DNA surface ligands can be used as programmable "bonds" to control the arrangement of nanoparticles into crystalline superlattices. Here, we study the intrinsic responsiveness of these DNA bonds to changes in local dielectric constant (εr) as a new approach to dynamically modulate superlattice structure. Remarkably, ethanol (EtOH) addition can be used to controllably tune DNA bond length from 16 to 3 nm and to increase bond stability by >40 °C, while retaining long-range order and crystal habit. Interestingly, we find that these structural changes, which involve the expansion and contraction of crystals by up to 75% in volume, occur in a cooperative fashion once a critical percentage of EtOH is reached. These results provide a facile and robust approach to create stimuli-responsive lattices, to access high volume fractions, and to improve thermal stability.
Electron microscopy (EM) represents the most powerful tool to directly characterize the structure of individual nanoparticles. Accurate descriptions of nanoparticle populations with EM, however, are currently limited by the lack of tools to quantitatively analyze populations in a high-throughput manner. Herein, we report a computational method to algorithmically analyze EM images that allows for the first automated structural quantification of heterogeneous nanostructure populations, with species that differ in both size and shape. This allows one to accurately describe nanoscale structure at the bulk level, analogous to ensemble measurements with individual particle resolution. With our described EM protocol and our inclusion of freely available code for our algorithmic analysis, we aim to standardize EM characterization of nanostructure populations to increase reproducibility, objectivity, and throughput in measurements. We believe this work will have significant implications in diverse research areas involving nanomaterials, including, but not limited to, fundamental studies of structural control in nanoparticle synthesis, nanomaterial-based therapeutics and diagnostics, optoelectronics, and catalysis.
Anisotropic gold nanoparticles often exhibit superior optical properties compared to spherical ones, in part due to intense electric field localization near sharp geometric features and a broadly tunable localized surface plasmon resonance. As a result, anisotropic nanoparticles are attractive building blocks for surface-enhanced Raman spectroscopy (SERS) substrates. To unlock the full potential of such substrates, one should be able to (1) generate a sufficient number of SERS hotspots with structures of controlled shape and size and (2) remove ligands so that analytes can easily access nanoparticle surface sites. Here, we develop a synthetic strategy for the shape- and size-controlled anisotropic growth of gold nanoparticles (concave rhombic dodecahedra and concave cubes, 70–135 nm characteristic length) from spherical seeds anchored on a structurally complex surface (common filter paper) and subsequently combine electrodynamics and electronic structure calculations with experiment to systematically characterize these substrates using SERS. Furthermore, we explore the generalizable functionality of these substrate-stabilized nanoparticles by using a continuous extraction method to partially remove surface ligands that were necessary for anisotropic growth, enabling the specific SERS detection of serotonin, a molecular neurotransmitter with a weak affinity for gold.
Polyurethane shape memory polymers (SMPs) with tunable thermomechanical properties and advanced processing capabilities have been synthesized, characterized, and implemented in the design of a microactuator medical device prototype. The ability to manipulate glass transition temperature (Tg) and crosslink density in low-molecular weight aliphatic thermoplastic polyurethane SMPs is demonstrated using a synthetic approach that employs UV catalyzed thiol-ene “click” reactions to achieve post-polymerization crosslinking. PUs containing varying C=C functionalization are synthesized, solution blended with polythiol crosslinking agents and photoinitiator and subjected to UV irradiation, and the effects of number of synthetic parameters on crosslink density are reported. Thermomechanical properties are highly tunable, including glass transitions tailorable between 30 and 105°C and rubbery moduli tailorable between 0.4 and 20 MPa. This new SMP system exhibits high toughness for many formulations, especially in the case of low crosslink density materials, for which toughness exceeds 90 MJ/m3 at select straining temperatures. To demonstrate the advanced processing capability and synthetic versatility of this new SMP system, a laser-actuated SMP microgripper device for minimally invasive delivery of endovascular devices is fabricated, shown to exhibit an average gripping force of 1.43 ± 0.37 N and successfully deployed in an in vitro experimental setup under simulated physiological conditions.
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