Nereida Cordeiro

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.

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.

Urethanes and polyurethanes from suberin: 1. Kinetic study

Abstract Within the context of a study on the preparation and the characterization of polyurethanes based on suberin, as a polyol, and conventional polyisocyanates, it was deemed necessary to carry out a preliminary study on the reactivity of the hydroxy functions of suberin. Aliphatic and aromatic mono- and di-isocyanates were tested and the kinetics of this system followed the classical second order up to conversions of about 85%. The influence of the steric hindrance and the electronic factors, linked to the specific structures of both types of isocyanates, was established.

Cork suberin as a new source of chemicals: 2. Crystallinity, thermal and rheological properties

Suberin samples, obtained by alkaline methanolysis from cork (Quercus suber L.), were submitted to various physical characterizations; DSC, TGA, optical microscopy, density and rheological properties. A substantial proportion of these oligomers possessed a microcrystalline character with a melting range between 0 and 50°C. The amorphous part was liquid at room temperature and did not display a detectable glass transition upon cooling because of its wide molecular weight distribution. The viscous behaviour of suberin at room temperature was both plastic and thixotropic because of the structuring role of the microcrystals.

Urethanes and polyurethanes from suberin 2: synthesis and characterization

Abstract Polyurethanes based on suberin from cork of Quercus suber L. and conventional isocyanate monomers were prepared and fully characterized in terms of both structure (FTIR and 1H NMR spectroscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). Two fractions were systematically isolated, namely (i) methylene-chloride soluble products, which corresponded to linear and branched macromolecules and (ii) methylene-chloride insoluble products, representing the crosslinked material. The structures of these polymers were regular and no appreciable side reactions were detected. DSC analyses provided information about the glass transition temperature of both fractions and this parameter was correlated with the stiffness of the isocyanate used. The TGA of these polyurethanes showed that they started to degrade at about 175°C and that the residue at 400°C was around 50%. The highest amounts of insoluble fractions, as well as the highest Tgs, were reached when an initial [NCO]/[OH] of unity was used.

Isolation and characterization of a lignin-like polymer of the cork of Quercus suber L.

A lignin-like polymer was successfully extracted from the cork of Quercus suber L. using an organosolv-based technique. This material was characterized by elemental analysis, functional group analysis, nitrobenzene oxidation followed by HPLC analysis of the oxidation products, FTIR and liquid 13 C NMR. The evidence thus obtained indicated that the extracted material was composed mainly of a lignin-like polymer covalently bound to residual aliphatic structures which are not present in common lignins and which have been assigned to suberin. The latter is likely to be attached to the oxygenated side chains of the phenolic polymer but bonding through the aromatic ring can also be envisaged. No residual carbohydrates were detected. The phenolic polymer, composed mainly of guaiacyl-type units and small amounts of syringyl-type units, had a low methoxy content and a high degree of condensation. This polymer showed the presence of a fraction containing C 6 C 0 units with n < 3 or even n < 2.

Variation on the adsorption efficiency of humic substances from estuarine waters using XAD resins

Abstract The XAD8 and XAD4 resins, used in series, show different behaviours in relation to the retention of dissolved organic matter (DOM) from estuarine water samples according to different salinities. For the XAD8 resin, the removal of DOM measured in terms of light absorbance at 250 nm varies from 69.4% ± 0.5 to 51.4% ± 3.5 and for the XAD4 resin it varies from 20.0% ± 1.0 to 25.2% ± 3.0 for salinities ranging from 0.6 to 33.4. The isolation, with XAD8, of DOM from samples increasing in salinity, measured in terms of emission fluorescence intensity at selected wavelengths (410, 440 and 460 nm) for an excitation of 340 nm, decreases. In the same experimental conditions, the increase of fluorescent organic matter (FOM) removed by the addition of XAD4 resin is always greater than 20%. However, addition of NaCl to the sample with the lowest salinity, shows that the retention in both resins is related more to the nature of DOM than to the ionic strength of the sample.

Biodegradable Nanocomposite Films Based on Sodium Alginate and Cellulose Nanofibrils

Biodegradable nanocomposite films were prepared by incorporation of cellulose nanofibrils (CNF) into alginate biopolymer using the solution casting method. The effects of CNF content (2.5, 5, 7.5, 10 and 15 wt %) on mechanical, biodegradability and swelling behavior of the nanocomposite films were determined. The results showed that the tensile modulus value of the nanocomposite films increased from 308 to 1403 MPa with increasing CNF content from 0% to 10%; however, it decreased with further increase of the filler content. Incorporation of CNF also significantly reduced the swelling percentage and water solubility of alginate-based films, with the lower values found for 10 wt % in CNF. Biodegradation studies of the films in soil confirmed that the biodegradation time of alginate/CNF films greatly depends on the CNF content. The results evidence that the stronger intermolecular interaction and molecular compatibility between alginate and CNF components was at 10 wt % in CNF alginate films.

Cork suberin as an additive in offset lithographic printing inks

Suberin oligomers, isolated from cork (Quercus suber L.), were used as additives in ‘Waterless’ and vegetable-oil ink formulations, in the range of 2‐10% w:w. The rheological behaviour of the suberin oligomers as well as of the inks, with and without suberin, were investigated as a function of temperature. It was shown that the addition of suberin induces a decrease of viscosity of both inks. The tack of pristine inks, suberin oligomers and their mixtures were determined at different temperatures: the variation of this parameter as a function of time provided information about the drying kinetics of these formulations. The tack of the ‘Waterless’ ink was found to increase with the

The Organosolv Fractionation of Cork Components

Summary Extractive-free cork from Quercus suber L. was submitted to organosolv fractionation and the effects of different process variables, such as ethanol/water ratio, temperature, time and the presence of acidic or alkaline catalysts, were studied. The variation of the relative proportions of extracted components, as a function of the processing conditions, could thus be established. Whereas the addition of 0.1Macetic acid only increased the yield of extracted materials from about 15 to 23 %, the use of sodium hydroxide, at the same concentration, produced a jump to 76 %. In the case of the alkaline organosolv fractionation, an increase in process temperature, time and catalyst concentration led to an increase in the extraction yield, although in some cases this increase did not follow a sustained trend, as in the case of reaction time. Increasing the ethanol/water ratio led to a higher selectivity in favour of suberin extraction. Residual cork from different organosolv processes was characterised by FTIR and 13C solid-state NMR. The latter technique provided some valuable information about both process selectivity and cork morphology, particularly with respect to the positioning of suberin macromolecules in the cell wall.