alkanoates and 1-alkanols, all with chain lengths ranging from C16 to C24. A second fraction, with an average molecular weight about three times higher, was detected by VPO, MS and GPC. The presence of this important fraction in cork suberin had not been recognized in earlier studies. Both fractions constitute interesting precursors for the elaboration of new materials.

Identification of New Hydroxy Fatty Acids and Ferulic Acid Esters in the Wood of Eucalyptus globulus

Summary The chemical composition of the dichloromethane extract of Eucalyptus globulus wood cultivated in Portugal was studied by gas chromatography-mass spectrometry, prior to and after alkaline hydrolysis. In addition to previously identified lipophilic extractives, 22 free or esterified compounds (14 fatty acids, 2 fatty alcohols and 6 aromatic compounds) were identified for the first time in E. globulus wood. One of these, ferulic acid, was esterified with three different fatty alcohols and with two α-hydroxyfatty acids. Some of the newly identified compounds, particularly the a-hydroxy-fatty acids are responsible for recently reported pitch problems during pulp production in a Portuguese mill. The differences found in the E. globulus chemical composition, when compared with published data, are expected to be related to variations in the location of growth and genetic factors.

Chemical characterisation of bark and of alkaline bark extracts from maritime pine grown in Portugal

Abstract The chemical composition of maritime pine (Pinus pinaster) bark and of alkaline bark extracts has been investigated with bark from trees grown in Portugal. Bark is composed of lignin and polyphenolics (ca. 44%), polysaccharides (ca. 39%), dichoromethane, ethanol and water extractives (ca. 17%) and ashes (ca. 1%). The lignin content determined by the Klason method, after the extraction of polyphenolics (tannin-rich fraction) from the bark by alkali solution, is 33.2%. Cellulose content is about 24%. Hemicelluloses (about 15% of bark dry weight) are suggested to be predominantly composed of arabinoglucuronoxylans and minor amounts of galactoglucomanans. The bark lignin is composed by p-hydrophenylpropane and guaiacylpropane units in proportions of 20:80. The condensed tannins are constituted mainly by catechin-type structural units. The direct extraction of bark with aqueous alkaline solutions yields extracts which contain sugars, lignin and condensed tannins. The number average molecular weights (Mn) of alkaline extracts are in the range 1000–1500. The composition and Mn of extracted substances depends on the alkaline extraction conditions.

Lipophilic Extractives of the Inner and Outer Barks of Eucalyptus globulus

Summary The chemical compositions of the dichloromethane extracts of inner and outer barks of E. globulus were studied by gas chromatography-mass spectrometry. The two fractions show very different chemical compositions: triterpenic acids, such as betulinic, ursolic and oleanolic acids, were the major components of the outer bark extract, whereas β-sitosterol and β-amirin along with palmitic, linoleic and oleic acids predominate in the inner bark extract. Several α-and β-hydroxy fatty acids, recently reported for the first time as E. globulus wood components, were also identified in the outer and inner barks. In the outer bark extract, minor amounts of ferulic acid esters, also previously reported to occur in E. globulus wood were identified. In general, the inner bark lipophilic extractives resemble more closely that of E. globulus wood.

Solid-State Nmr Studies Of Wood And Other Lignocellulosic Materials

Solid-state NMR spectroscopy has been extensively applied to the structural characterization of the main components of wood, carbohydrate and lignin. The knowledge of the in situ structure and behaviour of such components is, however, of extreme importance since they determine the properties of wood materials under a variety of conditions. Some of the first applications of NMR to the direct study of wood involved the use of low-resolution measurements for the study of water within the wood fibre. With the development of high-resolution NMR techniques, an increasing number of in situ studies of wood have been carried out in order to investigate the behaviour of wood and wood-derived systems upon conditions such as stage of tree growth, susceptibility to biodegradation, response to pulping and bleaching and use in composite materials. Reference is also made to cork, another lignocellulosic material of economic interest to which solid-state NMR has been applied in an attempt to understand the origins of cork functional properties.

13C solid-state nuclear magnetic resonance and Fourier transform infrared studies of the thermal decomposition of cork

The thermal decomposition of cork has been studied by Fourier transform infrared (FTIR) spectroscopy and 13C solid-state nuclear magnetic resonance (NMR) spectroscopy with cross-polarization and magic-angle spinning (CP-MAS), high-power 1H decoupling (HPDEC) and cross-polarization depolarization-polarization (CPDP). Waxes and other soluble components of cork begin to decompose at ca. 150 degrees C. This is accompanied by partial decomposition of suberin, probably initiated at the points of attachment to the cell wall. The carbohydrates begin to decompose at ca. 200 degrees C. The decomposition of lignin begins at 250-300 degrees C, while suberin undergoes further degradation. Significant amounts of coke are formed in the process. At 400 degrees C cork has been transformed into coke with traces of partially decomposed suberin. The thermal decomposition of cork is dependent on the calcination time, particularly in the 200-350 degrees C range.

