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showing 10 items of 13546 documents

Total Synthesis of Lavendamycin by a [2+2+2] Cycloaddition

2011

The total synthesis of the bacterial-derived, pentacyclic, antitumor antibiotic lavendamycin has been achieved through a highly convergent strategy. The key step of this synthesis is a ruthenium-catalyzed [2+2+2] cycloaddition of an electron-deficient nitrile to an alkynyl-ynamide to prepare the carboline scaffold. The elaborate cycloaddition substrate is obtained in few steps by an N-ethynylation using alkynyliodonium salt chemistry and two palladium-catalyzed cross-coupling reactions. An efficient synthesis of a halogenated quinoline-5,8-dione building block starting from hydroquinone is presented.

inorganic chemicalsDiketoneNitrileHydroquinoneOrganic ChemistryRegioselectivityTotal synthesisChemical synthesisCycloadditionchemistry.chemical_compoundchemistryOrganic chemistryPhysical and Theoretical ChemistryLavendamycinEuropean Journal of Organic Chemistry
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Pumice-Supported Nickel Catalysts

1997

A series of nickel catalysts supported on pumice was prepared by precipitation and impregnation techniques. The influence of the calcination and reduction temperatures on the structural properties such as lattice parameters and particle dimensions of the oxide precursors and of the reduced catalysts was investigated by X-ray diffraction measurements. The effect of structural changes on the catalytic activity in the hydrogenation of carbon monoxide has been evaluated. The turnover frequencies, as well as product distributions, are discussed in terms of the influence of the support properties and of its interaction with the metal. Changes of the C2+yield over CH4yield ratio versus nickel disp…

inorganic chemicalsInorganic chemistryOxideSinteringchemistry.chemical_elementHeterogeneous catalysisCatalysislaw.inventionCatalysischemistry.chemical_compoundNickelchemistryTransition metallawCalcinationPhysical and Theoretical ChemistryCarbon monoxideJournal of Catalysis
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DFT insights into the oxygen-assisted selective oxidation of benzyl alcohol on manganese dioxide catalysts

2020

Abstract The reactivity pattern of the MnO2 catalyst in the selective aerobic oxidation of benzyl alcohol is assessed by density functional theory (DFT) analysis of adsorption energies and activation barriers on a model Mn4O8 cluster. DFT calculations predict high reactivity of defective Mn(IV) sites ruling a surface redox mechanism, L-H type, involving gas-phase oxygen. Bare and promoted (i.e., CeOx and FeOx) MnOx materials with high surface exposure of Mn(IV) sites were synthesized to assess kinetic and mechanistic issues of the selective aerobic oxidation of benzyl alcohol on real catalysts (T, 333–363 K). According to DFT predictions, the experimental study shows: i) comparable activity…

inorganic chemicalsInorganic chemistrychemistry.chemical_elementAlcoholManganese010402 general chemistry01 natural sciencesRedoxCatalysisInorganic Chemistrychemistry.chemical_compoundAdsorptionBenzyl alcoholMaterials ChemistryReactivity (chemistry)Physical and Theoretical ChemistryReaction mechanismBenzoic acidDFT analysi010405 organic chemistryActive siteorganic chemicalsMnO2 catalyst0104 chemical scienceschemistrySettore CHIM/03 - Chimica Generale E InorganicaBenzyl alcoholActive sites; Benzyl alcohol; DFT analysis; MnO; 2; catalyst; Reaction mechanism; Selective oxidationSelective oxidation
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Catalytic activity of solvated and unsolvated lanthanide halides in Friedel–Crafts acylations

2000

Abstract Anhydrous lanthanide halides — chlorides and bromides — can act as homogeneous catalysts of Friedel–Crafts acylations. The catalytic activity is related to the solubility of these anhydrous salts. More soluble THF or dioxane (Diox.) neodymium and samarium adducts are more active catalysts.

inorganic chemicalsLanthanideChemistryProcess Chemistry and Technologychemistry.chemical_elementHalideHomogeneous catalysisCatalysisCatalysisSamariumPolymer chemistryAnhydrousOrganic chemistryPhysical and Theoretical ChemistrySolubilityFriedel–Crafts reactionJournal of Molecular Catalysis A: Chemical
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Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.

