Computer Simulations of Responsive Nanogels at Lipid Membrane.

The swelling and collapse of responsive nanogels on a planar lipid bilayer are studied by means of mesoscopic computer simulations. The effects of molecular weight, cross-linking density, and adhesion strength are examined. The conditions for collapse-mediated engulfing by the bilayer are found. In particular, the results show that at low hydrophobicity level the increase in the nanogel softness decreases the engulfing rate. On the contrary, for stronger hydrophobicity level the trend changes to the opposite one. At the same time, when the cross-linking density is too low or the adhesion strength is too high the nanogel deformation at the membrane suppresses the engulfing regardless of the network swelling ratio. Finally, for comparative reasons, the behavior of the nanogels is also studied at the solid surface. These results may be useful in the design of soft particles capable of tuning of their elasticity and porosity for successful intracellular drug delivery.

Magnetically Recyclable Nanoscale Zero-Valent Iron-Mediated PhotoRDRP in Ionic Liquid toward Smart, Functional Polymers.

A facile method based on recyclable nanoscale zero-valent iron (nZVI)-mediated photoinduced reversible deactivation radical polymerization in ionic liquid (IL) leads to the synthesis of narrow disperse poly(tert-butyl methacrylate) (PTBMA), amphiphilic PTBMA-block-poly(poly(ethylene glycol)methacrylate) diblock copolymer and double hydrophilic poly(methacrylic acid)-block-poly(poly(ethylene glycol)methacrylate) (PMAA-b-PPEGMA) diblock copolymers thereof. Stimuli response of the synthesized PMAA-b-PPEGMA diblock copolymer against variation in pH and temperature is assessed. Recyclability of the nZVI (catalyst) and IL (solvent) is established. Polymerization may be switched ON or OFF, simply by turning the UVA light irradiation ON or OFF, offering temporal control. The diblock copolymer self-aggregates into spherical nanoaggregates which are employed for encapsulation of coumarin 102 (C102, a typical hydrophobic dye), describing their potential application in drug delivery applications. The facile synthesis strategy may open up new avenues for the preparation of intelligent functional polymers for engineering and biomedical applications.

Advancements in Polymer-Assisted Layer-by-Layer Fabrication of Wearable Sensors for Health Monitoring.

Recent advancements in polymer-assisted layer-by-layer (LbL) fabrication have revolutionized the development of wearable sensors for health monitoring. LbL self-assembly has emerged as a powerful and versatile technique for creating conformal, flexible, and multi-functional films on various substrates, making it particularly suitable for fabricating wearable sensors. The incorporation of polymers, both natural and synthetic, has played a crucial role in enhancing the performance, stability, and biocompatibility of these sensors. This review provides a comprehensive overview of the principles of LbL self-assembly, the role of polymers in sensor fabrication, and the various types of LbL-fabricated wearable sensors for physical, chemical, and biological sensing. The applications of these sensors in continuous health monitoring, disease diagnosis, and management are discussed in detail, highlighting their potential to revolutionize personalized healthcare. Despite significant progress, challenges related to long-term stability, biocompatibility, data acquisition, and large-scale manufacturing are still to be addressed, providing insights into future research directions. With continued advancements in polymer-assisted LbL fabrication and related fields, wearable sensors are poised to improve the quality of life for individuals worldwide.

Metal-Ligand Bonds Based Reprogrammable and Re-processable Supramolecular Liquid Crystal Elastomer Network.

Dynamic covalent bonds endow liquid crystal elastomers (LCEs) with network rearrangeability, facilitating the fixation of mesogen alignment induced by external forces and enabling reversible actuation. In comparison, the bond exchange of supramolecular interactions is typically too significant to stably maintain the programmed alignment, particularly under intensified external stimuli. Nevertheless, the remaking and recycling of supramolecular interaction-based polymer networks are more accessible than those based on dynamic covalent bonds, as the latter are difficult to completely dissociate. Thus, preparing an LCE that possesses both supramolecular-like exchangeability and covalent bond-level stability remains a significant challenge. In this work, we addressed this issue by employing metal-ligand bonds as the crosslinking points of LCE networks. As such, mesogen alignment can be repeatedly encoded through metal-ligand bond exchange and stably maintained after programming, since the bond exchange rate is sufficiently slow when the programming and actuation temperatures are below the bond dissociation temperature. More importantly, the metal-ligand bonds can be completely dissociated at high temperatures, allowing the LCE network to be dissolved in a solvent and reshaped into desired geometries via solution casting. Building on these properties, our LCEs can be fabricated into versatile actuators, such as reversible folding origami, artificial muscles, and soft robotics.

