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Free, publicly-accessible full text available January 28, 2026
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Modern materials design strategies take advantage of the increasing amount of materials property data available and increasingly complex algorithms to take advantage of those data. However, viscoelastic materials resist this trend towards increased data rates due to their inherent time-dependent properties. Therefore, viscoelasticity measurements present a roadblock for data collection in an important aspect of material design. For thermorheologically simple (TRS) materials, time–temperature superposition (TTS) made relaxation spectrum measurements faster relative to, for example, very long creep experiments. However, TTS itself currently faces a speed limit originating in the common logarithmic discrete frequency sweep (DFS) mode of operation. In DFS, the measurement time is proportional (by a factor much greater than one) to the lowest frequency of measurement. This state of affairs has not improved for TTS for half a century or more. We utilize recent work in experimental rheometry on windowed chirps to collect three decades of complex modulus data simultaneously, resulting in aB500% increase in data collection. In BOTTS, we superpose several isothermal chirp responses to produce a master curve in a fraction of time required by the traditional DFS-TTS technique. The chirp responses have good, albeit nontrivial, signal-to-noise properties. We use linear error propagation and a noise-weighted least squares approach to automatically incorporate all the data into a reliable shifting method. Using model thermoset polymers, we show that DFS- TTS and BOTTS results are comparable, and therefore BOTTS data represent a first step towards a faster method for master curve generation from unmodified rheological measurement instrumentsmore » « less
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Abstract Combining surface‐initiated, TdT (terminal deoxynucleotidyl transferase) catalyzed enzymatic polymerization (SI‐TcEP) with precisely engineered DNA origami nanostructures (DONs) presents an innovative pathway for the generation of stable, polynucleotide brush‐functionalized DNA nanostructures. We demonstrate that SI‐TcEP can site‐specifically pattern DONs with brushes containing both natural and non‐natural nucleotides. The brush functionalization can be precisely controlled in terms of the location of initiation sites on the origami core and the brush height and composition. Coarse‐grained simulations predict the conformation of the brush‐functionalized DONs that agree well with the experimentally observed morphologies. We find that polynucleotide brush‐functionalization increases the nuclease resistance of DONs significantly, and that this stability can be spatially programmed through the site‐specific growth of polynucleotide brushes. The ability to site‐specifically decorate DONs with brushes of natural and non‐natural nucleotides provides access to a large range of functionalized DON architectures that would allow for further supramolecular assembly, and for potential applications in smart nanoscale delivery systems.more » « less
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