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  1. Free, publicly-accessible full text available August 1, 2023
  2. Free, publicly-accessible full text available February 1, 2023
  3. This work reveals the influence of pendant hydrogen bonding strength and distribution on self-assembly and the resulting thermomechanical properties of A-AB-A triblock copolymers. Reversible addition-fragmentation chain transfer polymerization afforded a library of A-AB-A acrylic triblock copolymers, wherein the A unit contained cytosine acrylate (CyA) or post-functionalized ureido cytosine acrylate (UCyA) and the B unit consisted of n-butyl acrylate (nBA). Differential scanning calorimetry revealed two glass transition temperatures, suggesting microphase-separation in the A-AB-A triblock copolymers. Thermomechanical and morphological analysis revealed the effects of hydrogen bonding distribution and strength on the self-assembly and microphase-separated morphology. Dynamic mechanical analysis showed multiple tan deltamore »(δ) transitions that correlated to chain relaxation and hydrogen bonding dissociation, further confirming the microphase-separated structure. In addition, UCyA triblock copolymers possessed an extended modulus plateau versus temperature compared to the CyA analogs due to the stronger association of quadruple hydrogen bonding. CyA triblock copolymers exhibited a cylindrical microphase-separated morphology according to small-angle X-ray scattering. In contrast, UCyA triblock copolymers lacked long-range ordering due to hydrogen bonding induced phase mixing. The incorporation of UCyA into the soft central block resulted in improved tensile strength, extensibility, and toughness compared to the AB random copolymer and A-B-A triblock copolymer comparisons. This study provides insight into the structure-property relationships of A-AB-A supramolecular triblock copolymers that result from tunable association strengths.« less
  4. Inclusions of basaltic melt trapped inside of olivine phenocrysts during igneous crystallization provide a rich, crystal-scale record of magmatic processes ranging from mantle melting to ascent, eruption, and quenching of magma during volcanic eruptions. Melt inclusions are particularly valuable for retaining information on volatiles such as H 2 O and CO 2 that are normally lost by vesiculation and degassing as magma ascends and erupts. However, the record preserved in melt inclusions can be variably obscured by postentrapment processes, and thus melt inclusion research requires careful evaluation of the effects of such processes. Here we review processes by which meltmore »inclusions are trapped and modified after trapping, describe new opportunities for studying the rates of magmatic and volcanic processes over a range of timescales using the kinetics of post-trapping processes, and describe recent developments in the use of volatile contents of melt inclusions to improve our understanding of how volcanoes work. ▪  Inclusions of silicate melt (magma) trapped inside of crystals formed by magma crystallization provide a rich, detailed record of what happens beneath volcanoes. ▪  These inclusions record information ranging from how magma forms deep inside Earth to its final hours as it ascends to the surface and erupts. ▪  The melt inclusion record, however, is complex and hazy because of many processes that modify the inclusions after they become trapped in crystals. ▪  Melt inclusions provide a primary archive of dissolved gases in magma, which are the key ingredients that make volcanoes erupt explosively.« less
  5. Abstract

    Interferometric scattering microscopy is increasingly employed in biomedical research owing to its extraordinary capability of detecting nano-objects individually through their intrinsic elastic scattering. To significantly improve the signal-to-noise ratio without increasing illumination intensity, we developed photonic resonator interferometric scattering microscopy (PRISM) in which a dielectric photonic crystal (PC) resonator is utilized as the sample substrate. The scattered light is amplified by the PC through resonant near-field enhancement, which then interferes with the <1% transmitted light to create a large intensity contrast. Importantly, the scattered photons assume the wavevectors delineated by PC’s photonic band structure, resulting in the ability tomore »utilize a non-immersion objective without significant loss at illumination density as low as 25 W cm−2. An analytical model of the scattering process is discussed, followed by demonstration of virus and protein detection. The results showcase the promise of nanophotonic surfaces in the development of resonance-enhanced interferometric microscopies.

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