Self-Assembled Microactuators Using Chiral Liquid Crystal Elastomers.

Materials that undergo reversible changes in form typically require top-down processing to program the microstructure of the material. As a result, it is difficult to program microscale, 3D shape-morphing materials that undergo non-uniaxial deformations. Here, a simple bottom-up fabrication approach to prepare bending microactuators is described. Spontaneous self-assembly of liquid crystal (LC) monomers with controlled chirality within 3D micromold results in a change in molecular orientation across thickness of the microstructure. As a result, heating induces bending in these microactuators. The concentration of chiral dopant is varied to adjust the chirality of the monomer mixture. Liquid crystal elastomer (LCE) microactuators doped with 0.05 wt% of chiral dopant produce needle-shaped actuators that bend from flat to an angle of 27.2 ± 11.3° at 180 °C. Higher concentrations of chiral dopant lead to actuators with reduced bending, and lower concentrations of chiral dopant lead to actuators with poorly controlled bending. Asymmetric molecular alignment inside 3D structure is confirmed by sectioning actuators. Arrays of microactuators that all bend in the same direction can be fabricated if symmetry of geometry of the microstructure is broken. It is envisioned that the new platform to synthesize microstructures can further be applied in soft robotics and biomedical devices.

Switching between 3D Surface Topographies in Liquid Crystal Elastomer Coatings Using Two-Step Imprint Lithography.

While dynamic surface topographies are fabricated using liquid crystal (LC) polymers, switching between two distinct 3D topographies remains challenging. In this work, two switchable 3D surface topographies are created in LC elastomer (LCE) coatings using a two-step imprint lithography process. A first imprinting creates a surface microstructure on the LCE coating which is polymerized by a base catalyzed partial thiol-acrylate crosslinking step. The structured coating is then imprinted with a second mold to program the second topography, which is subsequently fully polymerized by light. The resulting LCE coatings display reversible surface switching between the two programmed 3D states. By varying the molds used during the two imprinting steps, diverse dynamic topographies can be achieved. For example, by using grating and rough molds sequentially, switchable surface topographies between a random scatterer and an ordered diffractor are achieved. Additionally, by using negative and positive triangular prism molds consecutively, dynamic surface topographies switching between two 3D structural states are achieved, driven by differential order/disorder transitions in the different areas of the film. It is anticipated that this platform of dynamic 3D topological switching can be used for many applications, including antifouling and biomedical surfaces, switchable friction elements, tunable optics, and beyond.

Rational Understanding of Loading and Release of Doxorubicin by UV-Light- and pH-Responsive Poly(NIPAM-co-SPMA) Micelle-like Aggregates.

A deep understanding of the interactions between micelle-like aggregates and antineoplastic drugs is paramount to control their adequate delivery. Herein, Poly(NIPAM-co-SPMA) copolymer nanocarriers were synthesized according to our previous published methodology, and the loading and release of poorly and highly water-soluble doxorubicin forms (Dox and Dox-HCl, respectively) were evaluated upon UV light irradiation and pH-variation stimuli. Capillary electrophoresis (CE) coupled to a fluorescence detector (LIF) allowed us to specifically characterize these systems and deeply study the loading and release processes. For this purpose, varying concentrations of doxorubicin were tested, and the loading/release rates were indirectly quantified thanks to the "free" doxorubicin concentration in solution. This study highlighted that Dox loading (9.4 µg/mg) was more effective than Dox-HCl loading (5.5 µg/mg). In contrast, 68 and 74% of Dox-HCl were respectively released after 2 min upon pH variation (from 7.4 to 6.0) and combined UV + pH 6.0 stimuli, while only 27% of Dox was invariably released upon application of the same stimuli. These results are coherent with the characteristics of both DoxHCl and Dox: Electrostatic interactions between Dox-HCl and the micelle-membrane structure (NIPAM) seemed predominant, while hydrophobic interactions were expected between Dox and the SP moieties at the inner part of the micelle-like aggregate, leading to different behaviors in both loading and release of the two doxorubicin forms. For doxorubicin loading concentrations higher than 3 µM, the electrophoretic profiles presented an additional peak. Thanks to CE characterizations, this peak was attributed to the formation of a complex formed between the nonaggregated copolymer and the doxorubicin molecules. This report therefore undergoes deep characterization of the dynamic formation of different micelle/drug complexes involved in the global drug-delivery behavior and therefore contributes to the development of more effective stimuli-responsive nanocarriers.

