Search results for "SELECTIVITY"
showing 10 items of 1148 documents
GraftFast Surface Engineering to Improve MOF Nanoparticles Furtiveness
2018
International audience; Controlling the outer surface of nanometric metal–organic frameworks (nanoMOFs) and further understanding the in vivo effect of the coated material are crucial for the convenient biomedical applications of MOFs. However, in most studies, the surface modification protocol is often associated with significant toxicity and/or lack of selectivity. As an alternative, how the highly selective and general grafting GraftFast method leads, through a green and simple process, to the successful attachment of multifunctional biopolymers (polyethylene glycol (PEG) and hyaluronic acid) on the external surface of nanoMOFs is reported. In particular, effectively PEGylated iron trime…
Benzo-Fused Periacenes or Double Helicenes? Different Cyclodehydrogenation Pathways on Surface and in Solution
2019
Controlling the regioselectivity of C-H activation in unimolecular reactions is of great significance for the rational synthesis of functional graphene nanostructures, which are called nanographenes. Here, we demonstrate that the adsorption of tetranaphthyl- p-terphenyl precursors on metal surfaces can completely change the cyclodehydrogenation route and lead to obtaining planar benzo-fused perihexacenes rather than double [7]helicenes during solution synthesis. The course of the on-surface planarization reactions is monitored using scanning probe microscopy, which unambiguously reveals the formation of dibenzoperihexacenes and the structures of reaction intermediates. The regioselective pl…
Halloysite Nanotube with Fluorinated Lumen: Non-Foaming Nanocontainer for Storage and Controlled Release of Oxygen in Aqueous Media
2014
Halloysite clay nanotubes were selectivity modified by adsorbing perfluoroalkylated anionic surfactants at the inner surface. The modified nanotubes formed kinetically stable dispersions due to the enhanced electrostatic repulsions exercised between the particles. We proved that the modified nanotubes can be used as non-foaming oxygen nanocontainers in aqueous media. The gas release from supersaturated dispersions can be controlled by external stimuli and system composition. In conclusion, we managed to put forward an easy strategy to develop smart materials from natural nanoclays, which can endow important applications like the storage and delivery of gas.
Synthesis of toxyloxanthone B
2014
A synthesis of the naturally occurring xanthone toxyloxanthone B is described, in which the key step is the regioselective addition of a methyl salicylate to a substituted benzyne, followed by cyclization of the intermediate aryl anion to form the xanthone, the regiochemistry of the aryne addition being confirmed by X-ray crystallography. Subsequent introduction of the pyran ring by [3,3]-rearrangement and deprotection completed the synthesis.
Selectivity of cyclodextrins as a parameter to tune the formation of pseudorotaxanes and micelles supramolecular assemblies. A systematic SANS study
2011
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. We studied the formation of polypseudorotaxanes formed with cyclodextrins (CDs) threading a copolymer chain that forms self-assembled structures in water. The size of the CD cavity was chosen such that it is block selective with respect to the formation of inclusion complexes and therefore in terms of altering the structure of the copolymer self-assemblies in a systematic fashio…
Synthesis, characterization and X-ray structure of heterocyclic systems prepared via 1,3-dipolar cycloaddition of nitrile oxides with benzimidazolone
2018
Abstract We report here a one-step synthesis of the new isoxazolyl-benzimidazolones and isoxazolinyl-benzimidazolones by 1,3-dipolar cycloaddition of the p-substituted benzonitrile oxides and mesitonitrile oxide with 1-cyclohex-1-en-1-yl-3-propargyl-benzimidazolone or 1-cyclohex-1-en-1-yl-3-allyl-benzimidazolone. In all cases these cycloadditions are completely regio- and chemoselective. The structures of new cycloadducts obtained are elucidated by their analytical and spectral data. The relative stereochemistry of the cycloadduct 8 was confirmed by single crystal X-ray analysis.
A DFT study of the role of Lewis acid catalysts in the mechanism of the 1,3-dipolar cycloaddition of nitrile imines towards electron-deficient acrylo…
2012
Abstract The role of the Mg complex formation in the reaction rate and regioselectivity of the 1,3-dipolar cycloaddition (13DC) reactions of nitrile imines (NIs) towards electron-deficient methacryloylpyrazolidinones has been theoretically studied using DFT methods at the B3LYP/6-31G * level. These 13DC reactions have an asynchronous concerted mechanism with a low polar character, displaying a high C regioselectivity induced by a steric repulsion between the phenyl substituent present at the C3 carbon of the NIs and the pyrazolidinone appendage present in the methacryloyl derivative, which increases with the formation of the bulky Mg–methacryloylpyrazolidinone complex. Solvent effect has be…
The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Exper…
2021
The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol−1 and an exergonic character of 28.4 kcal·mol−1 that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite P…
Synthesis of the new ring system pyrrolizino[2,3-b]indol-4(5H)-one
2011
Derivatives of the new ring system pyrrolizino[2,3-b]indol-4(5H)-one were prepared in four steps starting from substituted benzonitriles bearing a functionalized amino group in the adjacent position. The unsubstituted- and the dimethoxy-pyrrolizinoindolones 5a and 5b exhibited modest activity against the HL-60(TB) human leukemia cell line, whereas the N-methylated dimethoxy-pyrrolizinoindolone 6b showed to be selective against MOLT-4 leukemia, A549/ATCC, HOP-92, and NCI-H460 non-small cell lung cancer, and CAKI-1 renal cancer cell lines.
A DFT study for the regioselective 1,3-dipolar cycloadditions of nitrile N-oxides toward alkynylboronates
2003
Abstract The mechanism for the 1,3-dipolar cycloaddition of benzonitrile oxide toward ethynyl and propynylboronate has been studied by using density functional theory (DFT) at B3LYP/6-31G* level. These cycloadditions are concerted [3+2] processes. The presence of the two oxygens on the boronic ester precludes the participation of the boron atom on [3+3] processes. The two regioisomeric channels associated to the formation of the isoxazoles bearing the boronic ester unit on the 4- or 5-positions have been characterized. The B3LYP/6-31G* activation parameters are in acceptable agreement with the experiments, allowing to explain the factors controlling these regioselective cycloadditions.