Search results for "Colloid"
showing 10 items of 1288 documents
Postsynthetic Approach for the Rational Design of Chiral Ferroelectric Metal–Organic Frameworks
2017
International audience; Ferroelectrics (FEs) are materials of paramount importance with a wide diversity of applications. Herein, we propose a postsynthetic methodology for the smart implementation of ferroelectricity in chiral metal−organic frameworks (MOFs): following a single-crystal to single-crystal cation metathesis, the Ca2+ counterions of a preformed chiral MOF of formula Ca6II{CuII24[(S,S)-hismox]12(OH2)3}·212H2O (1), where hismox is a chiral ligand derived from the natural amino acid l-histidine, are replaced by CH3NH3+. The resulting compound, (CH3NH3)12{CuII24[(S,S)-hismox]12(OH2)3}·178H2O (2), retains the polar space group of 1 and is ferroelectric below 260 K. These results op…
Phosphido- and Amidozirconocene Cation-Based Frustrated Lewis Pair Chemistry
2015
Methyl abstraction from neutral [Cp2ZrMe(ERR')] complexes 1 (E = N, P; R, R' = alkyl, aryl) with either B(C6F5)3 or [Ph3C][B(C6F5)4] results in the formation of [Cp2Zr(ERR')][X] complexes 2 (X(-) = MeB(C6F5)3(-), B(C6F5)4(-)). The X-ray structure of amido complexes [Cp2Zr(NPh2)][MeB(C6F5)3] (2d) and [Cp2Zr(N(t)BuAr)][B(C6F5)4] (2e', Ar = 3,5-C6H3(CH3)2) is reported, showing a sterically dependent Zr/N-π interaction. Complexes 2 catalyze the hydrogenation of electron-rich olefins and alkynes under mild conditions (room temperature, 1.5 bar H2). Complex 2e binds CO2, giving [Cp2Zr(CO2)(N(t)BuAr)]2[MeB(C6F5)3]2 (3e). Amido complex 2d reacts with benzaldehyde yielding [Cp2Zr(OCH2Ph)((OC)PhNPh2)…
Decoding the Consequences of Increasing the Size of Self-Assembling Tricarboxamides on Chiral Amplification
2019
A complete series of experimental and theoretical investigations on the supramolecular polymerization of chiral (1 and 2) and achiral (3) oligo(phenylene ethynylene) tricarboxamides (OPE-TAs) is reported. The performance of seargents-and-soldiers (SaS) and majority rules (MR) experiments has allowed deriving a full set of thermodynamic parameters, including the helix reversal penalty (HRP) and the mismatch penalty (MMP). The results described illustrate the influence exerted by the number of stereogenic centers per monomeric unit and the temperature on the chiral amplification phenomenon. While the HRP decreases upon decreasing the number of chiral side chains, the MMP follows an opposite t…
Mechanism of the Oxidation of Sulfides by Dioxiranes. 1. Intermediacy of a 10-S-4 Hypervalent Sulfur Adduct
2002
Earlier studies established that dimethyldioxirane (1a) reacts with sulfides 2 in two consecutive concerted electrophilic oxygen-transfer steps to give first sulfoxides 3 and then sulfones 4. The same sequential electrophilic oxidation model was assumed for the reaction of sulfides 2 with the strongly electrophilic methyl(trifluoromethyl)dioxirane (1b). In this paper we report on a systematic and general study on the mechanism of the reaction of simple sulfides 2 with DMDO (1a) and TFDO (1b) which provides clear evidence for the involvement of hypervalent sulfur species in the oxidation process. In the oxidation of sulfides 2a-c, diphenyl sulfide (2d), para-substituted aryl methyl sulfides …
Viscometric behaviour of polymer blends based on poly (vinylidene fluoride)
1994
The viscosity behaviour of dilute dimethylformamide solutions of poly(vinylidene fluoride)-poly (methyl methacrylate) and poly(vinylidene fluoride)-polystyrene has been studied at 25°C. The polymer concentration ranges are such that neither phase separation nor microgel formation occurs, although we are very close to theta conditions. The intrinsic viscosity and viscosity interaction parameter of the ternary mixtures have been calculated. The estimation of the compatibility of the above polymer pairs has been studied based on: a) specific viscosities; b) viscosity interaction parameters, according to Krigbaum and Wall formalism, and c) viscosity interaction parameters of a system formed by …
Correlation between transport and equilibrium properties through the ternary interaction parameter for cosolvent and cononsolvent polymeric systems
1992
A study of the ternary polymer systems dimethyl formamide-ethyl acetate-polystyrene, chloroform-1,4 dioxane-polystyrene and tetrahydrofuran-chloroform-polystyrene was carried out by viscosity and light scattering at 298 K. A good correlation has been found between the excess intrinsic viscosity, unperturbed polymer dimensions, second virial coefficient and the excess Gibbs free energy by using a ternary interaction parameter, dependent on molecular weight. This modification enables the conversion between transport and equilibrium properties.
Soluble Complexes of Cobalt Oxide Fragments Bring the Unique CO2 Photoreduction Activity of a Bulk Material into the Flexible Domain of Molecular Sci…
2021
The deposition of metal oxides is essential to the fabrication of numerous multicomponent solid-state devices and catalysts. However, the reproducible formation of homogeneous metal oxide films or of nanoparticle dispersions at solid interfaces remains an ongoing challenge. Here we report that molecular hexaniobate cluster anion complexes of structurally and electronically distinct fragments of cubic-spinel and monoclinic Co3O4 can serve as tractable yet well-defined functional analogues of bulk cobalt oxide. Notably, the energies of the highest-occupied and lowest-unoccupied molecular orbitals (HOMO and LUMO) of the molecular complexes, 1, closely match the valence- and conduction-band (VB…
Bio-inspired surface modification of iron oxide nanoparticles for active stabilization in hydrogels
2020
Biological materials employ a variety of dynamic interactions in sophisticated composite structures to function adaptively on different time and length scales. Inspired by such designs we develop a novel surface modification approach to promote dynamic interactions between nanoparticles and polymer chains in physical and double network hydrogels. Physical hydrogels are formed via reversible complexation of borate ions with poly(vinyl alcohol) (PVA) and chemical crosslinks are introduced by electron beam irradiation. Dopamine is used for surface modification of magnetic iron oxide nanoparticles (MNPs) in two different ways: the direct treatment results in anchoring via catechol groups, where…
Über eine Beziehung zwischen Verdünnunasentropie und Verdünnungsenthalpie in Lösungen von Polystyrol und Polymethylmethacrylat
1973
Durch Lichtstreuungsmessungen wurde der Entropieanteil und der Enthalpieanteil des 2. osmotischen Virialkoeffizienten (A2) von athermischen und exothermischen Losungen von Polystyrol (PS) und Polymethylmethacrylat (PMMA) bei 25°C und Normaldruck bestimmt. Zur Auffindung von athermischen und exothermischen Losungsmitteln fur diese Polymeren wurde die Temperaturabhangigkeit des STAUDINGERindex verwendet. Die ermittelten thermodynamischen Grosen A2, A2,S und A2,H ergeben zusammen mit fruheren Messungen eine beziehung, die nahezu unabhangig vom speziellen System ist. The second osmotic virial coefficient A2 and its entropic and enthalpic parts of athermal and exothermal solutions of polystyrene…