Electro-Responsive Aggregation and Dissolution of Cationic Polymer Using Reversible Redox Reaction of Electron Mediator.

Stimuli-responsive aggregation of polymer chains in water has found a variety of applications in polymer science, biology, and chemical engineering. To date, the majority of the phase transitions between the aggregated and dissolved forms has been observed by changing the solution temperature, and an active and precise control on the phase transition with a high time resolution has been challenging. Herein, a reversible phase transition of poly(allylamine-co-allylurea) (PAU) in an aqueous electrolyte is achieved by electrochemical redox cycling of hexacyanoferrate(II/III) ([Fe(CN)6 ]4-/3- ) ion pair. The aggregation and dissolution cycle can be completed in a high-resolution time frame of as short as 5 s. The strong electrostatic interaction between the protonated primary amino group of PAU and the tetravalent [Fe(CN)6 ]4- anion induces the aggregation, while the oxidation to the trivalent [Fe(CN)6 ]3- anion reduces the attractive force, and the polymer chain redissolves in solution. The ureido group of PAU helps the chain-folding process through the formation of inter/intrachain hydrogen-bonding networks, resulting in the sharp phase transition. By using [Fe(CN)6 ]4-/3- as the electron mediator, the electrochemical control on the large transparency change of polymer aqueous solution is realized for the first time.

Double Stimuli-Responsive di- and Triblock Copolymers of Poly(N-isopropylacrylamide) and Poly(1-vinylimidazole): Synthesis and Self-Assembly.

For the first time, double stimuli-responsive properties of poly(N-isopropylacrylamide) (PNIPA) and poly(1-vinylimidazole) (PVIM) block copolymers in aqueous solutions were studied. The synthesis of PNIPA60-b-PVIM90 and PNIPA28-b-PVIM62-b-PNIPA29 was performed using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by size exclusion chromatography and 1H NMR spectroscopy. The conformational behavior of the polymers was studied using dynamic light scattering (DLS) and fluorescence spectroscopy (FS). It was found that PNIPA and block copolymers conformation and ability for self-assembly in aqueous medium below and above cloud point temperature depend on the locus of hydrophobic groups derived from the RAFT agent within the chain. Additionally, the length of PVIM block, its locus in the chain and charge perform an important role in the stabilization of macromolecular micelles and aggregates below and above cloud point temperature. At 25 °C the average hydrodynamic radius (Rh) of the block copolymer particles at pH 3 is lower than at pH 9 implying the self-assembling of macromolecules in the latter case. Cloud points of PNIPA60-b-PVIM90 are ~43 °C and ~37 °C at a pH of 3 and 9 and of PNIPA28-b-PVIM62-b-PNIPA29 they are ~35 °C and 31 °C at a pH of 3 and 9. Around cloud point independently of pH, the Rh value for triblock copolymer rises sharply, achieves the maximum value, then falls and reaches the constant value, while for diblock copolymer, it steadily grows after reaching cloud point. The information about polarity of microenvironment around polymer obtained by FS accords with DLS data.

Eco-Conscious Approach to Thermoresponsive Star-Comb and Mikto-Arm Polymers via Enzymatically Assisted Atom Transfer Radical Polymerization Followed by Ring-Opening Polymerization.

