The kinetics of the sphere-to-rod transition was studied in aqueous micelle solutions of triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) pluronic P103 (PEO(17)PPO(60)PEO(17)). This transition was triggered by a temperature jump from the sphere phase to the rod phase and monitored with dynamic light scattering. The combination of the scattering intensity and the hydrodynamic radius were used to show that the micelles grow steadily as rods throughout the growth process. The transition was found to exhibit a single exponential behavior even in the case of large deviations from equilibrium. The linear increase in the decay rate with increasing copolymer concentration shows that the transition is dominated by a mechanism involving fusion and fragmentation of proper micelles. The decays of the sphere-to-rod transition were simulated for two pathways: random fusion fragmentation and successive addition of spherical micelles to rods. We show that micelle growth most likely occurs via random fusion-fragmentation. The second order rate constant for fusion and the fragmentation rate are calculated for the case of random fusion-fragmentation.

DNA dynamics and flow properties are of great importance for understanding its functions. DNA is a semiflexible polymer chain characterized by having a large persistence length of around 50 nm and high charge density; DNA chains are interacting efficiently at high concentrations, in dependence of the ionic concentration. In relation with DNA molecular characteristics, it is also known that DNA solutions are able to form liquid crystalline phases over a critical polymer concentration. In this work, the supramolecular organization in calf-thymus DNA solution, with low degree of entanglement, appearing under flow was studied in a wide DNA concentration range from 2 to 10 mg/mL, at a pH of 7.3 and 20 °C. The rheological behavior of the system was studied using steady state flow and oscillatory measurements. Transient regimes were also tested by imposing controlled shear rates on a short time up to steady state. Furthermore, a combination of visual observations and flow birefringence measurements was proposed to reach a better understanding of the obtained rheological behavior. The presence of a shear-induced texture is revealed under flow for the calf-thymus DNA solutions at C DNA> 5 mg/mL and attributed to organized domains of DNA molecules, named in the text as crystalline parts, which are progressively oriented under shear. Finally, at high shear rates (over 100 s–1), it is shown that for the DNA solutions the orientation of these organized DNA domains and connecting chains under flow goes to an anisotropic monodomain.

Due to their slow kinetics, the dynamical pathways of block copolymer micelles are as important as the copolymer architecture, particularly when making self-assembled nanostructures.Two types of dynamical pathways could govern these dynamics: insertion/expulsion of copolymer chains and fusion/fission of micelles. However, quantifying and understanding the fusion and fission processes remains very limited in copolymer micelles, especially at equilibrium. In this article, it was demonstrated the use of a fluorescent technique, using randomization of a highly hydrophobic pyrene derivative between micelles, as a tool to quantify the fusion and fission at equilibrium in a series of triblock copolymers micelles Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) in aqueous solution. The temperature dependence of fusion and fission is investigated for copolymers with various core block lengths (NPPO) in the spherical regime. Fusion and fission rates were found to strongly decrease with increasing the core block length. The dependence of the fission rate on NPPO is analyzed in terms of thin corona and starlike micelle models which suggest that fission is mainly dominated by the core interfacial tension as predicted by Halperin et al. The comparison between fission and expulsion kinetics and their dependence on PPO block is also reported. Finally, fusion is found to follow the same temperature and core length dependencies as fission, which is an indication that the interfacial tension plays a relevant role in the fusion kinetic.

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Nanostructured films with electrical conductivity in the semiconductor region were prepared in a polymeric matrix of poly(vinyl alcohol) (PVA) with nanostructures of chitosan-gold nanoparticles (AuNPs)/single-wall carbon nanotubes carboxylic acid functionalized (SWCNT-COOH) (chitosan-AuNPs/SWCNT-COOH) self-assembled. Dispersion light scattering (DLS) was used to determine the average particle sizes of chitosan-AuNPs, z-average particle size (Dz) and number average particle size (Dn), and the formation of crystalline domains of AuNPs was demonstrated by X-ray diffraction (XRD) patterns and observed by means of transmission electron microscopy (TEM). The electrostatic interaction was verified by Fourier transform infrared spectroscopy (FTIR). The electrical conductivity of PVA/chitosan-AuNPs/SWCNT-COOH was determined by the four-point technique and photocurrent. The calculated Dn values of the chitosan-AuNPs decreased as the concentration of gold (III) chloride trihydrate (HAuCl4·3H2O) increased: the concentrations of 0.4 and 1.3 mM were 209 and 90 nm, respectively. Average crystal size (L) and number average size (D) of the AuNPs were calculated in the range of 13 to 24 nm. Electrical conductivity of PVA/chitosan-AuNPs/SWCNT-COOH films was 3.7 × 10−5 σ/cm determined by the four-point technique and 6.5 × 10−4 σ/cm by photocurrent for the SWCNT-COOH concentration of 0.5 wt.% and HAuCl4·3H2O concentration of 0.4 mM. In this investigation, the protonation of the amine group of chitosan is fundamental to prepare PVA films with nanostructures of self-assembled chitosan-AuNPs/SWCNT-COOH.

The interactions of proteins and other molecules and their adsorption onto substrates is a fascinating topic that has been applied to surface technologies, biosensors, corrosion studies, biotechnologies, and other fields. The success of these applications requires a previous characterization using some analytical techniques that, ordinarily, are not electrochemical. This work proposes analyzing the variation of the double-layer capacitance obtained through impedance electrochemical spectroscopy as an alternative strategy to show evidence of the interactions between proteins and triblock copolymers. The proposal is supported through the study of the interaction and adsorption of bovine serum albumin (BSA) and a commercial triblock copolymer (P103) in phosphate buffer on a gold electrode. The double-layer capacitance and the apparent interface thickness vs polarization potential curves as well as the potential of zero charge for pure P103 (0.6 wt %, corresponding to 6 g L –1 ), pure BSA (3 mg mL –1 ), and P103-BSA solutions (0.6 wt % and 3 mg mL –1 , respectively) are sensitive enough to show not only the interaction and the adsorption of the species but also the polarization potential where these interactions are taking place. A qualitative and quantitative analysis concerning the double-layer capacitance behavior is given. The significance and impact of this work is also presented.