Structural Behavior of Amphiphilic Triblock Copolymer P104/Water System.

A detailed study of the different structural transitions of the triblock copolymer PEO27-PPO61-PEO27 (P104) in water, in the dilute and semi-dilute regions, is addressed here as a function of temperature and P104 concentration (CP104) by mean of complimentary methods: viscosimetry, densimetry, dynamic light scattering, turbidimetry, polarized microscopy, and rheometry. The hydration profile was calculated through density and sound velocity measurements. It was possible to identify the regions where monomers exist, spherical micelle formation, elongated cylindrical micelles formation, clouding points, and liquid crystalline behavior. We report a partial phase diagram including information for P104 concentrations from 1 × 10-4 to 90 wt.% and temperatures from 20 to 75 °C that will be helpful for further interaction studies with hydrophobic molecules or active principles for drug delivery.

Helicity degree of carrageenan conformation determines the polysaccharide and water interactions.

The polysaccharide in solution at critical concentration, Cc (g/L), is assimilated to a nano hydrogel (nHG) made of a single polysaccharide chain. Taking as reference the characteristic temperature of 20 ± 2 °C at which kappa-carrageenan (κ-Car) nHG swelling is greater with a Cc = 0.55 ± 0.05 g/L, the temperature of the minimum deswelling in the presence of KCl was found at 30 ± 2 °C for 5 mM with a Cc = 1.15 ± 0.05 g/L but not measurable above 100 °C for 10 mM of which Cc = 1.3 ± 0.05 g/L. Lowering the temperature to 5 °C, contraction of the nHG and further coil-helix transition with self-assembly increases the sample's viscosity, which steadily evolves with time in a logarithmic scale. Accordingly, the relative increment of the viscosity per unit of concentration, Rv (L/g), should increase in agreement with increasing polysaccharide concentration. But the Rv decreases for κ-Car samples above 3.5 ± 0.5 g/L in the presence of 10 mM KCl under steady shear 15 s-1. This reflects a decrease of κ-Car helicity degree knowing that the polysaccharide is rather hydrophilic when its helicity degree is the lowest.

Stability of Fluid Ultrathin Polymer Films in Contact with Solvent-Loaded Gels for Cultural Heritage.

The removal of ultrathin amorphous polymer films in contact with an aqueous gelled solution containing small amounts of good solvent is addressed by means of specular and off-specular neutron reflectometry. The distribution of heavy water and benzyl alcohol is revealed inside Laropal A81, often employed as a protective varnish layer for Culture Heritage in the restoration of easel paintings. The swelling kinetics, interface roughness, and film morphologies were recorded as a function of temperature and increasing benzyl alcohol concentration in the dispersion of Pemulen TR-2, a hydrophobically modified acrylic acid copolymer. The addition of small amounts of good solvent results in the appearance of water-filled cavities inside the varnish, which grow with time. It is shown that while increasing the solvent concentration greatly enhances the hole growth kinetics, an increase in temperature above the glass transition temperature does not have such a big effect on the kinetics.

Swelling, dewetting and breakup in thin polymer films for cultural heritage.

The removal of ultrathin amorphous polymer films in contact with nonsolvent/solvent binary mixtures is addressed by means of neutron reflectometry and atomic force microscopy. The high resolution of neutron scattering makes it possible to resolve the distribution profiles of heavy water and benzyl alcohol inside Laropal®A81, often employed as a protective varnish layer for Culture Heritage in restoration of easel paintings. The swelling kinetics and distribution profiles were recorded as a function of time and increasing benzyl alcohol concentration in water. The varnish film swells by penetration of the good solvent. At higher concentrations water-filled cavities appear inside the varnish and grow with time. Contrary to homogeneous dissolution dewetting is observed at late stages of exposure to the liquid which leads to the Breakup of the film. The high resolution measurements are compared to bulk behaviour characterized by the ternary phase diagram and the Flory-Huggins interaction parameters are calculated and used to predict the swelling and solvent partition in the films. Distinct differences of the thin film to bulk behaviour are found. The expectations made previously for the behaviour of solvent/non-solvent mixtures on the removal of thin layers in the restoration of easel paintings should be revised in view of surface interactions.

Exchange dynamics between amphiphilic block copolymers and lipidic membranes through hydrophobic pyrene probe transfer.

Vectorization has experienced significant development over the last few years and has been used to control the distribution of active ingredients to a target by their association with a vector. However, controlled drug delivery suffers from "burst release" as the drugs are released before the targeted site. Very few studies have examined the collective mechanisms of fission-fusion on micelles in the transport and expulsion of active ingredients. Endocytosis and exocytosis of cells are examples of fusion and fission in biological matter. Understanding these dynamics becomes crucial for the design and the control of new materials and new processes effective in controlled drug delivery. In this work, a study of the exchange dynamics between amphiphilic block copolymers and lipid membranes for vectorization of hydrophobic molecules using a fluorescence technique is presented. A highly hydrophobic alkylated pyrene, PyC18, is used as a fluorescent probe that can be exchanged between amphiphilic block copolymer micelles and liposomes via different mechanisms. It is demonstrated that the exchange dynamics evaluated for different liposome concentrations is a collective mechanism characterized by having two rate constants.

Fusion and fission inhibited by the same mechanism in electrostatically charged surfactant micelles.