This study explores the synthesis, characterization, and application of a heterofunctional initiator derived from 2-hydroxypropyl cyclodextrin (HP-ß-CD), having eight bromoester groups and thirteen hydroxyl groups allowing the synthesis of mikto-arm star-shaped polymers. The bromoesterification of HP-ß-CD was achieved using α-bromoisobutyryl bromide as the acylation reagent, modifying the cyclodextrin (CD) molecule as confirmed by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR), attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy analysis, and differential scanning calorimetry (DSC) thermograms. The initiator's effectiveness was further demonstrated by obtaining star-comb and mikto-arm polymers via an enzymatically assisted atom transfer radical polymerization (ATRP) method and subsequent ring-opening polymerization (ROP). The ATR polymerization quality and control depended on the type of monomer and was optimized by the way of introducing the initiator into the reaction mixture. In the case of ATRP, high conversion rates for poly(ethylene oxide) methyl ether methacrylate (OEOMA), with molecular weights (Mn) of 500 g/mol and 300 g/mol, were achieved. The molecular weight distribution of the obtained polymers remained in the range of 1.23-1.75. The obtained star-comb polymers were characterized by different arm lengths. Unreacted hydroxyl groups in the core of exemplary star-comb polymers were utilized in the ROP of ε-caprolactone (CL) to obtain a hydrophilic mikto-arm polymer. Cloud point temperature (TCP) values of the synthesized polymers increased with arm length, indicating the polymers' reduced hydrophobicity and enhanced solvation by water. Atomic force microscopy (AFM) analysis revealed the ability of the star-comb polymers to create fractals. The study elucidates advancements in the synthesis and utilization of hydrophilic sugar-based initiators for enzymatically assisted ATRP in an aqueous solution for obtaining complex star-comb polymers in a controlled manner.

Adhesion, proliferation, and detachment of various cell types on thermoresponsive microgel coatings.

Cutting-edge biomedical applications require increasingly complex and fastidious cell systems, for example, various classes of primary or stem cells. Their cultivation, however, still differs little from 30 years ago. This especially applies to the use of indiscriminative proteases for nonspecific cell detachment. A far more gentle alternative changes the adhesive properties of the cell culture substrates through coatings based on thermoresponsive polymers. Such polymers mediate cell adhesion at 37°C, but become repulsive upon a cell-compatible temperature drop to, for example, 32°C. While the high functionality of this method has already been well proven, it must also be easy and reproducible to apply. Here, we emphasize the potential of standard cell culture materials coated by spraying with thermoresponsive microgels for routine cultivation and beyond. On these surfaces, we successfully cultivated and detached various cell types, including induced pluripotent stem cells and cells in serum-free culture. In addition, we evaluated the compatibility of the microgel-sprayed surfaces with adhesion-promoting proteins, which are essential for, for example, stem cells or neuronal cells. Finally, we demonstrate that the microgel surfaces do not impair proliferation and show their long-term stability. We conclude that for cell detachment, thermoresponsive cell culture substrates can fully substitute proteases, like trypsin, by employing a comparably straightforward protocol that is compatible with many industrial processing lines.

Microgels and Nanogels for the Delivery of Poorly Water-Soluble Drugs.

While microgels and nanogels are most commonly used for the delivery of hydrophilic therapeutics, the water-swollen structure, size, deformability, colloidal stability, functionality, and physicochemical tunability of microgels can also offer benefits for addressing many of the barriers of conventional vehicles for the delivery of hydrophobic therapeutics. In this review, we describe approaches for designing microgels with the potential to load and subsequently deliver hydrophobic drugs by creating compartmentalized microgels (e.g., core-shell structures), introducing hydrophobic domains in microgels, leveraging host-guest interactions, and/or applying "smart" environmentally responsive materials with switchable hydrophobicity. In particular, the challenge of promoting hydrophobic drug loading without compromising the inherent advantages of microgels as delivery vehicles and ensuring practically relevant release kinetics from such structures is highlighted, with an eye toward the practical translation of such vehicles to the clinic.

Donor-Acceptor Stenhouse Adduct-Polydimethylsiloxane-Conjugates for Enhanced Photoswitching in Bulk Polymers.

Donor-acceptor Stenhouse adducts (DASAs) are a rapidly emerging class of visible light-activated photochromes and DASA-functionalized polymers hold great promise as biocompatible photoresponsive materials. However, the photoswitching performance of DASAs in solid polymer matrices is often low, particularly in materials below their glass transition temperature. To overcome this limitation, DASAs are conjugated to polydimethylsiloxanes which have a glass transition temperature far below room temperature and which can create a mobile molecular environment around the DASAs for achieving more solution-like photoswitching kinetics in bulk polymers. The dispersion of DASAs conjugated to such flexible oligomers into solid polymer matrices allows for more effective and tunable DASA photoswitching in stiff polymers, such as poly(methyl methacrylate), without requiring modifications of the matrix. The photoswitching of conjugates with varying polymer molecular weight, linker type, and architecture is characterized via time-dependent UV-vis spectroscopy in organic solvents and blended into polymethacrylate films. In addition, DASA-functionalized polydimethylsiloxane networks, accessible via the same synthetic route, provide an alternative solution for achieving fast and efficient DASA photoswitching in the bulk owing to their intrinsic softness and flexibility. These findings may contribute to the development of DASA-functionalized materials with better tunable, more effective, and more reversible modulation of their optical properties.

