RESUMO
We report a fluoride-catalyzed deblocking of urethanes as "blocked" isocyanates. Organic and inorganic sources of fluoride ion proved effective for deblocking urethanes and for converting polyurethanes to small molecules. Distinct from conventional deblocking chemistry involving organometallic compounds and high temperatures, the method we describe is metal-free and operates at or slightly above room temperature. The use of fluorescent blocking agents enabled visual and spectroscopic monitoring of blocking/deblocking reactions, and the selected conditions proved applicable to urethanes containing a variety of blocking groups. The method additionally enabled a one pot deblocking and polymerization with α,ω-diols. Overall, this deblocking/polymerization strategy offers a convenient and efficient solution to problems that have limited the breadth of applications of polyurethane chemistry.
RESUMO
We describe polymer-stabilized droplets capable of recognizing and picking up nanoparticles from substrates in experiments designed for transporting hydroxyapatite nanoparticles that represent the principal elemental composition of bone. Our experiments, which are inspired by cells that carry out materials transport in vivo, used oil-in-water droplets that traverse a nanoparticle-coated substrate driven by an imposed fluid flow. Nanoparticle capture is realized by interaction of the particles with chemical functionality embedded within the polymeric stabilizing layer on the droplets. Nanoparticle uptake efficiency is controlled by solution conditions and the extent of functionality available for contact with the nanoparticles. Moreover, in an elementary demonstration of nanoparticle transportation, particles retrieved initially from the substrate were later deposited "downstream," illustrating a pickup and drop-off technique that represents a first step toward mimicking point-to-point transportation events conducted in living systems.
RESUMO
Five dioxynaphthalene[38]-crown-10 (DNP38C10) macrocycles bearing one, two, three, or four allyl moieties have been synthesized and their ability to spontaneously self-assemble with methyl viologen to form [2]pseudorotaxanes has been evaluated. Association constants between methyl viologen and several of the allyl-functionalized DNP38C10 macrocycles are found to be comparable to that of methyl viologen and unfunctionalized DNP38C10, however, the enthalpic and entropic factors that underlie overall binding free energy vary systematically with increasing allyl substitution. These variations are explained through a combination of solution phase and solid-state analysis of the macrocycles and their complexes. The utility of endowing DNP38C10 macrocycles with allyl moieties is further demonstrated by the ease with which they can be functionalized through thiol-ene click chemistry.
RESUMO
Base-catalyzed thiol-maleimide click chemistry has been applied to the synthesis of neutral donor-acceptor [2]rotaxanes in good yield. This method is extended further to the synthesis of a glutathione-functionalized [2]pseudorotaxane, a precursor to integrated conjugates of interlocked molecules with proteins and enzymes.