Stimuli-responsive polymers that release small molecules under mechanical stress are appealing targets for applications ranging from drug delivery to sensing. Here, we describe a modular mechanophore design platform molecular via mechanically triggered cascade reaction. Mechanochemical activation of furan–maleimide Diels–Alder adduct reveals latent furfuryl carbonate subsequently decomposes mild conditions covalently bound cargo molecule. The computationally guided reactive secondary enables...

We introduce the concept of mechanochemically gated photoswitching. Mechanical regulation a photochemical reaction is exemplified using newly designed mechanophore based on cyclopentadiene–maleimide Diels–Alder adduct. Ultrasound-induced mechanical activation photochemically inert in polymers generates diarylethene photoswitch via retro-[4 + 2] cycloaddition that photoisomerizes between colorless and colored states upon exposure to UV visible light. Control experiments demonstrate thermal...

Polymers that release small molecules in response to mechanical force are promising materials for a variety of applications ranging from sensing and catalysis targeted drug delivery. Within the rapidly growing field polymer mechanochemistry, stress-sensitive known as mechanophores particularly attractive enabling covalently bound payloads with excellent selectivity control. Here, we review recent progress development mechanophore-based molecular platforms provide an optimistic, yet critical...

Polymers that release functional small molecules in response to mechanical force are appealing targets for drug delivery, sensing, catalysis, and many other applications. Mechanically sensitive called mechanophores uniquely suited enable molecular with excellent selectivity control, but mechanophore designs capable of releasing cargo diverse chemical functionality limited. Here, we describe a general highly modular platform based on masked 2-furylcarbinol derivatives spontaneously decompose...

This paper describes a mechanical approach to inducing the atropisomerization of parallel diarylethene into its antiparallel diastereomers exhibiting distinct chemical reactivity. A congested mechanophore in (Ra,Sa)-configuration with mirror symmetry is atropisomerized C2 under ultrasound-induced force field. The resulting stereochemistry-converted material gains symmetry-allowed reactivity toward conrotatory photocyclization.

In this study, we present a novel self-cleaning, photoresponsive membrane that is capable of removing predeposited foulant layers upon changes in surface morphology response to UV or visible light irradiation while maintaining stable pore size and water permeance. These membranes were prepared by creating thin film composite (TFC) coating porous support with layer comb-shaped graft copolymers at two side-chain lengths featuring polyacrylonitrile (PAN) backbones photoreactive side chains,...

Understanding structure–mechanical activity relationships (SMARs) in polymer mechanochemistry is essential for the rational design of mechanophores with desired properties, yet SMARs noncovalent mechanical transformations remain relatively underexplored. In this study, we designed a subset diarylethene based on lever-arm hypothesis and systematically investigated their toward noncovalent-yet-chemical conversion atropisomer stereochemistry. Results from Density functional theory (DFT)...

Polymers that release small molecules in response to mechanical force are attractive materials for a wide variety of applications. Here, we report new mechanophore platform based on masked 2-furylcarbinol derivative incorporates 5-aryloxy group, which serves as both an electron-rich substituent accelerate molecular and the position polymer attachment proximal furan-maleimide junction. The is readily synthesized efficiently releases phenol arylamine payloads following activation.

Free-standing, stimuli-responsive polyelectrolyte multilayer films enabled by light-induced degradation of sacrificial compartments are introduced. Two examples described: i) a triple responsive film that uses light, redox, and pH for different functions, ii) wavelengths light functions. This approach to multiresponsive materials offers simple design chemical synthesis while enabling stimuli perform separate functions in the same material.

We report photolabile polyelectrolyte multilayers (PEMs), produced by the layer-by-layer (LbL) approach, which comprise commercially available photoinert polyanions and polycations. Photochemical degradation of synthetic polycations renders these PEMs soluble in near neutral aqueous solutions. Taking advantage vast array photocleavable chromophores that absorb different wavelengths light with quantum yields photolysis, we designed four (P1–P4), each containing groups: dialkylaminocoumarin...