2016

The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows …

inorganic chemicalsMagnetic Resonance SpectroscopyStereochemistryPyridinesPyridonesPotentiometric titrationProtonationChemistry Techniques Synthetic010402 general chemistry010403 inorganic & nuclear chemistryElectrochemistryCrystallography X-Ray01 natural sciencesMedicinal chemistryAntioxidantsCoordination complexInorganic Chemistrychemistry.chemical_compoundStructure-Activity RelationshipCoordination ComplexesHumansChelationPhysical and Theoretical ChemistryCell ProliferationChelating Agentschemistry.chemical_classificationLigandHydrogen-Ion Concentration0104 chemical scienceschemistryPotentiometrySpectrophotometry UltravioletCyclic voltammetryDerivative (chemistry)CopperHeLa CellsInorganic chemistry
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Influence of Ge doping level on the EPR signal of Ge(1), Ge(2) and E'Ge defects in Ge-doped silica

2011

Abstract We present an experimental investigation on the Ge doping level dependence of the Electron Paramagnetic Resonance (EPR) signal spectral features of the Ge(1), Ge(2) and E'Ge defects induced in Ge doped silica. We have studied samples produced by sol–gel or PCVD techniques and doped with different amounts of Ge up to 20% by weight. The samples were gamma or beta ray irradiated and successively they were thermally treated to isolate the EPR signals of the different point defects. The data show that the EPR line shapes of the Ge(1) and the Ge(2) centers are progressively modified for doping level higher than 1%, whereas the line shape of the E'Ge defect appears independent from the do…

inorganic chemicalsMaterials scienceAnalytical chemistrychemistry.chemical_elementGermaniumSilica paramagnetic point defects Ge-doped silicasilice drogata difetti di punto risonanza magneticalaw.inventionsymbols.namesakeraman spectroscopylawCondensed Matter::SuperconductivityBeta particleMaterials ChemistryIrradiationElectron paramagnetic resonanceSol-gelSettore FIS/01 - Fisica SperimentaleDopingtechnology industry and agricultureCondensed Matter PhysicsCrystallographic defectElectronic Optical and Magnetic MaterialschemistryCeramics and Compositessymbolslipids (amino acids peptides and proteins)Condensed Matter::Strongly Correlated ElectronsRaman spectroscopyhuman activitiesJournal of Non-Crystalline Solids
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Studies of structural composition distribution heterogeneity in ethylene/1-hexene copolymers using thermal fractionation technique (SSA)

2005

Abstract Investigations into the compositional heterogeneity of ethylene/1-hexene copolymers obtained with various zirconocene/MAO catalysts, either homogeneous or supported on inorganic carriers such as a complex of magnesium chloride with tetrahydrofuran or methyl alcohol, were conducted. The dependence between metallocene structure, as well as catalyst immobilization, and the compositional heterogeneity of the related products was investigated. It was found that the heterogeneity of copolymers is determined by the metallocene catalyst structure. The amount of peaks on the DSC thermograms of copolymers and their division increase with the increase of bulkiness of the ligand in the catalyt…

inorganic chemicalsMaterials scienceEthyleneMagnesiumchemistry.chemical_elementPost-metallocene catalystCondensed Matter PhysicsCatalysischemistry.chemical_compoundchemistryChemical engineeringPolymer chemistryCopolymerPhysical and Theoretical ChemistryZiegler–Natta catalystInstrumentationMetalloceneTetrahydrofuranThermochimica Acta
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Thermal Properties, Raman Spectroscopy and Tem Images of Neutron-Bombarded Graphite

