Elucidating the Role of Interfacial Hydrogen Bonds on Glass Transition Temperature Change in a Poly(Vinyl Alcohol)/SiO2 Polymer-Nanocomposite by Noncovalent Interaction Characterization and Atomistic Molecular Dynamics Simulations.

A thorough experimental investigation of polymer-glass transition temperature (Tg ) is performed on poly(vinyl alcohol) (PVA) and fumed silica nanoparticle (SiNP) composite. This is done together with atomistic molecular dynamics simulations of PVA systems in contact with bare and fully hydroxylated silica. Experimentally, PVA-SiNP composites are prepared by simple solution casting from aqueous solutions followed by its characterization using Fourier-transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), and dynamic scanning calorimetry (DSC). Both theoretical and experimentally deduced Tg are correlated with the presence of hydrogen bonding interactions involving OH functionality present on the surface of SiNP and along PVA polymer backbone. Further deconvolution of FTIR data show that inter-molecular hydrogen bonding present between PVA and SiNP surface is directly responsible for the increase in Tg . SiNP filler and PVA matrix ratio is also optimized for a desired Tg increase. An optimal loading of SiNP exists, in order to yield the maximum Tg increase arising from the competition between hydrogen bonding and crowding effect of SiNP.

Vesicle-Templated Polymerization, a Review.

Vesicle-templated polymerization has developed into a mature research area over the last 35 years. The main purpose of this approach was to produce hollow polymeric nanocapsules from low-cost chemicals, utilizing a simple emulsion-polymerization-like process. Over the years, understanding of the different varieties of the approach has grown. In retrospect, the characterization methods utilized to determine the morphologies are essential to draw the right conclusions. In this Review, first, an overview of the earlier attempts to produce nanocapsules with uniformous wall thickness will be given, looking at the results with the current understandings, greatly enhanced by quantification of the different morphologies through cryo-TEM images. The latest approach, reactive oligomer assisted transcriptive synthesis, seems to be able to fulfill the initial purpose and almost 100% of nanocapsule morphologies can be formed under the right conditions.

Morphology Control of Liposome - RAFT Oligomer Precursors to Complex Polymer Nanostructures.

Different types of butyl acrylate (BA)-co-acrylic acid (AA) oligomers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization and mixed with extruded 200 nm dimethyldioctadecylammonium bromide vesicles. The resulting precursor structures form the basis for subsequent vesicle-templated polymerizations. Systematic variations in temperature, pH, oligomer length, and oligomer composition and their effects on precursor morphology were studied. Surprisingly, different morphologies were obtained, including capsules, protruded capsules, solid spheres, and multicompartment structures. For example, capsules and multicompartment structures were found to result from higher AA contents, and protruded capsules and solid particles resulted from lower AA contents. Subsequent chain extension of the RAFT oligomers resulted in polymer nanostructures resembling the precursor morphologies.

Reversible Photo- and Thermoresponsive, Self-Assembling Azobenzene Containing Zwitterionic Polymers.

Commercially available azo dyes bearing amino groups were grafted to zwitterionic copolymers composed of cyclic anhydride functionality. The zwitterionic copolymers were prepared for the first time by polymerizing sulfobetaine (SB) monomer with maleic anhydride (MA) under conventional free radical polymerization as well as reversible addition-fragmentation chain transfer (RAFT) polymerization. Poly(SB- co-MA) self-assembled in deionized water. Azobenzene grafted zwitterionic poly((SB- co-MA)- g-Azo) exhibited multiresponsive behavior. As confirmed by UV-vis spectroscopy, trans → cis isomerization of the azo group was responsible for the photo- and thermal responsive behavior. The photoisomerization was reversible, and no photoaging was detected during the repeated exposure to UV and visible light. The water-soluble nature of photoresponsive azo dye grafted copolymers makes it suitable for applications in biological systems.