ABSTRACT
The synthesis and structural characterization of azahelicene platinum complexes obtained from cis-PtCl2(NCEt)(PPh3) and from ligands that differ in terms of both the position of the nitrogen atom and the number of fused rings are reported. These square-planar complexes of the general formula PtCl2(nHm)(PPh3) (n = 4, 5; m = 5, 6) display mainly a cis configuration. However, by X-ray crystallographic analysis, we show that for both PtCl2(4H6)(PPh3) and PtCl2(5H6)(PPh3) there is chirality control of the cis/trans stereochemistry. Indeed, starting from a racemic mixture of aza[6]helicene, platinum complexes with a cis configuration are invariably obtained, and the more thermodynamically stable trans isomers are formed when using enantiopure ligands. We further corroborated these results by NMR analysis in solution.
ABSTRACT
Oil-filled microcapsules of kraft lignin were synthesized by first creating an oil in water emulsion followed by a high-intensity, ultrasound-assisted cross-linking of lignin at the water/oil interface. The rationale behind our approach is based on promoting documented lignin hydrophobic interactions within the oil phase, followed by locking the resulting spherical microsystems by covalent cross-linking using a high intensity ultrasound treatment. As further evidence in support of our rationale, confocal and optical microscopies demonstrated the uniformly spherical morphology of the created lignin microparticles. The detailed elucidation of the cross-linking processes was carried out using gel permeation chromatography (GPC) and quantitative (31)P NMR analyses. The ability of lignin microcapsules to incorporate and release Coumarin-6 was evaluated in detail. In vitro studies and confocal laser scanning microscopy analysis were carried out to assess the internalization of capsules into Chinese hamster ovary (CHO) cells. This part of our work demonstrated that the lignin microcapsules are not cytotoxic and readily incorporated in the CHO cells.
Subject(s)
Capsules/chemistry , Capsules/chemical synthesis , Lignin/chemistry , Sonication , Animals , CHO Cells , Capsules/administration & dosage , Capsules/metabolism , Coumarins/administration & dosage , Coumarins/metabolism , Cricetulus , Hydrophobic and Hydrophilic Interactions , Lignin/administration & dosage , Lignin/chemical synthesis , Lignin/metabolism , Molecular Structure , Particle Size , Surface Properties , Thiazoles/administration & dosage , Thiazoles/metabolismABSTRACT
Tannins and flavonoids are secondary metabolites of plants that display a wide array of biological activities. This peculiarity is related to the inhibition of extracellular enzymes that occurs through the complexation of peptides by tannins. Not only the nature of these interactions, but more fundamentally also the structure of these heterogeneous polyphenolic molecules are not completely clear. This first paper describes the development of a new analytical method for the structural characterization of tannins on the basis of tannin model compounds employing an in situ labeling of all labile H groups (aliphatic OH, phenolic OH, and carboxylic acids) with a phosphorus reagent. The ³¹P NMR analysis of ³¹P-labeled samples allowed the unprecedented quantitative and qualitative structural characterization of hydrolyzable tannins, proanthocyanidins, and catechin tannin model compounds, forming the foundations for the quantitative structural elucidation of a variety of actual tannin samples described in part 2 of this series.
Subject(s)
Anti-Infective Agents/chemistry , Chemistry, Agricultural/methods , Models, Chemical , Tannins/chemistry , Anti-Infective Agents/metabolism , Catechin/chemistry , Catechin/metabolism , Hydrolyzable Tannins/chemistry , Hydrolyzable Tannins/metabolism , Isotope Labeling , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Phosphorus Isotopes , Proanthocyanidins/chemistry , Proanthocyanidins/metabolism , Solubility , Tannins/metabolismABSTRACT
An unprecedented analytical method that allows simultaneous structural and quantitative characterization of all functional groups present in tannins is reported. In situ labeling of all labile H groups (aliphatic and phenolic hydroxyls and carboxylic acids) with a phosphorus-containing reagent (Cl-TMDP) followed by quantitative ³¹P NMR acquisition constitutes a novel fast and reliable analytical tool for the analysis of tannins and proanthocyanidins with significant implications for the fields of food and feed analyses, tannery, and the development of natural polyphenolics containing products.
Subject(s)
Antioxidants/chemistry , Chemistry, Agricultural/methods , Hydrolyzable Tannins/chemistry , Proanthocyanidins/chemistry , Antioxidants/metabolism , Catechin/chemistry , Catechin/metabolism , Food Analysis/methods , Hydrolyzable Tannins/metabolism , Isotope Labeling , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Phosphorus Isotopes , Proanthocyanidins/metabolism , SolubilityABSTRACT
The degree of polymerization (DP) of softwood and hardwood milled wood lignin samples and their branching degrees were quantitatively evaluated by a novel end-group titration approach composed of QQ-HSQC, (31)P NMR, and DFRC coupled with (31)P NMR analysis techniques. The DP of lignin can be calculated when the C9 formula, the amounts of phenolic groups, pinoresinol (ß-ß), diphenylethane (ß-1), and phenolic diphenyl (5-5') lignin subunits have been determined. Data on the degree of polymerization of lignin obtained by NMR techniques were not affected by supramolecular aggregation processes. (31)P NMR analysis coupled with DFRC and QQ-HSQC allowed a detailed evaluation of the occurrence of condensed units in lignin and showed the terminal nature of diphenyl ether and diphenyl subunits. The resulting data unequivocally show that milled wood lignin is a linear oligomer.
Subject(s)
Lignin/chemistry , Wood/chemistry , Acetylation , Fagus/chemistry , Magnetic Resonance Spectroscopy , Molecular Weight , Oxidation-Reduction , Phenols/chemistry , Picea/chemistry , Sulfotransferases , Carbohydrate SulfotransferasesABSTRACT
A novel multienzyme biocatalyst, based on coimmobilization of the laccase and horseradish peroxidase by cross linking and layer-by-layer coating with polyelectrolyte, was designed, synthesized and applied at the development of an oxidative cascade process on lignin. The efficiency and specificity of the new LbL-multienzyme system, the occurrence of a synergy of the co-immobilized enzymes, the lignin oxidation pathway and the nature of the structural modifications occurred in treated lignins have been investigated in the present effort by means of GPC analysis and quantitative (31)P NMR techniques.
