Organic nanofibers embedding stimuli-responsive threaded molecular components

TL;DR

This study demonstrates the integration of stimuli-responsive molecular machines into electrospun nanofibers, enabling chemical and photonic actuation that alters their mechanical properties for potential sensing and actuation applications.

Contribution

The paper introduces a novel embedding of a self-assembling rotaxane system into polymer nanofibers, showing controlled molecular motion and macroscopic property changes upon stimuli.

Findings

Molecular dethreading and rethreading occur in nanofibers similar to solution behavior.

External stimuli induce measurable changes in nanofiber Young's modulus.

Embedded systems have potential for chemical sensing and photonic actuation.

Abstract

While most of the studies on molecular machines have been performed in solution, interfacing these supramolecular systems with solid-state nanostructures and materials is very important in view of their utilization in sensing components working by chemical and photonic actuation. Host polymeric materials, and particularly polymer nanofibers, enable the manipulation of the functional molecules constituting molecular machines, and provide a way to induce and control the supramolecular organization. Here, we present electrospun nanocomposites embedding a self-assembling rotaxane-type system that is responsive to both optical (UV-visible light) and chemical (acid/base) stimuli. The system includes a molecular axle comprised of a dibenzylammonium recognition site and two azobenzene end groups, and a dibenzo[24]crown-8 molecular ring. The dethreading and rethreading of the molecular components in nanofibers induced by exposure to base and acid vapors, as well as the photoisomerization of the azobenzene end groups, occur in a similar manner to what observed in solution. Importantly, however, the nanoscale mechanical function following external chemical stimuli induces a measurable variation of the macroscopic mechanical properties of nanofibers aligned in arrays, whose Young's modulus is significantly enhanced upon dethreading of the axles from the rings. These composite nanosystems show therefore great potential for application in chemical sensors, photonic actuators and environmentally responsive materials.