Search results for "Mphi"

Spectroscopic and structural characterization of pure and FeCl3-containing tri-n-butyl phosphate

2014

The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3 − n ] n+ and FeCl4 − complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attri…

1995

Polystyrene-block-poly-1-azabicyclooctane[4,2,0] has been modified by protonation or alkylation of the polyamine moiety. Short chain alkyl iodides lead to quantitatively quarternized products while longer alkyl chains or alkyl-bromides give incomplete conversion. The viscosimetric behavior of the charged blockcopolymers is dominated by the polyelectrolyte block although the polyelectrolyte effect is drastically reduced by the presence of the polystyrene block. The blockcopolymers are insoluble in water, but concentrated solutions of the polymers in DMF can be diluted with any amount of water without any precipitation. Although the blockcopolymers have an amphiphilic structure they do not ex…

Role of Topology and Amphiphilicity for Guest Encapsulation in Functionalized Hyperbranched Poly(ethylenimine)s

2004

The promising potential of dendrimers in a variety of areas, such as catalysis, materials science and biomedicine is related to their globular shape, large number of modifiable surface functionalities and the presence of internal reservoirs.1 Their use in liquidliquid-phase transfer protocols, based on the encapsulation of guest molecules as drug delivery vehicles for pharmaceutical application, represents an important issue.2 Unfortunately, dendrimer synthesis is timeconsuming, which currently limits practical use to laboratory scale. For that reason, hyperbranched polymers prepared from ABm-type monomers in one-step processes have gained increasing interest.3 The development of the slow m…

Combining oxyanionic polymerization and click-chemistry: a general strategy for the synthesis of polyether polyol macromonomers

2014

We describe a synthetic pathway to tailor-made amphiphilic macromonomers by a combination of anionic ring-opening polymerization and copper-catalyzed azide–alkyne cycloaddition (CuAAC). Linear polyglycerol and poly(glyceryl glycerol) were synthesized in a controlled manner by anionic ring-opening polymerization of ethoxyethyl glycidyl ether or isopropylidene glyceryl glycidyl ether, respectively, with narrow and monomodal molecular weight distributions (Mw/Mn < 1.20) and molecular weights ranging from 850 g mol−1 to 2500 g mol−1. After end-capping with propargyl bromide and removal of the protecting groups, the hydrophilic precursors were quantitatively clicked to a series of hydrophobic az…

Structural variations in amphiphiles: Discoidal multivalent cations

1986

Fourteen cationic multipolar amphiphiles have been synthesized with pyridinium or trimethylammonium head groups. The hydrophobic cores are planar ring systems (benzene or triphenylene) to which two, three, four, or six decylene or undecylene alkyl chains are attached by ester linkages. The hydrophilic head groups are bound to the outer ends of the alkyl chains.

Oxidation-responsive polyether block copolymers lead to non-ionic polymer surfactants with multiple amine N-oxides

2019

Block copolymers consisting of a nonpolar poly(propylene oxide) block and a poly(glycidyl amine) block were prepared by anionic ring-opening polymerization (AROP). The tertiary amine groups of the block copolymers were quantitively transformed into the corresponding zwitterionic amine N-oxides, as confirmed by 1H NMR and 15N NMR spectroscopy. This leads to strongly amphiphilic polyether block copolymers with multiple N-oxides. Full oxidation of the amine groups was also possible in situ in an emulsion, demonstrating the oxidation-responsive character of this new class of non-ionic polymeric surfactants.

Consecutive Selective Adsorption of Pentamidine and Phosphate Biomolecules on a Self-Assembled Layer:  Reversible Formation of a Chemically Selective…

1996

In situ ellipsometric film thickness measurements, FT-IR external reflectance spectroscopy, and potentiometric measurements indicated that the amphiphile pentamidine (PAM), a bisbenzamidine, associated by self-assembly with a preformed self-assembled monolayer of a mercaptoalkanoic acid on gold. The structural properties of PAM and the nature of the substrate were ideal for the formation of a densely packed monolayer. This process was fully reversible, as demonstrated by changing the pH of the surrounding medium. Thus, disassembly−reassembly occurred when the pH was cycled between 8.7 and 3. The bilayer structure, featuring a positively charged amidinium surface, was subsequently used for s…

Monolayers of Bolaform Amphiphiles: Influence of Alkyl Chain Length and Counterions

1994

We have prepared self-assembled monolayers of novel cationic bolaform amphiphiles on negatively charged substrates. Most of these amphiphiles form smooth, defect-free monolayers which can be used to reverse the substrate surface charge and thus allow subsequent adsorption of anionic molecules and construction of multilayers. Atomic force microscopy, surface force measurement, and surface plasmon spectroscopy were combined to probe the molecular orientation and ordering, mechanical properties, and surface electrical properties of the monolayers. In addition, the amphiphile aggregation behavior at an air-water interface was studied by surface tension measurement, and lyotropic phase behavior …

Synthetic approaches towards new polymer systems by the combination of living carbocationic and anionic polymerizations

1996

This study summarizes recent efforts to obtain by combination of living carbocationic and anionic polymerizations block copolymers which are potential precursors for building new well-defined polymeric architectures with microphase separated morphology. Living carbocationic polymerization (LCCP) yields telechelic polyisobutylene (PIB) chains with a variety of useful endgroups, such as tert-chlorine, isopropenyl, primary hydroxyl, tolyl etc. When tolyl-ended PIB was used as precursor for macroinitiator of living anionic polymerization of 2-(tert-butyldimethylsilyloxy)ethyl methacrylate (tBuMe2SiOEMA), mixtures of homopolymers and block copolymers were formed due to incomplete lithiation of t…

A clickable NHC–Au(i)-complex for the preparation of stimulus-responsive metallopeptide amphiphiles

2018

We report the synthesis of an alkyne functionalised NHC-Au(i)-complex which is conjugated with amphiphilic oligopeptides using a copper(i) catalysed cycloaddition. The resulting Au(i)-metalloamphiphiles are shown to self-assemble into charge-regulated stimulus-responsive supramolecular polymers in water via a weakly cooperative polymerisation mechanism.