The photosensitivity of ROMP gels to UV light is broadly tunable based on the structure <italic>o</italic>-nitrobenzyl-derived crosslinkers.

Mechanophores are molecules that undergo productive, covalent chemical transformations in response to mechanical force. Over the last decade, a variety of mechanochromic mechanophores have been developed enable direct visualization stress polymers and polymeric materials through changes color chemiluminescence. The recent introduction mechanochemically gated photoswitching extends repertoire polymer mechanochromism by decoupling activation from visible response, enabling history be recorded...

Abstract Diarylethenes are an important class of photoswitches that usually exist in interconvertible parallel (photoinert) and antiparallel (photochromic) conformational states. Recent research afforded sterically congested diarylethenes as stable separable configurational atropisomers. Rational manipulation stereochemistry is a robust strategy for regulating diarylethene photochemistry. Here, we present brief account the conformer/atropisomer-dependent photochromism photoswitches, discuss...

Combining the numerous advantages of using light as a stimulus, simple free radical random copolymerization, and easy, all-aqueous preparation polyelectrolyte complexes (PECs), we prepared photolabile PEC nanoparticles demonstrated their rapid degradation under UV light. As proof concept demonstration, dye Nile Red was encapsulated in PECs successfully released into surrounding solution nanocomplex carriers dissolved upon irradiation.

We report a directly photopatternable polythiophene derivative PToNB with o-nitrobenzyl (oNB)-functionalized side chains. has unique phototunable solubilities programmed through three stages: (i) organic-soluble/aqueous-insoluble, (ii) organic-insoluble/aqueous-insoluble, and (iii) organic-insoluble/aqueous soluble. The capability to control conjugated polymer solubility spatiotemporal precision orthogonal developer solvents stages allows for direct patterning of this provides flexibility...

This communication describes photoresponsive gels, prepared using ring‐opening metathesis polymerization (ROMP), that dissolve upon irradiation with ultraviolet light. Exposure of mixtures norbornene‐type ROMP monomers and new photoreactive cross‐linkers comprising two norbornene units bound through a chain containing o‐ nitrobenzyl esters (NBEs) to well‐known ruthenium carbene catalysts gave cross‐linked polymer networks swelled in organic solvents or water depending on the structure...

This paper describes polyelectrolyte multilayer films prepared by the layer-by-layer (LbL) technique capable of undergoing dissolution upon exposure to either ultraviolet or near-infrared light. Film is driven photochemical deprotection a random methacrylic copolymer with two types side chains: (i) 6-bromo-7-hydroxycoumarinyl esters, photocleavable groups that are known have substantial two-photon photolysis cross sections, and (ii) cationic residues from commercially available monomer...

Self-immolative chemistry has received significant attention in drug delivery and controlled release, leveraging a unique mechanism where triggering event initiates reaction cascade that releases molecular payloads. Herein, we introduce the concept of supramolecular gated self-immolative chemistry, allowing for control covalent bond scission through noncovalent host-guest interactions. Supramolecular regulation self-immolation is exemplified using newly designed ethylenediamine-based,...

Understanding structure-mechanical activity relationships (SMARs) in polymer mechanochemistry is essential for the rational design of mechanophores with desired properties, yet SMARs noncovalent mechanical transformations remain relatively underexplored. In this study, we designed a subset diarylethene based on lever-arm hypothesis and systematically investigated their toward noncovalent-yet-chemical conversion atro-pisomer stereochemistry. Results from DFT calculations, single-molecule...

Understanding structure-mechanical activity relationships (SMARs) in polymer mechanochemistry is essential for the rational design of mechanophores with desired properties, yet SMARs noncovalent mechanical transformations remain relatively underexplored. In this study, we designed a subset diarylethene based on lever-arm hypothesis and systematically investigated their toward noncovalent-yet-chemical conversion atro-pisomer stereochemistry. Results from DFT calculations, single-molecule...