ABSTRACT
The serial connection of multiple stimuli-responses in polymer architectures enables the logically conjunctive gating of functional material processes on demand. Here, a photoswitchable diarylethene (DAE) acts as a crosslinker in poly(N-vinylcaprolactam) microgels and allows the light-induced shift of the volume phase-transition temperature (VPTT). While swollen microgels below the VPTT are susceptible to force and undergo breakage-aggregation processes, collapsed microgels above the VPTT stay intact in mechanical fields induced by ultrasonication. Within a VPTT shift regime, photoswitching of the DAE transfers microgels from the swollen to the collapsed state and thereby gates their response to force as demonstrated by the light-gated activation of an embedded fluorogenic mechanophore. This photoinduced mechanical cloaking system operates on the polymer topology level and is thereby principally universally applicable.
ABSTRACT
Enhancing NMR signals of biomacromolecules by hyperpolarization offers exciting opportunities for diagnostic applications. However, their hyperpolarization via parahydrogen remains challenging as specific catalytic interactions are required, which are difficult to tune due to the large size of the biomolecule and its insolubility in organic solvents. Herein, we show the unprecedented hyperpolarization of the cancer-targeting DNA aptamer AS1411. By screening different molecular motifs for an unsaturated label in nucleosides and in DNA oligomers, we were able to identify structural prerequisites for the hyperpolarization of AS1411. Finally, adjusting the polarity of AS1411 by complexing the DNA backbone with amino polyethylene glycol chains allowed the hydrogenation of the label with parahydrogen while the DNA structure remains stable to maintain its biological function. Our results are expected to advance hyperpolarized molecular imaging technology for disease detection in the future.
