Nanoarchitectonics with photoresponsive Hemiindigo amphiphiles into supramolecularly assembled soft robotics for controlled macroscopic motions.

Synthetic aqueous supramolecular assemblies mimic the natural biomolecular functions. One of the key material advancements of aqueous supramolecular assemblies is constructing life-like macroscopic materials with photoresponsive molecules via supramolecular strategies. Visible-light controlled indigoid-based aqueous supramolecular assemblies have been reported, but the photocontrolled robotic function and the hydrolytic stability of indigoid systems remain unexplored.

Supramolecular Interactions Determined Macroscopic Robotic Actuation Processes of Azobenzene Amphiphiles.

Inspired by nature, supramolecular assembling propensity of biomimetic units can be finely preprogrammed by supramolecular interactions. Supramolecular robotic system, as the junior members to soft robotic systems, is implemented with high intrinsic dynamicity, photoresponsiveness, and bioactive cell-material interfaces. However, reported supramolecular robotic systems are sensitive to subtle molecular structural modifications and lose its inherent robotic functions.

Peripheral Designed Indigo Bola-Amphiphiles for Supramolecular Assembled Nanoarchitectonics in Aqueous Media.

Indigo, an ancient natural dye, featured excellent biodegradability to advance in sustainable polymer. Indigo amphiphiles can pave a way for sustainable supramolecular polymers in aqueous media for potential biomedical functional materials. However, contemporary indigo amphiphiles supramolecular commonly assemble into low aspect ratio nanostructures, which hampers the macroscopic soft scaffolds fabrications and smart functional material applications.

Supramolecular assemblies of amphiphilic donor-acceptor Stenhouse adducts as macroscopic soft scaffolds.

In the design of photoharvesting and photoresponsive supramolecular systems in aqueous medium, the fabrication of amphiphilic photoswitches enables a noninvasive functional response through photoirradiation. Although most aqueous supramolecular assemblies are driven by high-energy and biodamaging UV light, we have previously reported a design of amphiphilic donor-acceptor Stenhouse adducts (DASAs) controlled by white light. Herein, we present a series of DASA amphiphiles (DAs) with minor structural modifications on the alkyl linker chain length connecting the DASA motif with the hydrophilic moiety.

Aqueous Supramolecular Transformations of Motor Bola-Amphiphiles at Multiple Length-Scale.

Molecular motor amphiphiles have already been widely attempted for dynamic nanosystems across multiple length-scale for developments of small functional materials, including controlling macroscopic foam properties, amplifying motion as artificial molecular muscles, and serving as extracellular matrix mimicking cell scaffolds. However, limiting examples of bola-type molecular motor amphiphiles are considered for constructing macroscopic biomaterials. Herein, this work presents the designed two second generation molecular motor amphiphiles, motor bola-amphiphiles (MBAs).

Visible-light controlled supramolecular transformations of donor-acceptor Stenhouse adducts amphiphiles at multiple length-scale.

Designing responsive, adaptive, and dynamic supramolecular systems in water, the incorporation of photoresponsive units in amphiphilic molecular structures enables functional responses in a non-invasive way by using light. However, in aqueous media, vast majority of reported synthetic photoresponsive molecular amphiphiles are commonly driven by high energy and bio-damaging UV-light for supramolecular transformation at multiple length-scale. Herein, we present newly designed visible-light controlled supramolecular assembly of donor-acceptor Stenhouse adducts amphiphiles (DA) with excellent stability and solubility in aqueous media.

2,2-difluorovinyl benzoates for diverse synthesis of gem-difluoroenol ethers by Ni-catalyzed cross-coupling reactions.

gem-Difluoroalkene is a bioisostere of carbonyl group for improving bioavailability of drug candidates. Herein we develop structurally diverse 2,2-difluorovinyl benzoates (BzO-DFs) as versatile building blocks for modular synthesis of gem-difluoroenol ethers (44 examples) and gem-difluoroalkenes (2 examples) by Ni-catalyzed cross coupling reactions. Diverse BzO-DFs derivatives bearing sensitive functional groups (e.