2013

Neutron-irradiated graphite to a total dose of 3.6 × 1016 n cm−2 was studied by DSC, Raman spectroscopy and transmission electron microscopy (TEM). The Wigner energy of neutron-irradiated graphite was 9.5 J/g as measured by DSC; it was released with an exothermal peak at 220°C. The Raman spectroscopy has confirmed the expected effect caused by neutron irradiation of the graphite substrate. The TEM imaging has shown that neutron-irradiated graphite can be effectively exfoliated by sonication in comparison to pristine graphite, which under similar conditions does not exfoliate at all. The interstitial Frenkel defects in neutron-irradiated graphite are intercalated between the graphene layers …

inorganic chemicalsMaterials scienceSonicationAnalytical chemistrylaw.inventionsymbols.namesakelawneutrons irradiationGeneral Materials ScienceNeutronSettore CHIM/01 - Chimica AnaliticaGraphitePhysical and Theoretical ChemistryWigner effectSettore CHIM/02 - Chimica FisicaWigner energySettore CHIM/03 - Chimica Generale e Inorganicaintegumentary systemGrapheneOrganic ChemistrygrapheneGraphite neutrons irradiation graphene exfoliation Wigner energy Raman spectroscopy TEM imagingtechnology industry and agricultureGraphite neutrons irradiation graphene exfoliation Wigner energy Raman spectroscopyTEM imagingexfoliationExfoliation jointAtomic and Molecular Physics and OpticsTransmission electron microscopyRaman spectroscopyTEM imagingbiological sciencessymbolsGraphitelipids (amino acids peptides and proteins)Raman spectroscopy
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Barrier properties of chitosan coated polyethylene

2012

The transfer properties of chitosan coated polyethylene (PE) films were studied. The barrier properties of non coated PE were not affected by relative humidity changes. The presence of the hydrophilic chitosan layer acted as a water reservoir on the polyethylene film surface which significantly promoted its sensitivity to the water vapour. The water vapour permeability increased 1.85 times at a higher RH. Coated PE films showed more than two-order decrease in the oxygen permeability (PO2) and three-order-decrease in the carbon dioxide permeability (PCO2). When the chitosan coated PE surface was exposed to the water vapour, the PO2 and the PCO2 were significantly increased. However, the perm…

inorganic chemicalsMaterials sciencetechnology industry and agricultureFiltration and Separationrespiratory systemengineering.materialPermeationPolyethyleneBiochemistryrespiratory tract diseasesSolventChitosanOxygen permeabilitychemistry.chemical_compoundchemistryChemical engineeringPermeability (electromagnetism)chitosan; barrier; permeability; polyethylene coating; biopolymer; thermal propertiesPolymer chemistryengineeringGeneral Materials ScienceRelative humidityBiopolymerPhysical and Theoretical Chemistrycirculatory and respiratory physiologyJournal of Membrane Science
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Prolin-benzylester als chirale Hilfsgruppen in asymmetrischen 1,3-dipolaren Cycloadditionen mit Nitriloxiden

1990

Proline Benzyl Esters as Chiral Auxiliaries in Asymmetric 1,3-Dipolar Cycloadditions N-Acryloylproline benzyl ester (1b) reacts with nitrile oxides at temperatures from −78 to 0°C to give isoxazolines 4/5 with diastereomeric ratios of ca. 3:1 and with the (5S) isomer as the predominating. The corresponding N-methacryloylproline benzyl ester (1c) gives inferior results. The diastereoselectivity is not influenced by the temperature and the substituents of the nitrile oxides. To prove the absolute configuration of the predominating stereoisomer, a reaction sequence is developed which makes use of an enantioselective hydrolysis with pig liver esterase as the key step to generate an optically ac…

inorganic chemicalsNitrileChemistryStereochemistryorganic chemicalsOrganic ChemistryEnantioselective synthesisDiastereomerAbsolute configurationEsterasechemistry.chemical_compoundHydrolysis13-Dipolar cycloadditionPhysical and Theoretical ChemistryTriethylamineLiebigs Annalen der Chemie
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