Search results for "polymer chemistry"

1984

Alkaline hydrolyses of anionic phenyl esters such as 4-acetoxy-3-nitrobenzoic acid and 4-butyryloxy-3-nitrobenzoic acid were examined in the presence of cationic and polymeric liposomes, liposomes of low molecular weight compounds, and micelles. All the additives accelerate the reaction due to the hydrophobic interaction between substrates and additives and the electrostatic interaction both between substrates and additives and between OH− and additives. In the Arrhenius plots of the reactions catalyzed by the liposomes, discontinuous regions were observed due to the phase transition of liposomes from the gel state to the liquid crystal state. Activation parameters ΔH≠, ΔS≠ and ΔV≠ for thes…

Gradientenabhängigkeit der Viskosität verdünnter Lösungen von Fadenmolekülen

1964

Es wird uber die Gradientenabhangigkeit der Viskositat von Polymeren mit hohem Molekulargewicht in Losungsmitteln ublicher Viskositat berichtet. Die Ermittlung von [η] fur verschwindenden Gradienten [η]G→0 und besonders fur sehr hohe Gradienten [η]G→∞ wird diskutiert.

Complexation of M3+Lanthanide Cations by Calix[4]arene-CMPO Ligands: A Molecular Dynamics Study in Methanol Solution and at a Water/Chloroform Interf…

2000

Abstract We report a molecular dynamics study on the 1:1 M3+ lanthanide (La3+, Eu3+ and Yb3+) inclusion complexes of an important extractant molecule L: a calix[4]arene-tetraalkyl ether substituted at the wide rim by four NH-C(O)-CH2-P(O)Ph2 arms. The M(NO3)3 and MCl3 complexes of L are compared in methanol solution and at a water / chloroform interface. In the different environments the coordination sphere of M3+ involves the four phosphoryl oxygens and three to four loosely bound carbonyl oxygens of the CMPO-like arms. Based on free energy simulations, we address the question of ion binding selectivity in pure liquid phases and at the liquid-liquid interface where L and the complexes are …

1976

The phenomenon of “true cosolvency”, which has only recently been observed in the system acetone/diethyl ether/polystyrene (AC/DEE/PS), is investigated with regard to its pressure dependence and compared with the thermodynamic behaviour of the corresponding binary sub-systems. For the determination of the limits of complete solubility, a pressure apparatus was used which had been constructed, in order to measure the turbidity of fluids in the temperature range of −70 to +500°Cand in the pressure range of 1 to 4000 bar (105 to 4·108 Nm−2). The critical line observed for the system DEE/PS (MPS=20400) looks similar to that reported for AC/PS in the literature, i.e. the upper critical solution …

Synthesis of hyperbranched poly(tert-butyl acrylate) by self-condensing atom transfer radical polymerization of a macroinimer

2000

Using 2-hydroxyethyl α-bromoisobuty-rate as initiator, atom transfer radical polymerization (ATRP) of tert-butyl acrylate leads to poly(tert-butyl acrylate) (PtBA) with a hydroxyl group at one and a bromine atom at the other end. Esterification of the hydroxyl group of these heterotelechelic polymers with acryloyl chloride yields PtBA (M n = 3060) with a polymerizable double bond at one end and a bromine atom at the other end which can act as an initiator in ATRP (macroinimer). Self-condensing ATRP of such a macroinimer leads to hyperbranched or highly branched PtBA. The polymer was characterized by GPC viscosity measurements. Even at M w = 78800, a rather low polydispersity index of M w M …

Mechanism of anionic polymerization of methyl methacrylate in the presence of aluminium alkyls

1995

Methyl methacrylate was polymerized with tert-butyl lithium in the presence of triethylaluminium or triisobutylaluminium at 78°C in toluene. As indicated by GPC and MALDI-TOF mass spectrometry, the polymerization is accompanied by side reactions. The lower oligomers were fractionated by distillation and characterised by NMR, FT-IR, UV and electron impact (EI) mass spectrometry. All these data show that part of the polymer chains are carrying exactly one tert-butyl isoprenyl ketone unit. In order to avoid the formation of tert-butyl isoprenyl ketone a molar ratio of Al/Li>2 is necessary.

New copolymers graft of α,β-poly(N-2-hydroxyethyl)-d,l-aspartamide obtained from atom transfer radical polymerization as vector for gene delivery

2012

Abstract New cationic α,β-poly(N-2-hydroxyethyl)- d , l -aspartamide (PHEA) graft copolymers were synthesized by ATRP, using diethylamino ethyl methacrylate (DEAEMA) as monomer for polymerization, yielding polycations (PHEA-pDEAEMA) able to condense DNA. Then, consecutive ATRP conditions were set up on PHEA-pDEAEMA to obtain copolymers containing also hydrophilic chains (PHEA-IB-pDMAEMA-pPEGMA) able to improve biocompatibility of polyplexes and to provide them stealth properties. Agarose gel studies showed that the copolymers effectively condensed plasmid DNA to form polyplexes. Light scattering studies were used to analyze the size and the ζ -potential of these polyplexes, showing that cop…

Tetraiodoethynyl resorcinarene cavitands as multivalent halogen bond donors

2014

The first examples of iodoethynyl resorcinarene cavitands as rigid 3D halogen bond (XB) donor molecules are presented. These concave macrocycles form strong, RXB = 0.78–0.83, halogen bonds with dioxane oxygen, pyridine nitrogen and a bromide anion in tetraproropyl ammonium bromide resulting in deep cavity cavitand structures.

Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl–salophen receptors enhanced by anion–π Interactions

2016

The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron- deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-p interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding.

Calix[4]arene-functionalized naphthalene and perylene imide dyes.

2002

[reaction: see text] Calix[4]arenes bearing one, two, or four 1,8-naphthyl imide groups at the wide rim and bis-calix[4]arenes connected via perylene-bisimide dye spacers have been synthesized. The low-temperature NMR spectrum of the tetranaphthylimide suggests, in agreement with a crystal structure, a C2-symmetrical pinched cone conformation stabilized via face-to-face pi-pi interactions between opposite naphthylimide groups. UV-vis and fluorescence studies have been carried out for the perylene bis-calix[4]arene dyes.