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Integrating mechanophores into multiple-network elastomers enables 20-fold toughness enhancement and 37% activation and provides insights into the toughening mechanismviabond scission visualization. 

Abstract Synthetic plastics sourced from petroleum have gained widespread use since the 1950s. Polystyrene (PS) is one of the most extensively used plastics, as it is colorless, has high mechanical strength, and exhibits excellent chemical and thermal stability; however, it is also one of the least recycled plastics because of the high cost and low profit in recycling. Herein, we demonstrate a mechanochemical recycling approach that allows PS to be efficiently degraded into benzene when it is ground in a ball mill with AlCl₃. For example, when 165 kDa PS pellets are milled with AlCl₃, the extent of degradation reaches 90% at 15 min. Isotope labeling experiments indicate that both ambient water and the polymer backbone can be proton sources for the formation of benzene. The benzene generated in the mechanochemical degradation can be used to synthesize styrene, which can be repolymerized to produce polystyrene, allowing for the closed‐loop recycling of PS. In addition, a mechanochemical Friedel–Crafts acylation between the generated benzene and the subsequently added benzoic anhydride produces benzophenone in 40%–50% yield. The mechanochemical degradation process demonstrated here is solvent‐free, cost‐effective, and energy‐efficient, providing a promising route for the chemical recycling and upcycling of PS. 

Abstract Femtosecond laser‐induced damage threshold (LIDT) testing is carried out at 515 nm on 4‐mm‐sized metalens arrays that are manufactured by direct nanoimprinting of a TiO₂nanoparticle (NP)‐based ink containing either polymeric or inorganic binders. The all‐inorganic TiO₂metalenses exhibit ≈80% absolute focusing efficiency and demonstrate an LIDT of ≈90 mJ cm⁻²based on a single‐shot determination using Liu's method, while the metalenses with the polymeric binder achieve ≈137 mJ cm⁻²and an efficiency of ≈76%. Despite the higher LIDT of the TiO₂‐polymer composite metalenses in the single‐shot experiment, these lenses exhibit significant damage at fluences as low as ≈8 mJ cm⁻²when subjected to ≈6 × 10⁸ pulses at 60 kHz. On the other hand, the all‐inorganic metalenses remain intact under identical conditions at ≈64 mJ cm⁻². That is, the inorganic binder provides superior long‐term stability relative to the polymeric binder and is a more viable solution for high‐energy applications. Structural damages observed in nanostructures result in a reduced deflection efficiency and increase light scattering at the focal plane of the metalens. The LIDT testing is also performed in the nanosecond regime at 532 and 1064 nm with the all‐inorganic metalenses, yielding thresholds of ≈0.5 and ≈5 J cm⁻², respectively. 

Abstract We report a new class of hydrophobic polymer ligands with quaternary ammonium head groups for surface modification of noble metal nanoparticles (NPs). Quaternary ammonium ligands bind NPs through non‐covalent electrostatic interactions, producing polymer‐grafted NPs with high colloidal and chemical stability. These polymers having charged head groups offer powerful strategies to tailor the structure and function of metal‐electrolyte interfaces in electrocatalytic systems. The ammonium head groups serve as ionic reservoirs that preconcentrate bicarbonate counterions at the surface of nanocatalysts, while the hydrophobic polymer backbones restructure local hydrogen‐bonding networks, modulating water and ion transport dynamics. These interfacial effects promote CO₂electroreduction, particularly under diffusion‐limited conditions, resulting in a CO Faradaic efficiency (FE) exceeding 90%. 

Abstract The distinct molecular states — single molecule, assembly, and aggregate — of two ionic macromolecules, TPPE‐APOSS and TPE‐APOSS, are easily distinguishable through their tunable fluorescence emission wavelengths, which reflect variations in intermolecular distances. Both ionic macromolecules contain aggregation‐induced emission (AIE) active moieties whose emission wavelengths are directly correlated to their mutual distances in solution: far away from each other as individual molecules, maintaining a tunable and relatively long distance in electrostatic interactions‐controlled blackberry‐type assemblies (microphase separation), or approaching van der Waals close distance in aggregates (macrophase separation). Furthermore, within the blackberry assemblies, the emission wavelength decreases monotonically with increasing assembly size, indicative of shorter intermolecular distances at nanoscale. The emission changes of TPPE‐APOSS blackberry assemblies can even be visually distinguishable by eyes when their sizes and intermolecular distances are tuned. Molecular dynamics simulations further revealed that macromolecules are confined in various conformations by controllable intermolecular distances within the blackberry structure, thereby resulting in fluorescence emission with tunable wavelength. 

Abstract Highly efficient metalens arrays designed for 550 nm are directly printed using UV‐assisted nanoimprint lithography (UV‐NIL) and a TiO₂nanoparticle (NP)‐based ink on 8″ optical wafers with imprint times less than 5 min. Approximately one‐thousand 4‐mm metalenses are fabricated per wafer with uniform optical performance using a reusable PDMS‐based elastomeric stamp. The absolute and relative focusing efficiencies are as high as 81.2% and 90.4%, respectively, matching closely with the simulated maximum efficiencies of 83% and 91% achievable with the given master design, indicating that future improvements are possible, and efficiencies are not limited by materials or process. The imprinted metalenses are free from organics due to a post‐imprint calcination step and exhibit outstanding dimensional and optical stabilities. The highest efficiencies are attained using imprint formulations comprised of mixtures of 10 and 20 nm TiO₂NPs, whose denser packing not only increases the refractive index (RI) of the calcined lenses up to 2.0 but also reduces the feature shrinkage relative to the master. 25 cycles of atomic layer deposition of TiO₂following imprinting increase the RI up to 2.3 without changing dimensions by uniform gap filling between NPs. This work opens a path for true, full‐scale additive manufacturing of metaoptics. 

