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  1. Free, publicly-accessible full text available September 14, 2024
  2. Abstract We investigate the effect of bis(imino)pyridine (BIP) ligands in guiding self-assembly of semiconducting CdSe/ZnS quantum dots (QDs) into three-dimensional multi-layered shells with diameters spanning the entire mesoscopic range, from 200 nm to 2 μm. The assembly process is directed by guest–host interactions between the BIP ligands and a thermotropic liquid crystal (LC), with the latter’s phase transition driving the process. Characterization of the shell structures, through scanning electron microscopy and dynamic light scattering, demonstrates that the average shell diameter depends on the BIP structure, and that changing one functional group in the chemical scaffold allows systematic tuning of shell sizes across the entire range. Differential scanning calorimetry confirms a relationship between shell sizes and the thermodynamic perturbation of the BIP molecules to the LC phase transition temperature, allowing analytical modeling of shell assembly energetics. This novel mechanism to controllably tune shell sizes over the entire mesoscale via one standard protocol is a significant development for research on in situ cargo/drug delivery platforms using nano-assembled structures. 
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  4. The concept of “cloaking” an object is a very attractive one, especially in the visible (VIS) and near infra-red (NIR) regions of the electromagnetic spectrum, as that would reduce the visibility of an object to the eye. One possible route to achieving this goal is by leveraging the plasmonic property of metallic nanoparticles (NPs). We model and simulate light in the VIS and NIR scattered by a core of a homogeneous medium, covered by plasmonic cloak that is a spherical shell composed of gold nanoparticles (AuNPs). To consider realistic, scalable, and robust plasmonic cloaks that are comparable, or larger, in size to the wavelength, we introduce a multiscale simulation platform. This model uses the multiple scattering theory of Foldy and Lax to model interactions of light with AuNPs combined with the method of fundamental solutions to model interactions with the core. Numerical results of our simulations for the scattering cross-sections of core-shell composite indicate significant scattering suppression of up to 50% over a substantial portion of the desired spectral range (400 - 600 nm) for cores as large as 900 nm in diameter by a suitable combination of AuNP sizes and filling fractions of AuNPs in the shell.

     
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  5. Abstract

    The authors reveal a thermal actuating bilayer that undergoes reversible deformation in response to low‐energy thermal stimuli, for example, a few degrees of temperature increase. It is made of an aligned carbon nanotube (CNT) sheet covalently connected to a polymer layer in which dibenzocycloocta‐1,5‐diene (DBCOD) actuating units are oriented parallel to CNTs. Upon exposure to low‐energy thermal stimulation, coordinated submolecular‐level conformational changes of DBCODs result in macroscopic thermal contraction. This unique thermal contraction offers distinct advantages. It's inherently fast, repeatable, low‐energy driven, and medium independent. The covalent interface and reversible nature of the conformational change bestow this bilayer with excellent repeatability, up to at least 70 000 cycles. Unlike conventional CNT bilayer systems, this system can achieve high precision actuation readily and can be scaled down to nanoscale. A new platform made of poly(vinylidene fluoride) (PVDF) in tandem with the bilayer can harvest low‐grade thermal energy and convert it into electricity. The platform produces 86 times greater energy than PVDF alone upon exposure to 6 °C thermal fluctuations above room temperature. This platform provides a pathway to low‐grade thermal energy harvesting. It also enables low‐energy driven thermal artificial robotics, ultrasensitive thermal sensors, and remote controlled near infrared (NIR) driven actuators.

     
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