Stimuli-Responsive Aggregation of High Molar Mass Poly(N,N-Diethylacrylamide)-b-Poly(4-Acryloylmorpholine) in Tetrahydrofuran.

The self-assembly of block copolymers constitutes a timely research area in polymer science with implications for applications like sensing or drug-delivery. Here, the unprecedented aggregation behavior of high molar mass block copolymer poly(N,N-diethylacrylamide)-b-poly(4-acryloylmorpholine) (PDEA-b-PAM) (Mn >400 kg mol-1 ) in organic solvent tetrahydrofuran (THF) is investigated. To elucidate the aggregation, dynamic light scattering, cryo-transmission electron microscopy, and turbidimetry are employed. The aggregate formation is assigned to the unprecedented upper critical solution temperature behavior of PAM in THF at elevated concentrations (> 6 wt.%) and high molar masses. Various future directions for this new thermo-responsive block copolymer are envisioned, for example, in the areas of photonics or templating of inorganic structures.

Antiseptic Materials on the Base of Polymer Interpenetrating Networks Microgels and Benzalkonium Chloride.

Polymer microgels, including those based on interpenetrating networks (IPNs), are currently vastly studied, and their practical applications are a matter of thriving research. In this work, we show the perspective for the use of polyelectrolyte IPN microgels either as scavengers or carriers of antiseptic substances. Here, we report that poly-N-isopropylacrylamide/polyacrylic acid IPN microgels can efficiently absorb the common bactericidal and virucidal compound benzalkonium chloride. The particles can form a stable aqueous colloidal suspension or be used as building blocks for soft free-standing films. Both materials showed antiseptic efficacy on the examples of Bacillus subtilis and S. aureus, which was approximately equal to the commercial antibiotic. Such polymer biocides can be used as liquid disinfectants, stable surface coatings, or parts of biomedical devices and can enhance the versatility of the possible practical applications of polymer microgels.

Photocrosslinked Bioreducible Polymeric Nanoparticles for Enhanced Systemic siRNA Delivery as Cancer Therapy.

Clinical translation of polymer-based nanocarriers for systemic delivery of RNA has been limited due to poor colloidal stability in the blood stream and intracellular delivery of the RNA to the cytosol. To address these limitations, this study reports a new strategy incorporating photocrosslinking of bioreducible nanoparticles for improved stability extracellularly and rapid release of RNA intracellularly. In this design, the polymeric nanocarriers contain ester bonds for hydrolytic degradation and disulfide bonds for environmentally triggered small interfering RNA (siRNA) release in the cytosol. These photocrosslinked bioreducible nanoparticles (XbNPs) have a shielded surface charge, reduced adsorption of serum proteins, and enable superior siRNA-mediated knockdown in both glioma and melanoma cells in high-serum conditions compared to non-crosslinked formulations. Mechanistically, XbNPs promote cellular uptake and the presence of secondary and tertiary amines enables efficient endosomal escape. Following systemic administration, XbNPs facilitate targeting of cancer cells and tissue-mediated siRNA delivery beyond the liver, unlike conventional nanoparticle-based delivery. These attributes of XbNPs facilitate robust siRNA-mediated knockdown in vivo in melanoma tumors colonized in the lungs following systemic administration. Thus, biodegradable polymeric nanoparticles, via photocrosslinking, demonstrate extended colloidal stability and efficient delivery of RNA therapeutics under physiological conditions, and thereby potentially advance systemic delivery technologies for nucleic acid-based therapeutics.

Stimuli-Responsive Multifunctional Phenylboronic Acid Polymers Via Multicomponent Reactions: From Synthesis to Application.

