Search results for "Catalysis"
showing 10 items of 5944 documents
Cooperativity of H-bonding and anion–π interaction in the binding of anions with neutral π-acceptors
2012
A rare anion-π complex between bromide and a neutral receptor is reported and related receptor systems are studied with a series of anions. The interaction is observed in the solid state and in solution, and further evidence for it is obtained by a computational study.
Chiral Monofluorobenzyl Carbanions: Synthesis of Enantiopure β‐Fluorinated β‐Phenylethylamines
2011
The preparation of a stabilized monofluorobenzyl carbanion by means of a remote homochiral sulfinyl group and its completely stereoselective reactions with N-p-tolylsulfinylimines are described. The use of these reactions followed by the simultaneous removal of both chiral auxiliaries with tBuLi, which occurs without epimerization at the benzylic position, provides the quickest entry to enantiomerically pure β-fluorinated β-phenylethylamines.
CH-Directed Anion-π Interactions in the Crystals of Pentafluorobenzyl-Substituted Ammonium and Pyridinium Salts
2010
Simple pentafluorobenzyl-substituted ammonium and pyridinium salts with different anions can be easily obtained by treatment of the parent amine or pyridine with the respective pentafluorobenzyl halide. Hexafluorophosphate is introduced as the anion by salt metathesis. In the case of the ammonium salt 4, water co-crystallisation seems to suppress effective anion-pi interactions of bromide with the electron-deficient aromatic system, whereas with salts 5 and 6 such interactions are observed despite the presence of water. However, due to asymmetric hydrogen-bonding interactions with ammonium side chains, the anion of 5 is located close to the rim of the pentafluorophenyl group (eta(1) interac…
Surface and Electronic Features of Fluorinated TiO 2 and Their Influence on the Photocatalytic Degradation of 1-Methylnaphthalene
2020
International audience; Surface fluorination improves the photocatalytic activity of TiO2, and the influences of various features of fluorinated TiO2 (TiO2–F) have often been discussed in the literature. The present paper addresses the changes induced by surface fluorination on the morphological, structural, surface, and electronic features of TiO2. In particular, X-ray diffraction, specific surface area analysis, and transmission and scanning electron microscopy give evidence that surface fluorination does not affect the structural properties and the morphology of TiO2 nanoparticles. In contrast, fluorination induces changes of surface and electronic properties. Chemical and thermogravimet…
A highly enantioselective abiotic receptor for malate dianion in aqueous solution
2006
The highly enantioselective molecular recognition of the malate dianion by a synthetic receptor in aqueous solution has been studied by potentiometric titrations, mass spectrometry (ESI-MS), diffusion measurements (PGSE NMR) and molecular modeling. Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es
[3.3]Ferrocenophanes with guanidine bridging units as multisignalling receptor molecules for selective recognition of anions, cations, and amino acid…
2007
The synthesis, electrochemical, and optical properties of a new [3.3]ferrocenophane framework in which two ferrocene subunits, with similar electronic environments, are linked through two substituted guanidine moieties, are reported. The receptors 4-7 have been prepared in good yields by the reaction of bis(carbodiimide) 3 with primary amines. This architecture is exceptionally "tunable" because a variety of "legs" may be appended to the basic [3.3]ferrocenophane scaffold to give a wide range of signaling units. These receptors show remarkable ion-sensing properties, due to the presence of a redox active unit (ferrocene), and an amphoteric binding site (guanidine). In this nitrogen-rich str…
Borate-driven gatelike scaffolding using mesoporous materials functionalised with saccharides.
2009
We report the development of an MCM-41 mesoporous support that is functionalised with saccharides at the pore outlets and contains the dye [Ru(bipy)(3)](2+) in the pores (solid S1; bipy = 2,2'-bipyridyl). For this hybrid system, the inhibition of mass transport of the dye from the pore voids to the bulk solution in the presence of borate is demonstrated in water at neutral pH. The formation of the corresponding boroester derivative is related to the selective reaction of borate with the appended saccharides. This control is selective and only anion borate, among several anions and cations, can act as a molecular tap and inhibit the delivery of the entrapped guest. Additionally, the S1-borat…
Synthesis, reactivity, and computational analysis of halophosphines supported by dianionic guanidinate ligands.
2012
The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo- and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding N-heterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide, and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P-N bond of the P-N-…
Sterically geared tris-thioureas; transmembrane chloride transporters with unusual activity and accessibility
2015
Tris-N-arylthioureas derived in one step from 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene are remarkably effective anion carriers. With optimised aryl substituents their activities come close to the best currently known, suggesting that they might find use as readily available standards in anion transport research.
Facilitated Anion Transport Induces Hyperpolarization of the Cell Membrane That Triggers Differentiation and Cell Death in Cancer Stem Cells
2015
Facilitated anion transport potentially represents a powerful tool to modulate various cellular functions. However, research into the biological effects of small molecule anionophores is still at an early stage. Here we have used two potent anionophore molecules inspired in the structure of marine metabolites tambjamines to gain insight into the effect induced by these compounds at the cellular level. We show how active anionophores, capable of facilitating the transmembrane transport of chloride and bicarbonate in model phospholipid liposomes, induce acidification of the cytosol and hyperpolarization of plasma cell membranes. We demonstrate how this combined effect can be used against canc…