A 13C SOLID STATE NUCLEAR MAGNETIC RESONANCE SPECTROSCOPIC STUDY OF CORK CELL WALL STRUCTURE : THE EFFECT OF SUBERIN REMOVAL

Solid state 13C NMR measurements of cork, before and after suberin removal, showed that aliphatic suberin is spatially separated from carbohydrate and lignin and experiences higher motional freedom. Two types of chain methylenes, differing in chemical shift and in dynamic properties, were identified in aliphatic suberin. Experimental evidence indicated that the more motionally hindered methylenes are those situated nearer the linkages of aliphatic suberin to the cell wall. These linkages were shown to involve -CH2O- groups, probably engaged in ester linkages to phenylpropane units and carbohydrate C6 carbons. Spectral intensity changes indicated that, during the first steps of alkaline desuberization, these linkages are broken and the shorter aliphatic suberin chains removed. Longer chains require hydrolysis of the ester linkages within the chains and are removed upon stronger alkaline treatment. T1(C), T1 rho (H) and T1 rho (C) relaxation times have shown that the removal of suberin from cork leads to a motionally restricted and more compact environment, on the megahertz and mid-kilohertz timescales. The properties of cork suberin showed that suberin organization in cork is distinct from that in potato tissue.

Chemical composition and structural features of the macromolecular components of Hibiscus cannabinus grown in Portugal

Different morphological regions of Hibiscus cannabinus plants grown in Portugal were submitted to chemical composition studies. General chemical composition was determined by established methods. The polysaccharides were fractionated by successive extractions of holocellulose with aqueous KOH solutions. The sugar composition was determined by hydrolysis of polysaccharides followed by gas chromatography (GC) analysis of neutral sugars and spectrophotometric determination of uronic acids. In situ lignins and milled wood lignins (MWL) were characterised by permanganate oxidation followed by GC and GC-MS (mass spectrometry) analysis of the methylated oxidation products. The results of general chemical analysis have evidenced the different relative abundance of holocellulose, lignin, proteins, extractives and ashes in bark, core and foliage, at different stages of maturity. About 70–80% of the core hemicelluloses (about 20% o.d. material) was easily extracted with 5% KOH aqueous solutions against 60–70% (about 15% o.d. material) for the hemicelluloses of the bark. This hemicellulose fraction was composed mainly by glucuronoxylans with high content of uronic acids (xylose: uronic acid: 3–5: 1 for bark and 5–10: 1 for core). The hemicellulose fraction extracted with 24% KOH aqueous solutions was composed mainly by glucuronoxylans (80–90%) and glucomannans (10–15%). The results obtained by the permanganate oxidation method indicated that kenaf lignins are H-G-S type with approximate H: G: S molar proportions of (9–13): (55–60): (27–34) in bark and (14–20): (57)-(74): (12–23) in core, which evidences a high content of H and G units and a relatively low content of S units when compared with traditional dicotyledons. The relative proportion of H, G and S units as well as the structural features of lignins depends on the stage of maturity and on the morphological region of the plant. Kenaf lignins present a lower degree of condensation when compared with traditional wood lignins.

Variations in chemical composition and structure of macromolecular components in different morphological regions and maturity stages of Arundo donax

Arundo donax plants were manually separated into fractions of different morphological regions (internodes, nodes and foliage) at different stages of maturity and submitted to chemical composition studies. General chemical composition was determined by established methods. The polysaccharides were fractionated by successive extractions of holocellulose with aqueous KOH solutions. The sugar composition was determined by hydrolysis of polysaccharides followed by GC analysis of neutral sugars as alditol acetates and spectrophotometric determination of uronic acids. In situ lignins, milled wood lignins (MWL) and dioxane lignin were characterised by permanganate oxidation followed by GC and GC-MS analysis of the methylated oxidation products and by quantitative 13C NMR spectroscopy. The results of general chemical analysis evidenced the different relative abundance of holocellulose, lignin, proteins, extractives and ashes in internodes, nodes and foliage, at different stages of maturity. In internodes, nodes and foliage about 70–80% of hemicelluloses (21–30% o.d. material) were easily extracted with 5% KOH aqueous solutions. The analysis of hemicelluloses indicated that they are constituted mainly by arabinoglucuronoxylans with a xylose:arabinose:uronic acid ratio of 91–93:5–7:2 for internodes. The high content of xylose in Arundo donax stem (24–27% o.d. material) and the easy extraction of hemicelluloses opens new perspectives for the use of this reed as a source of pentosans. The results obtained by the permanganate oxidation method indicated that Arundo donax lignins are essentially H-G-type with approximate H:G:S proportions of (32–36):(59–61):(5–8) in internodes. The H units are constituted mainly by esterified p-coumaric acid. These results were confirmed by quantitative 13C NMR spectroscopy of isolated dioxane lignin. The quantity of condensed structures in in situ lignin decreases from the older to the younger parts of the stems and is much higher in nodes than internodes.

Oxidative delignification in the presence of molybdovanadophosphate heteropolyanions: mechanism and kinetic studies

Abstract The catalytic effect of molybdovanadophosphate heteropolyanions (HPAs) on the delignification of wood by oxygen has been investigated. The VO2+ ions produced via the dissociation of HPA in acidic conditions are suggested to have a much stronger catalytic effect on the oxidation of lignin than parent HPA. The influence on delignification of the pH, medium composition and the partial reduction of HPA prior to its use in catalysis are discussed in terms of the reaction mechanisms. Kinetic studies show that the catalyst diffusion in the wood tissue is the rate-limiting step of delignification, while the lignin oxidation rate is determined by the HPA/VO2+ catalytic oxidation step.