6533b7dcfe1ef96bd1272176
RESEARCH PRODUCT
Increased conformational rigidity of humic substances by oxidative biomimetic catalysis
Pietro TagliatestaPellegrino ConteAlessandro Piccolosubject
conformationMagnetic Resonance SpectroscopySpectrophotometry InfraredPolymers and PlasticsDiffuse reflectance infrared spectroscopy (DRIFT)Biomimetic materialsaromatic compoundgel permeation chromatographyMolecular ConformationPhotochemistryIron compoundslaw.inventionPolymerizationenvironmental managementcovalent bondlawSize exclusion chromatographyBiomimetic catalysisBiomimeticsMaterials ChemistryOrganic chemistryHumic acidElectron paramagnetic resonanceInfrared spectroscopyChromatography High Pressure Liquidchemistry.chemical_classificationSettore CHIM/03 - Chimica Generale e InorganicaCarbon IsotopesChromatographyindustryCatalystsChemistrytetra(2articleelectrophoretic mobilitybiomimetic materialNuclear magnetic resonance spectroscopyunclassified drugConformationsacetic acidpriority journalCovalent bondSpectrophotometrySynthesis (chemical)High Pressure Liquidtechnology6 dichloro 3 sulfonatophenyl)porphyrinic acid derivativeInfraredOxidation-Reductionmolecular stabilityHumic materialsoxidationSettore AGR/13 - Chimica AgrariaSupramolecular chemistryBioengineeringcomplex mixturesCatalysisCatalysisdiffuse reflectance spectroscopyhumic substanceBiomaterialsalkyl etherElectron spin resonance spectroscopycomplex formationParticle SizeNuclear magnetic resonance spectroscopyHumic Substancesfree radicalbiomimetic oxidative humicelectron spin resonanceHigh performance size exclusion chromatography (HPSEC)ferrous chloridemolecular weightsolid statecarbon nuclear magnetic resonancePolymerizationSolubilitychemical structureOxidative coupling of methaneCatalysts; Conformations; Electron spin resonance spectroscopy; Infrared spectroscopy; Iron compounds; Nuclear magnetic resonance spectroscopy; Oxidation; Polymerization; Size exclusion chromatography; Solubility; Synthesis (chemical); Biomimetic catalysis; Diffuse reflectance infrared spectroscopy (DRIFT); High performance size exclusion chromatography (HPSEC); Humic materials; Biomimetic materials; acetic acid; alkyl ether; aromatic compound; biomimetic material; ferrous chloride; free radical; tetra(26 dichloro 3 sulfonatophenyl)porphyrinic acid derivative; unclassified drug; article; carbon nuclear magnetic resonance; catalysis; catalyst; chemical structure; complex formation; conformation; covalent bond; diffuse reflectance spectroscopy; electron spin resonance; electrophoretic mobility; environmental management; gel permeation chromatography; humic substance; industry; molecular stability; molecular weight; oxidation; polymerization; priority journal; solid state; technology; Biomimetics; Carbon Isotopes; Catalysis; Chromatography High Pressure Liquid; Electron Spin Resonance Spectroscopy; Humic Substances; Magnetic Resonance Spectroscopy; Molecular Conformation; Oxidation-Reduction; Particle Size; Spectrophotometry Infraredcatalystdescription
A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe(TDCPPS)Cl, was employed as a biomimetic catalyst in the oxidative coupling of terrestrial humic materials. High-performance size-exclusion chromatography (HPSEC), solid-state nuclear magnetic resonance (CPMAS-(13)C NMR), electron paramagnetic resonance (EPR), and diffuse reflectance infrared spectroscopy (DRIFT) were used to follow conformational and structural changes brought about in different humic materials by the oxidative coupling. Increase in apparent weight-average molecular weight (Mw(a)) occurred invariably for all humic substances with the oxidative polymerization catalyzed by Fe(TDCPPS)Cl. HPSEC further showed that the polymerization reaction turned the loosely bound humic supramolecular structures into more stable conformations which could no longer be disrupted by the disaggregating effect of acetic acid. DRIFT spectroscopy suggested the formation of new alkyl and aromatic ethers following the oxidative coupling with the biomimetic catalyst. CPMAS-(13)C NMR and EPR spectra suggested a reduced molecular mobility of humic components and enhanced stabilization of free radicals in larger oxidized fragments. All findings concur in indicating that the biomimetic catalysis by Fe(TDCPPS)Cl increased the molecular mass and chemical rigidity of humic materials by formation of intermolecular covalent bonds via a free-radical mechanism. The development of a technology based on oxidative polymerization by biomimetic catalysis may be of importance in controlling the properties and reactivity of humic matter for industrial and environmental applications.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2005-01-01 |