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  1. The growth of photochemistry and high throughput experimentation in well plates and flow drives interest in photochemical platforms that provide spatially uniform irradiation of reactions. Here, we present a design of a versatile, uniform light platform for photochemistry to enable increased performance and reproducibility for high throughput experimentation in shallow well plates, in-plane flow reactors, and droplets. The design of the platform is driven by the development of an open-source ray tracing light simulation package. Radiometry provides experimental validation of the system's irradiance and irradiance uniformity. The usefulness of the approach is demonstrated by application to the photoinduced electron transfer–reversible addition–fragmentation chain transfer polymerization of methyl acrylate. 
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  2. Autonomous experimental systems offer a compelling glimpse into a future where closed-loop, iterative cycles—performed by machines and guided by artificial intelligence (AI) and machine learning (ML)—play a foundational role in materials research and development. This perspective draws attention to the roles of networks and interfaces—of and between humans and machines—for the purpose of generating knowledge and accelerating innovation. Polymers, a class of materials with massive global impact, present a unique opportunity for the application of informatics and automation to pressing societal challenges. To develop these networks and interfaces in polymer science, the Community Resource for Innovation in Polymer Technology (CRIPT)—a polymer data ecosystem based on novel polymer data model, representation, search, and visualization technologies—is introduced. The ongoing co-design efforts engage stakeholders in industry, academia, and government to uncover rapidly actionable, high-impact opportunities to build networks, bridge interfaces, and catalyze innovation in polymer technology. 
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  3. Favorable polymer-substrate interactions induce surface orientation fields in block copolymer (BCP) melts. In linear BCP processed near equilibrium, alignment of domains generally persists for a small number of periods (∼4–6 D 0 ) before randomization of domain orientation. Bottlebrush BCP are an emerging class of materials with distinct chain dynamics stemming from substantial molecular rigidity, enabling rapid assembly at ultrahigh (>100 nm) domain periodicities with strong photonic properties (structural color). This work assesses interface-induced ordering in PS- b -PLA bottle b rush diblock copolymer films during thermal annealing between planar surfaces. To clearly observe the decay in orientational order from surface to bulk, we choose to study micron-scale films spanning greater than 200 lamellar periods. In situ optical microscopy and transmission UV-Vis spectroscopy are used to monitor photonic properties during annealing and paired with ex situ UV-Vis reflection measurement, cross-sectional scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS) to probe the evolution of domain microstructure. Photonic properties were observed to saturate within minutes of annealing at 150 °C, with distinct variation in transmission response as a function of film thickness. The depth of the highly aligned surface region was found to vary stochastically in the range of 30–100 lamellar periods, with the sharpness of the orientation gradient decreasing substantially with increasing film thickness. This observation suggests a competition between growth of aligned, heterogeneously nucleated, grains at the surface and orientationally isotropic, homogeneously nucleated, grains throughout the bulk. This work demonstrates the high potential of bottlebrush block copolymers in rapid fabrication workflows and provides a point of comparison for future application of directed self-assembly to BBCP ordering. 
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  4. Abstract

    The properties of a polymer are known to be intrinsically related to its molecular weight distribution (MWD); however, previous methodologies of MWD control do not use a design and result in arbitrary shaped MWDs. Here we report a precise design to synthesis protocol for producing a targeted MWD design with a simple to use, and chemistry agnostic computer-controlled tubular flow reactor. To support the development of this protocol, we constructed general reactor design rules by combining fluid mechanical principles, polymerization kinetics, and experiments. The ring opening polymerization of lactide, the anionic polymerization of styrene, and the ring opening metathesis polymerization are used as model polymerizations to develop the reactor design rules and synthesize MWD profiles. The derivation of a mathematical model enables the quantitative prediction of the experimental results, and this model provides a tool to explore the limits of any MWD design protocol.

     
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  5. Additive manufacturing of functional materials is limited by control of microstructure and assembly at the nanoscale. In this work, we integrate nonequilibrium self-assembly with direct-write three-dimensional (3D) printing to prepare bottlebrush block copolymer (BBCP) photonic crystals (PCs) with tunable structure color. After varying deposition conditions during printing of a single ink solution, peak reflected wavelength for BBCP PCs span a range of 403 to 626 nm (blue to red), corresponding to an estimated change in d-spacing of >70 nm (Bragg- Snell equation). Physical characterization confirms that these vivid optical effects are underpinned by tuning of lamellar domain spacing, which we attribute to modulation of polymer conformation. Using in situ optical microscopy and solvent-vapor annealing, we identify kinetic trapping of metastable microstructures during printing as the mechanism for domain size control. More generally, we present a robust processing scheme with potential for on-the-fly property tuning of a variety of functional materials. 
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