Reversible Thermo-Optical Response Nanocomposites Based on RAFT Symmetric Triblock Copolymers (ABA) of Acrylamide and N-Isopropylacrylamide and Gold Nanoparticles.

The development of composite materials with thermo-optical properties based on smart polymeric systems and nanostructures have been extensively studied. Due to the fact of its ability to self-assemble into a structure that generates a significant change in the refractive index, one of most attractive thermo-responsive polymers is poly(N-isopropylacrylamide) (PNIPAM), as well as its derivatives such as multiblock copolymers. In this work, symmetric triblock copolymers of polyacrylamide (PAM) and PNIPAM (PAMx-b-PNIPAMy-b-PAMx) with different block lengths were prepared by reversible addition-fragmentation chain-transfer polymerization (RAFT). The ABA sequence of these triblock copolymers was obtained in only two steps using a symmetrical trithiocarbonate as a transfer agent. The copolymers were combined with gold nanoparticles (AuNPs) to prepare nanocomposite materials with tunable optical properties. The results show that copolymers behave differently in solution due to the fact of variations in their composition. Therefore, they have a different impact on the nanoparticle formation process. Likewise, as expected, an increase in the length of the PNIPAM block promotes a better thermo-optical response.

Hydrolyzed Polyacrylamide as an In Situ Assistant in the Nucleation and Growth of Gold Nanoparticles.

The modulation of nanoparticles' size, shape, and dispersion by polymers has attracted particular attention in different fields. Nevertheless, there is a lack of information regarding the use of charged macromolecules as assistants in the nanostructures' nucleation and growth processes. Prompted by this, the in situ synthesis of gold nanoparticles (AuNPs) aided by hydrolyzed polyacrylamides (HPAM), with different chemical structures, was developed. In contrast to the conventional synthesis of nanostructures assisted by polyacrylamide, here, the polymerization, hydrolysis, and nanostructure formation processes were carried out simultaneously in the same milieu. Likewise, the growing chains acted as a template for the nanoparticles' growth, so their conformations and chemical structure, especially the amount of charges along the chain, played an important role in the AuNPs' morphology, size, and some of the final composite features. The nanocomposite was thoroughly characterized with appropriate techniques, including ATR-FTIR, GPC, UV-Vis, and SEM.

Polymers as Versatile Players in the Stabilization, Capping, and Design of Inorganic Nanostructures.

The integration of simple components to generate sophisticated hybrid materials with fine-tuned properties represents a significant scientific challenge. Herein, we present recent advances in the use of polymers to control the synthesis and properties of three of the most relevant inorganic nanoparticles, namely, quantum dots (QDs), magnetic nanoparticles (MNPs), and noble metal nanoparticles (NMNPs). We show relevant examples of how polymeric structures synthesized by techniques such as ATRP, RAFT, and living cationic polymerization are used to aid in the synthesis and stabilization of the nanostructures to generate nanocomposites with outstanding capabilities. Special emphasis is placed on describing how some of the exceptional physicochemical properties of polymers are used as nanoreactors to facilitate the synthesis of the nanostructure by providing an adequate chemical environment. Additionally, we also describe how polymers are utilized to protect the integrity of the nanostructure from chemical degradation. The integration of polymeric structures and the nanostructures has a strong impact on the dispersion and morphology of the latter and, consequently, endow them with novel and promising features. The advances described here, particularly the use of polymers to modulate and provide new properties to nanoparticles, exemplify the great versatility of polymers and how these may expand the capabilities of inorganic nanostructures that can be used to generate novel and sophisticated hybrid materials.