Abstract Macroion‐counterion interaction is essential for regulating the solution behaviors of hydrophilic macroions, as simple models for polyelectrolytes. Here, we explore the interaction between uranyl peroxide molecular cluster Li₆₈K₁₂(OH)₂₀[UO₂(O₂)OH]₆₀(U₆₀) and multivalent counterions. Different from interaction with monovalent counterions that shows a simple one‐step process, isothermal titration calorimetry, combined with light/X‐ray scattering measurements and electron microscopy, confirm a two‐step process for their interaction with multivalent counterions: an ion‐pairing betweenU₆₀and the counterion with partial breakage of hydration shells followed by strongU₆₀‐U₆₀attraction, leading to the formation of large nanosheets with severe breakage and reconstruction of hydration shells. The detailed studies on macroion‐counterion interaction can be nicely correlated to the microscopic (self‐assembly) and macroscopic (gelation or phase separation) phase transitions in the diluteU₆₀aqueous solutions induced by multivalent counterions. 

We study the ground state thermodynamics of a model class of geometrically frustrated assemblies, known as warped-jigsaw particles. While it is known that frustration in soft matter assemblies has the ability to propagate up to mesoscopic, multi-particle size scales, notably through the selection of the self-limiting domain, little is understood about how the symmetry of shape-misfit at the particle scale influences emergent morphologies at the mesoscale. Here we show that polarity in the shape-misfit of warped-jigsaw puzzles manifests at a larger scale in the morphology and thermodynamics of the ground-state assembly of self-limiting domains. We use a combination of continuum theory and discrete particle simulations to show that the polar misfit gives rise to two mesoscopically distinct polar, self-limiting ribbon domains. Thermodynamic selection between the two ribbon morphologies is controlled by a combination of the binding anisotropy along distinct neighbor directions and the orientation of polar shape-misfit. These predictions are valuable as design features for ongoing efforts to program self-limiting assemblies through the synthesis of intentionally frustrated particles, further suggesting a generic classification of frustrated assembly behavior in terms of the relative symmetries of shape-misfit and the underlying long-range inter-particle order it frustrates. 

Abstract We present a fundamental study that supports the feasibility of delaying the onset of presbyopia and age‐related cataracts via the utilization of surface‐functionalized poly(amidoamine) (PAMAM) dendrimers. These PAMAM derivatives are known to have the added benefit of permeating the human cornea with possible absorption/distribution into the crystalline lens, indicating the potential for use in a topically applied eye solution. Mature onset cataract formation occurs because of γ‐crystallin and β‐crystallin aggregation in the human lens over time. As the molecular chaperone α‐crystallin becomes saturated with unfolded γ‐crystallins, the ability to prevent aggregation becomes limited. PAMAM dendrimers containing either sodium carboxylate‐ or succinamic acid‐surface functionality are employed as synthetic chaperones to evaluate the effect of structure and local concentration on γ‐crystallin aggregation. The chaperone/γ‐crystallin blends are examined via DLS, zeta potential measurements, and fluorescence spectroscopy. DLS studies show a reduction in hydrodynamic size for γ‐crystallin in the presence of PAMAM dendrimers and their small molecule counterparts compared to the control. Structural identity and local concentration of functionality are found to impact solution behavior. Zeta potential measurements and fluorescence studies indicate that synthetic chaperones can have multiple modes of non‐covalent interactions and are the most effective in preventing or reducing γ‐crystallin aggregation. 

Abstract Organic emitters that exhibit room‐temperature phosphorescence (RTP) in neat films have application potential for optoelectronic devices, bio‐imaging, and sensing. Due to molecular vibrations or rotations, the majority of triplet excitons recombine rapidly via non‐radiative processes in purely organic emitters, making it challenging to observe RTP in amorphous films. Here, a chemical strategy to enhance RTP in amorphous neat films is reported, by utilizing through‐space charge‐transfer (TSCT) effect induced by intramolecular steric hindrance. The donor and acceptor groups interact via spatial orbital overlaps, while molecular motions are suppressed simultaneously. As a result, triplets generated under photo‐excitation are stabilized in amorphous films, contributing to phosphorescence even at room temperature. The solvatochromic effect on the steady‐state and transient photoluminescence reveals the charge‐transfer feature of involved excited states, while the TSCT effect is further experimentally resolved by femtosecond transient absorption spectroscopy. The designed luminescent materials with pronounced TSCT effect show RTP in amorphous films, with lifetimes up to ≈40 ms, comparable to that in a rigid polymer host. Photoluminescence afterglow longer than 3 s is observed in neat films at room temperature. Therefore, it is demonstrated that utilizing intramolecular steric hindrance to stabilize long‐lived triplets leads to phosphorescence in amorphous films at room temperature.