Acrylamide derivatives of bile acids are chosen as a hydrophobic comonomer to copolymerize with acrylamide via reversible addition and fragmentation chain transfer (RAFT) polymerization to afford a series of copolymers of P(AAm-co-CAA). These copolymers exhibit a sharp and reversible insoluble-soluble transition in water upon heating to a mixing temperature (T) related to the upper critical solution temperature (UCST). T of these copolymers can be conveniently tuned to a practical temperature range, around 37 °C for biomedical applications. T rises with increasing molar fraction of the bile acid-based acrylamide and increasing concentration of the aqueous solution of the copolymers. The addition of a natural host molecule β-cyclodextrin lowered the T. The insoluble-soluble transition of the copolymers was also evidenced by dynamic light scattering and transmission electron microscopy. The biocompatible nature of the bile acids and β-cyclodextrins may make these copolymers potentially useful for biomedical applications.
Optical
tweezers provide a platform for both manipulating and probing
the chemistry of a single polymer molecule tethered between dielectric
microspheres. It has been challenging to adapt this technology to
organic solvents, in part due to the limited availability of optically
trappable materials possessing the necessary diameter and refractive
index contrast. Here we report on the development of broadly accessible
optical trapping in aqueous and organic solvents that utilizes zinc
oxide-silica core/shell microspheres (beads). The addition of a silica
shell allows otherwise highly scattering zinc oxide nanoparticles
to be stably trapped and readily functionalized. Trapping was observed
in water, chloroform, tetrahydrofuran, and ethyl acetate. We demonstrate
how these beads can be used to measure the force–extension
curves of DNA and poly(methyl methacrylate) respectively utilizing
antibody/antigen complementation or strain-promoted azide/alkyne cycloaddition
to form linkages in situ. In the latter, a strong,
contiguous chain of covalent bonds is formed between the microspheres;
therefore, UV bond photolysis was used to count the number of rupture
steps and control for single-molecule link formation. In addition
to being trappable in many solvents, ZnO@SiO2 core/shell
beads can be used as solid support during harsh synthetic conditions
and can be readily prepared in the presence of atmospheric oxygen.
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