This paper revises the general idea about the role of intermicellar and intramiceller interactions in inhibiting fusion of self-assembled surfactant micelles. Fusion and fission of micelles are usually thought to be limited by different mechanisms. While fission is accepted to be controlled by surface instabilities (intramicellar interactions), fusion is commonly thought to be rate limited by the barrier to the close approach between two micelles due to the steric or Coulombic repulsions (intramicellar interactions). Here we describe the role of electrostatic repulsions in inhibiting fusion and fission kinetics in self-assembled micelles. We use stopped flow-fluorescence technique with hydrophobic pyrene to quantify fusion and fission in ionic/nonionic mixed micelles (Triton X-100/SDS). We show that the fusion and fission rates decrease with the same tendency with increasing the fraction of the ionic charges, while their ratio remains constant. Our results are interpreted to mean that, in slightly charged micelles, fusion shares the same limiting step with fission, which most likely involves surface instabilities and intramiceller interactions.

Various modes of void closure during dry sintering of close-packed nanoparticles.

Film formation from aqueous suspensions of polymer nanoparticles is an important process in many environmental friendly applications and particularly for waterborne coatings. This process occurs via three mains steps: concentration, sintering, and interdiffusion. During the sintering step, the particles in close-packed morphology deform and the interstices between them close under Laplace pressure. This step is crucial in the film formation process since it is where the suspension turns into a uniform defect-free film. Most of the experimental and theoretical studies on sintering assume that the interstices close uniformly over the entire film. We use small-angle neutron scattering to probe void closure between polystyrene nanoparticles. We show that the voids close simultaneously and uniformly throughout the annealing process in large particles. For particles with a diameter smaller than 60 nm, we interpret the results to show that the interstices close heterogeneously at the nanoscopic level: in the beginning of annealing, some interstices close while others enlarge, and eventually they all vanish. The difference between the behavior of large and small particles is related to the high polydispersity of small particles compared to the larger ones.

Reduction of the glass transition temperature of confined polystyrene nanoparticles in nanoblends.

The role of nanoconfinement on the glass transition temperature (T(g)) of polymers has been extensively studied in the thin film geometry. This work looks at the T(g) of nanoconfined polystyrene (PS) in spherical nanoparticles (27-200 nm) , individually dispersed in crosslinked polybuthylmethacrylate matrices. A reduction of T(g) compared to the bulk was observed in PS nanospheres via neutron scattering mechanical tests and was found to decrease with decreasing diameter for D<50 nm . The general trend of T(g) depression in nanospheres was found to be similar to the results on thin film geometry.

Exchange mechanisms for sodium dodecyl sulfate micelles: high salt concentration.

Solute exchange experiments for the pyrene-labeled triglyceride TG-Py solubilized in sodium dodecyl sulfate (SDS) micelles in the presence and absence of salt show that the "observed" rate constant k(obs) for solute exchange varies by over 6 orders of magnitude as the free sodium ion concentration [Na(+)](aq) is varied between 10 and 850 mM. There is a sharp break in the log-log plot of k(obs) versus [Na(+)](aq) in the range of [Na(+)](aq) = 200 mM, with the exchange rate showing a weaker dependence on [Na(+)](aq) above this concentration. Up to 100 mM added NaCl, this exchange takes place essentially exclusively by a micelle fission mechanism in which each submicelle carries off one of the solutes. At higher salt concentrations, a bimolecular process becomes increasingly important. This fusion process, which involves formation of a transient supermicelle followed by fission back to two normal micelles, becomes the dominant process at high salt concentrations. The fission rate appears to level off for salt concentrations above 300-400 mM. These fission and fusion processes are related in an intimate way to the changes in the size and shape of the SDS micelles with increasing salt concentration.

Salt effects on solute exchange in sodium dodecyl sulfate micelles.

We describe the influence of sodium chloride on the rate of solute exchange in aqueous SDS micelles for a water-insoluble solute, a pyrene-containing triglyceride 1. The initially prepared solutions contained a small fraction of micelles containing two molecules of 1 and a large excess of empty micelles. These solutions showed a measurable excimer emission (of intensity I(E)) that was stable for days to weeks in the absence of added salt. Following additions of salt, I(E) decayed exponentially (rate constant, k(obs)) accompanied by an increase in pyrene monomer emission. Values of k(obs) increased strongly with ionic strength (k(obs) similar [Na(+)](4)). There was no contribution of the empty micelle concentration beyond its contribution to the sodium ion concentration. We conclude that the solute exchange involves spontaneous fragmentation of the SDS micelles into two submicelles, each bearing a molecule of 1, which then grow back to normal micelles through condensation of SDS monomers. We propose a model for the fragmentation process in which large amplitude surface fluctuations "pinch off" a subunit that becomes a submicelle. These fluctuations bring sulfate headgroups into close proximity. Fluctuations leading to fission become important only in the presence of sufficient counterion concentration to reduce the electrostatic repulsion between neighboring headgroups.

Aggregation Behavior of Nonionic Surfactants Synperonic A7 and A50 in Aqueous Solution.

The aggregation behavior of Synperonic A7 and A50, fatty alcohol ethoxylate nonionic surfactants (C(m)E(n)) with mean polyoxyethylene chain lengths of 7 and 50, respectively, was investigated in aqueous solution by means of surface tension, laser light scattering, steady-state fluorescence, and fluorescence quenching experiments. Surface tension measurements at room temperature indicate that the critical micelle concentration of A7 is 0.1 g/L (0.22 mM) and that of A50 is 0.17 g/L (0.07 mM). Static light scattering measurements reveal that the averaged aggregation number of A7 in water is 417 and that of A50 is 23. When solutions of A7 were allowed to age over a period of months at room temperature, the micelle M(w) and hydrodynamic radius increased. The aggregation numbers found from fluorescence quenching measurements, using excimer formation from 1-ethylpyrene as a probe, were about 300 for freshly prepared solutions of A7 and about 40 for A50. We also found that the presence of air has a strong effect on the data obtained from the fluorescence quenching measurements. Copyright 2001 Academic Press.