No abstract

Linear homopolymers of norbornene (NBE) derivatives equipped with short-chain alcohol pendant groups were prepared by ring-opening metathesis polymerization (ROMP) and subsequently assembled into well-defined structures in alcohol solvents. The ratios of hydrophobic carbons and hydrophilic alcohol groups at the repeating monomeric unit in these short-chain amphiphilic polymers were found to play an important role in determining the size and distribution of the final globular structures. Unlike the assembly of other linear homo- and copolymers possessing long-chain amphiphilicity, NBE-based linear polymers were readily transformed into spherical particles with a layered conformation, whose sizes range from a few hundred nanometers to micrometers with narrow distributions, simply by controlling the concentration and molecular weights of the linear homopolymers without using any surfactants. In addition, the degree of the intermolecular forces with solvents (e.g., solvation) possessing different surface tensions and polarities highly affected the final diameter and distribution of the polymer particles, implying the importance of the selection of a proper solvent to regulate their structural features. As such, understanding the assembly of these types of short-chain homopolymers into uniform particles can allow for regulating the transformation of diverse linear amphiphilic polymers into precisely controlled structures for various applications.

This work describes the empirical screening of base types and amounts on the catalytic property of gold‐polymer composite particles in the aerobic homocoupling of arylboronic acid. As these particles notably improve the yields of biaryl in the presence of bases, various bases and their amounts are systematically tested to experimentally identify an ideal base that can provide high reactivity and recyclability of the composite particles in mild and green conditions. Interestingly, the following conditions ‐ soluble strong bases at sub‐stoichiometric quantities (0.5 eq.) and insoluble weak bases at excess amounts (3.0 eq.) in EtOH ‐ significantly enhance the catalytic activities of the composite particles. Upon screening two ideal bases, overall catalytic properties of the composite particles including reaction rate at three different temperatures, activation energy (51–52 kJ/mole), and recyclability (7 cycles) were compared. Understanding the effect of bases and fine‐tuning reaction conditions can potentially improve overall reactivity and recyclability of the composite particles as a green quasi‐homogenous catalyst.

This report describes the systematic incorporation of gold nanoparticles (AuNPs) onto mesoporous TiO2 (MPT) particles without strong attractive forces to efficiently serve as reactive and recyclable catalysts in the homocoupling of arylboronic acid in green reaction conditions. Unlike using nonporous TiO2 particles and conventional SiO2 particles as supporting materials, the employment of MPT particles significantly improves the loading efficiency of AuNPs. The incorporated AuNPs are less than 10 nm in diameter, regardless of the amount of applied gold ions, and their surfaces, free from any modifiers, act as highly reactive catalytic sites to notably improve the yields in the homocoupling reaction. The overall physical properties of the AuNPs integrated onto the MPT particles are thoroughly examined as functions of the gold content, and their catalytic functions, including the rate of reaction, activation energy, and recyclability, are also evaluated. While the rate of reaction slightly increases with the improved loading efficiency of AuNPs, the apparent activation energies do not clearly show any correlation with the size or distribution of the AuNPs under our reaction conditions. Understanding the formation of these types of composite particles and their catalytic functions could lead to the development of highly practical, quasi-homogeneous catalysts in environmentally friendly reaction conditions.