Physicochemical properties of pH-controlled polyion complex (PIC) micelles of poly(acrylic acid)-based double hydrophilic block copolymers and various polyamines.

The physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted of electrostatic complexes of two oppositely charged polyelectrolytes. The pH-sensitive micelles were obtained with double hydrophilic block copolymers containing a poly(acrylic acid) block linked to a modified poly(ethylene oxide) block and various polyamines (polylysine, linear and branched polyethyleneimine, polyvinylpyridine, and polyallylamine). The pH range of micellization in which both components are ionized was determined for each polyamine. The resulting PIC micelles were characterized using dynamic light scattering and small-angle X-ray scattering experiments (SAXS). The PIC micelles presented a core-corona nanostructure with variable polymer density contrasts between the core and the corona, as revealed by the analysis of the SAXS curves. It was shown that PIC micelle cores constituted by polyacrylate chains and polyamines were more or less dense depending on the nature of the polyamine. It was also determined that the density of the cores of the PIC micelles depended strongly on the nature of the polyamine. These homogeneous cores were surrounded by a large hairy corona of hydrated polyethylene oxide block chains. Auramine O (AO) was successfully entrapped in the PIC micelles, and its fluorescence properties were used to get more insight on the core properties. Fluorescence data confirmed that the cores of such micelles are quite compact and that their microviscosity depended on the nature of the polyamine. The results obtained on these core-shell micelles allow contemplating a wide range of applications in which the AO probe would be replaced by various cationic drugs or other similarly charged species to form drug nanocarriers or new functional nanodevices.

Interactions of surfactants with living cells. Induction of apoptosis by detergents containing a beta-lactam moiety.

The toxicity of new surfactants containing a beta-lactam ring has been established by studying their interaction with a hybridoma cell line. An hour of contact is sufficient to generate an apoptotic signal after two days of culture. Under the experimental conditions chosen for the experiments, surfactants have been divided into three categories: i) biocompatible and non-apogenic; ii) surfactants triggering an apoptotic signal without inducing cell necrosis; iii) surfactants triggering an apoptotic signal at low concentrations and destroying the cells by necrosis at higher concentrations. The necrosis inducing surfactants also had haemolytic properties. These properties were related to the values of the hydrophilic-lipophilic balance of the molecules.

Possible effects of counterions on biological activities of anionic surfactants.

The aggressiveness in terms of apogenic and necrotic activities of lysine-derived anionic surfactants towards a mammalian cell line (U937) were studied. We used N(alpha)N(epsilon)-dioctanoyl lysine as the model surfactant with lysine, tris, Na(+) or Li(+) as counterions. The aggressiveness of the different surfactants was assessed as the concentrations leading to apoptosis or necrosis after the cells were incubated in the presence of surfactants and then cultivated in their absence. Used in the same conditions, acetates associated with the same cations, had no effects on the cells. Our results show that the aggressiveness of the surfactants depended on the nature of the counterions: it was high when surfactants were associated with small counterions, and low with large counterions.

Derivatives of glutamic acid as new surfactants.

Starting from glutamic acid, different types of surfactants have been synthesised by using original trimodular strategies. Monosubstituted zwitterionic amides of glutamic acid obtained with excellent yields show good surface activity. The grafting of a second hydrophobic side-chain leads to bicatenar cationic surfactants or to disubstituted nonionic cyclic compounds. In order to reduce the hydrophobic character of the bicatenar surfactants, a second synthetic method has been developed, allowing the introduction of a polar sugar group into these molecules. The surfactant properties of several of the products have been determined by physico-chemical methods such as surface tension measurements and compression isotherm studies by means of a Langmuir balance.

Al(30): A Giant Aluminum Polycation.

Simple hydrothermal treatment of the well-known aluminum polycation varepsilon-Al(13) produces the novel Al(30) structure (see picture), the largest polycation yet observed. Its characterization, by X-ray diffraction and NMR spectroscopy, also solved previously unassigned signals in (27)Al NMR spectra of other Al - O species.