Fernando M. J. Domingues

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.

Phenolic constituents from the core of Kenaf (Hibiscus cannabinus)

Four lignans, boehmenan H [2-(4-hydroxy-3-methoxyphenyl)-5-[3-(4-hydroxy-3-methoxycinnamoyloxy)propyl]-3-hydroxymethyl-7-methoxybenzodihydrofuran], boehmenan K [2-(4-hydroxy-3-methoxyphenyl)-5-[3-(4-hydroxycinnamoyloxy)-1-propenyl]-3-(4-hydroxy-3-methoxycinnamoyloxymethyl)-7-methoxybenzodihydrofuran], threo-carolignan H [threo-1-(4-hydroxy-3-methoxyphenyl)-2-[4-[3-(4-hydroxy-3-methoxycinnamoyloxy)propyl]-2-methoxyphenoxy]-1,3-propanodiol], and threo-carolignan K [threo-1-(4-hydroxy-3-methoxyphenyl)-3-(4-hydroxy-3-methoxycinnamoyloxy)-2-[4-[3-(4-hydroxycinnamoyloxy)-1-propenyl]-2-methoxyphenoxy]-1-propanol] as well as several other lignans, aldehydes and a tyramine derivative were isolated from the acetone extract of core of kenaf (Hibiscus cannabinus). All the structures were established by spectroscopic methods. The hitherto unreported 13C NMR spectra of some compounds are also presented and discussed. 2D NMR techniques have allowed the revision of certain previously reported 13C NMR assignments of some scarce naturally occurring compounds.

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.

Amphiphilic phthalocyanine-cyclodextrin conjugates for cancer photodynamic therapy.

Three phthalocyanines (Pcs) conjugated with α-, β- and γ-cyclodextrins (CDs) were prepared and their application as photosensitizer (PS) agents was assessed by photophysical, photochemical and in vitro photobiological studies. The photoactivity of Pc-α-CD and Pc-γ-CD ensures their potential as PDT drugs against UM-UC-3 human bladder cancer cells.

Lignanamides and other phenolic constituents from the bark of kenaf (Hibiscus cannabinus)

Two new acyclic phenylpropane lignanamides, grossamide K and erythro-canabisine H, and the naphthol glucoside 2,5-dimethyl-3-O-beta-D-glucopyranosylnaphthol, along with six known compounds were isolated from the acetone extract of bark of Hibiscus cannabinus. All structures were established by spectroscopic methods including 2D NMR techniques, which allowed the correction of certain previously reported 13C NMR assignments of grossamide.

Chemical composition of the light petroleum extract of Hibiscus cannabinus bark and core

GC/MS studies of the light petroleum extracts obtained from different morphological regions of kenaf (Hibiscus cannabinus) showed large differences between the composition of the bark and of the core. The non-polar lipid constituents were essentially fatty acids (30.7% in bark; 53.3% in core), long chain alcohols (19.3% in bark), alkanes (22.0% in bark), sterols (12.5% in bark; 25.4% in core) and triterpenes (11.2% in bark). Octacosanyl eicosanoate (15.7%) was detected only in the bark extract and was identified by NMR and MS experiments, and by GC/MS after transesterification. Motiol, stigmast-4-en-3,6-dione (both reported here for the first time in the genus Hibiscus), β-sitosterol and stigmast-4-en-3-one were isolated by TLC and their structures confirmed by NMR experiments and by MS. The NMR structural characterisations reported permit the correction of some previously recorded 13C NMR data. Copyright

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.

Triterpenes from Acacia Dealbata

Abstract From the leaves, flowers and seeds of A. dealbata four lupene type triterpenes, lupenone, lupeol, lupenyl palpimate and lupenyl cinnamate, not previously reported in this genus, have been isolated. Their structures were established by spectroscopic means and by comparison with literature references.

CHLOROSULFONATION OF N-ARYLMALEIMIDES

Abstract N-phenylmaleimides, o-, m-and p-substituted (1) reacted with excess chlorosulfonic acid to give the corresponding sulphonyl chlorides (2–5). These were condensed with amines and phenols to give derivatives (7–29) which underwent hydrolysis or ammonolysis to give respectively the sulfamoyl maleamic acids (31–34) and sulfamoyl maleamides (35–39).

Basic density and pulp yield relationship with some chemical parameters in eucalyptus trees

The objective of this work was to evaluate the use of basic density and pulp yield correlations with some chemical parameters, in order to differentiate an homogeneous eucalyptus tree population, in terms of its potential for pulp production or some other technological applications. Basic density and kraft pulp yield were determined for 120 Eucalyptus globulus trees, and the values were plotted as frequency distributions. Homogenized samples from the first and fourth density quartiles and first and fourth yield quartiles were submitted to total phenols, total sugars and methoxyl group analysis. Syringyl/guaiacyl (S/G) and syringaldehyde/vanillin (S/V) ratios were determined on the kraft lignins from wood of the same quartiles. The results show the similarity between samples from high density and low yield quartiles, both with lower S/G (3.88-4.12) and S/V (3.99-4.09) ratios and higher total phenols (13.3-14.3 g gallic acid kg-1 ). Woods from the high yield quartile are statistically distinguished from all the others because of their higher S/G (5.15) and S/V (4.98) ratios and lower total phenols (8.7 g gallic acid kg-1 ). Methoxyl group and total sugars parameters are more adequate to distinguish wood samples with lower density.