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Polymer mechanochemistry utilizes mechanical force to activate latent functionalities in macromolecules and widely relies on ultrasonication techniques. Fundamental constraints of frequency and power intensity have prohibited the application of the polymer mechanochemistry principles in a biomedical context up to now, although medical ultrasound is a clinically established modality. Here, a universal polynucleotide framework is presented that allows the binding and release of therapeutic oligonucleotides, both DNA- and RNA-based, as cargo by biocompatible medical imaging ultrasound. It is shown that the high molar mass, colloidal assembly, and a distinct mechanochemical mechanism enable the force-induced release of cargo and subsequent activation of biological function in vitro and in vivo. Thereby, this work introduces a platform for the exploration of biological questions and therapeutics development steered by mechanical force.
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http://dx.doi.org/10.1002/adma.202403752 | DOI Listing |
Proc Natl Acad Sci U S A
September 2025
McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712.
Many soft, tough materials have emerged in recent years, paving the way for advances in wearable electronics, soft robotics, and flexible displays. However, understanding the interfacial fracture behavior of these materials remains a significant challenge, owing to the difficulty of quantifying the respective contributions from viscoelasticity and damage to energy dissipation ahead of cracks. This work aims to address this challenge by labeling a series of polymer networks with fluorogenic mechanophores, subjecting them to T-peel tests at various rates and temperatures, and quantifying their force-induced damage using a confocal microscope.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan.
A collection of mechanophores was computationally studied using the extended artificial force induced reaction (EX-AFIR) method, which utilizes two different sets of forces to determine the activation force level () practically and efficiently. Identifying a mechanophore's is a focus of mechanochemistry. As have been done in an existing framework, we generated the Δ- curve, where is the value of external force and Δ denotes the force-coupled free energy barrier of a specific reaction under .
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Adolphe Merkle Institute, University of Fribourg, Chemin des Verdiers 4, Fribourg, 1700, Switzerland.
Optical mechanophores offer a powerful platform for the real-time, nondestructive detection of mechanically induced damage in polymers. However, the exploitation of mechanophores for fundamental investigations of deformation processes and the prediction of failure in technologically critical applications has been constrained by their responsivity to other stimuli, laborious synthesis, and limited control of their photophysical and mechanical properties. Here, we report a cyclobutane-based mechanophore that activates a fluorescent coumarin dye through the application of mechanical stress in solution and in the solid state.
View Article and Find Full Text PDFPolymers (Basel)
August 2025
Institute of Polymers, Composites and Biomaterials, National Research Council of Italy (IPCB-CNR), Via Campi Flegrei 34, 80078 Pozzuoli, Italy.
In this study, multicomponent PLA-based biocomposites were developed. In particular, both native fibrous cellulose and cellulose with modified morphology obtained through ball milling treatments were incorporated into the polyester matrix in combination with an oligomeric plasticizer, specifically a lactic acid oligomer (OLA). The resulting materials were analyzed in terms of their morphology, thermal and mechanical properties over time, water vapor permeability, and degradation under soil burial conditions in comparison to neat PLA and unplasticized PLA/cellulose composites.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, Stanford University, Stanford, California 94305, United States.
Mechanical force can induce and perturb chemical reactivity. By embedding force-responsive molecules, known as mechanophores, within polymer chains, forces can be precisely applied at specific locations within the molecules. Significant advances in polymer mechanochemistry over the past two decades have enhanced our understanding of how to design and control mechanical reactivity of molecular structures, enabled new types of (macro)molecular transformations that are inaccessible via thermal or photochemical manifolds, and led to the development of stress-sensing and toughening materials.
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