We report a modular
approach toward novel arylazotriazole photoswitches
and their photophysical characterization. Addition of lithiated TIPS-acetylene
to aryldiazonium tetrafluoroborate salts gives a wide range of azoacetylenes,
constituting an underexplored class of stable intermediates.
In situ
desilylation transiently leads to terminal arylazoacetylenes
that undergo copper-catalyzed cycloadditions (CuAAC) with a diverse
collection of organoazides. These include complex molecules derived
from natural products or drugs, such as colchicine, taxol, tamiflu,
and arachidonic acid. The arylazotriazoles display near-quantitative
photoisomerization and long thermal
Z
-half-lives.
Using the method, we introduce for the first time the design and synthesis
of a diacetylene platform. It permits implementation of consecutive
and diversity-oriented approaches linking two different conjugants
to independently addressable acetylenes within a common photoswitchable
azotriazole. This is showcased in the synthesis of several photoswitchable
conjugates, with potential applications as photoPROTACs and biotin
conjugates.
The article discusses the television series The Simpsons in the context of disability studies. Referring to David Mitchell and Sharon Snyder's theory of narrative prosthesis, the argument is that their notion of disability as a metaphorical device falls short of the specific function of disability in satire as both a source of humor and social commentary. As the reading of The Simpsons suggests, the show uses images of the grotesque as a form of graphic humor; furthermore, these images provide potentials of distanciation and critical thinking concerning the objectification of disability in the dominant discourse and the visualization of it in the media.
The cultural climate of the 1990s has rendered irony the dominant mode
of both media consumption and production. This chapter highlights The
Simpsons’ pivotal role as a TV show contributing to the cultivation of what
I dub “meta-television culture” in reference to John Fiske’s key work in
television studies, 1987’s Television Culture. More specifically, I argue that,
by working elements of spectator culture into the parodic framework of
an animated sitcom, The Simpsons has both tapped into and reinforced
a cultural sensibility of meta-media humor, which characterized the
zeitgeist of young adults in the 1980s and 1990s.
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