Synthesis and Characterization of a Thermoresponsive Copolymer with an LCST–UCST-like Behavior and Exhibiting Crystallization

In this work, the diblock copolymer methoxy-poly(ethylene glycol)-block-poly(ε-caprolactone) (MPEG–b-PCL) was synthesized with a block composition that allows this polymer in aqueous media to possess both an upper critical solution temperature (UCST) and a lower critical solution temperature (LCST) over a limited temperature interval. The value of the UCST, associated with crystallization of the PCL-block, depended on heating (H) or cooling (C) of the sample and was found to be CPUCSTH = 32 °C and CPUCSTC = 23 °C, respectively. The LCST was not affected by the heating or cooling scans; assumed a value of 52 °C (CPLCSTH = CPLCSTC). At intermediate temperatures (e.g., 45 °C), dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM) showed that the solution consisted of a large population of spherical core–shell particles and some self-assembled rodlike objects. At low temperatures (below 32 °C), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS) in combination with SAXS disclosed the formation of crystals with a cylindrical core–shell structure. Cryo-TEM supported a thread-like appearance of the self-assembled polymer chains. At temperatures above 52 °C, incipient phase separation took place and large aggregation complexes of amorphous morphology were formed. This work provides insight into the intricate interplay between UCST and LCST and the type of structures formed at these conditions in aqueous solutions of MPEG–b-PCL diblock copolymers.publishedVersio

Interactions in Aqueous Mixtures of Cationic Hydroxyethyl Cellulose and Different Anionic Bile Salts

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Supramolecular Structures of Poly(γ-benzyl-L-glutamate) Self-Assembled on Mica Surface

This article reports the results of structural studies of poly (-benzyl-L-glutamate) (PBLG) layers self-assembled from dilute solutions in organic solvents on mica surface. Polarized dynamic light scattering and atomic force microscopy were used to study polymer properties in solutions and on the surface. The hierarchy of self-assembly from PBLG solutions in different solvents was investigated as a function of polymer concentration and solvent polarity. We show that the surface–polymer interaction is suppressed in polar solvents that is interpreted in terms of suppressed charge–dipole interaction. The transformation of the PBLG surface structure occurs upon addition of different amounts of trifluoroacetic acid to polymer solution in dioxane. Rigid-rod PBLG molecules experience rod–globular transition while assembling on nonmodified mica from the very dilute solutions. A scheme is proposed describing different stages of PBLG fibrogenesis on a charged surface

Lipid-Block Copolymer-Immiscibility

We have investigated the binary system of a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), EO5PO68EO5, in water. The ternary system with the same polymer, water and soybean phosphatidylcholine (lecithin) has also been studied. Small-angle X-ray scattering (SAXS), 2H NMR and differential scanning calorimetry (DSC) were used to characterize these systems. The phase diagram of the binary system is presented together with the characteristic parameters in the lamellar and hexagonal phases. In the ternary system, it was found that the lecithin and the block copolymer are essentially immiscible, forming separate phases. In a differential scanning calorimetry experiment it was found that the presence of the block copolymer did not affect the melting temperature of dipalmitoyl phosphatidyl choline. Again indicating immiscibility. The alkane hexadecane is a bad solvent for polypropylene oxide at room temperature. We conclude that it is the difference in hydrophobicity (or polarity) of the hydrophobic parts of the lecithin (lipid) and the block copolymer that explains their immiscibilit

Spontaneous vesicle formation in a block copolymer system

We have investigated the formation of vesicles in the binary system of a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) with the average composition EO5PO68EO5 in water. Vesicles are formed when a solution of unimers is heated into a two-phase region where, at equilibrium, a concentrated lamellar phase coexists with a dilute solution of unimers. The vesicles were characterized by cryo-TEM, static and dynamic light scattering, and NMR experiments. The average vesicle radius is approximately 60 nm, with an exponential size distribution, and the concentration of vesicles depends strongly on the temperature. The vesicles remain stationary on the time scale of hours. A striking observation is that, on this time scale, both the vesicle size distribution and the concentration of vesicles are reversible with respect to temperature cycles. However, on the time scale of weeks a sedimentation is observed in the solutions

Forces Controlling the Rate of DNA Ejection from Page λ

The goal of this work was to investigate how internal and external forces acting on DNA affect the rate of genome ejection from bacteriophage λ after the ejection is triggered in vitro by a λ receptor. The rate of ejection was measured with time-resolved static and dynamic light scattering, while varying such parameters as temperature and packaged DNA length, as well as adding DNA-binding proteins to the host solution. We found that temperature has a strong effect on the ejection rate, with an exponential increase of the initial ejection rate as a function of temperature. This can possibly be explained by the temperature-induced conformational changes in the tail pore-forming proteins where the “open” conformation dominates over “closed”, at elevated temperatures. The DNA length also had an effect on initial ejection rate, with a nearly linear dependence comparing the three different genomes (37.7, 45.7 and 48.5 kb DNA), with faster ejection rate for longer genomes. Since the initial rate of ejection increases in an almost direct relationship with the length of the genome, the total time needed to eject DNA completely appeared to be nearly constant for all three DNA length phage mutants. The increased initial rate of ejection with increasing DNA length is due to the increased DNA bending and inter-strand repulsion forces for the longer DNA chains. Finally, we also show that addition of non-specific DNA-binding proteins (HU and DNase I) increases the rate of ejection by exerting additional “pulling” forces on the DNA that is being ejected