Stimuli-responsive polymers undergo changes under different environmental conditions. Among them, phenylboronic acid (PBA) containing polymers (PBA-polymers) are unique, because they can selectively react with diols to generate borates that are sensitive to pH, sugars, and H2 O2 , and can be effectively used to synthesize smart drug carriers and self-healing hydrogels. Recently, multifunctional PBA-polymers (MF-PBA-polymers) have been developed using multicomponent reactions (MCRs) to introduce PBA groups into polymer structures. These MF-PBA-polymers have features similar to those of traditional PBA-polymers; moreover, they exhibit additional properties, such as fluorescence, antimicrobial activity, and antioxidant capability, when different MCRs are used. In this mini review, the preparation of these MF-PBA-polymers are summarized and the new properties/functions that have been introduced into these polymers using different MCRs are discussed. The uses of these MF-PBA-polymers as fluorescent cell anticoagulants, drug carriers, and gelators of functional self-healing hydrogels have been discussed. Additionally, the challenges encountered during their preparation are discussed and also the future developments in this field are touched upon.

Membrane Anchored Polymers Modulate Amyloid Fibrillation.

The nucleating role of cellular membrane components, such as lipid moieties on amyloid beta (Aß1-40 ) fibrillation, has been reported in recent years. The influence of conjugates fabricated from lipid anchors (cholesterol, diacylglycerol) and hydrophilic polymers on Aß1-40 fibrillation is reported here, aiming to understand the impact of polymers cloud point temperature (Tcp ) and its hydrophobic tails on the amyloid fibrillation. Novel lipid-polymer conjugates, consisting of poly(oligo(ethylene glycol)m acrylates) and hydrophobic groups (diacylglyceryl-, cholesteryl-, octyl-, decyl-, hexadecyl-) as anchors are synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization, allowing to tune the hydrophilic-hydrophobic profile of the conjugates by varying both, the degree of polymerization (n) and number of ethylene glycol units (m) in their side chain. The impact of these conjugates on Aß1-40 fibrillation is investigated via in vitro kinetic studies and transmission electron microscopy (TEM). Hydrophobic lipid-anchors are significantly delaying fibrillation (both lag- and half times), observing similar fibrillar structures via TEM when compared to native Aß1-40 . Other hydrophobic end groups are also delaying fibrillation of Aß1-40 , irrespective of their "n" and "m," whereas more hydrophilic polymers (both with longer ethylene glycol-sidechains, m = 3 for octyl, decyl and m = 5 for cholesterol) are only marginally inhibited fibrillation.

Anisotropic and Self-Healing Copolymer with Multiresponsive Capability via Recyclable Alloy-Mediated RDRP.

A novel triple stimuli sensitive block copolymer is prepared by magnetically separable and reusable (up to multiple cycles) Ni-Co alloy nanoparticles mediated reversible deactivation radical polymerization (RDRP) at 25 °C, that responds to changes in temperature, pH, and light. Design of this block copolymer constitutes a temperature-sensitive N-isopropylacrylamide (NIPAM), an acid-sensitive lysine methacrylamide (LysMAM), and a light responsive umbelliferone (UMB) end group. The stimuli response, in response to one stimulus as well as combinations of stimuli, has been evaluated. Responsiveness to light allows the construction of self-healing materials. Density functional theory calculations rationalize the underlying mechanism of the polymerization.

From Molecules to Polymers-Harnessing Inter- and Intramolecular Interactions to Create Mechanochromic Materials.

The development of mechanophores as building blocks that serve as predefined weak linkages has enabled the creation of mechanoresponsive and mechanochromic polymer materials, which are interesting for a range of applications including the study of biological specimens or advanced security features. In typical mechanophores, covalent bonds are broken when polymers that contain these chemical motifs are exposed to mechanical forces, and changes of the optical properties upon bond scission can be harnessed as a signal that enables the detection of applied mechanical stresses and strains. Similar chromic effects upon mechanical deformation of polymers can also be achieved without relying on the scission of covalent bonds. The dissociation of motifs that feature directional noncovalent interactions, the disruption of aggregated molecules, and conformational changes in molecules or polymers constitute an attractive element for the design of mechanoresponsive and mechanochromic materials. In this article, it is reviewed how such alterations of molecules and polymers can be exploited for the development of mechanochromic materials that signal deformation without breaking covalent bonds. Recent illustrative examples are highlighted that showcase how the use of such mechanoresponsive motifs enables the visual mapping of stresses and damage in a reversible and highly sensitive manner.