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  1. A new N-alkynylated dithieno[3,2- b :2′,3′- d ]pyrrole (DTP) monomer was synthesized using a Buchwald–Hartwig amination of 3,3′-dibromo-2,2′-bithiophene with pent-4-yn-1-amine. The obtained monomer was investigated for the possibility of a pre-polymerization modification via Huisgen 1,3-dipolar cycloaddition (“click”) reaction with azide-containing organic compounds. The synthesized N-alkynylated DTP monomer is soluble in a number of organic solvents and reacts with organic azides via “click” reactions in mild conditions, achieving high yields. The N-alkynylated DTP monomer and its “click”-modified derivative can be electropolymerized to form polymeric films. Herein, the synthesis and characterization of a “click” modified DTP monomer, its pre-modified derivative, and their corresponding polymers are described. The developed method is a facile route to synthesize a new generation of various N-functionalized DTP homopolymers. 
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  2. Abstract

    The cold sintering process (CSP) is a low temperature processing technique that utilizes a transient phase to synthesize dense ceramics. However, some CSP parts contain microflaws that arise due to inhomogeneities in pressure, temperature, and transient phase. This work uses 20 MHz ultrasound to verify the presence of defects in CSP ZnO samples of varying densities (84%–97%). Acoustic metrics used in this work include wave speed, which is affected by differences in the effective elastic properties of the medium, and attenuation, which quantifies wave energy loss due to scattering from defects. Wave speed maps were inhomogeneous, suggesting density gradients which were verified with scanning electron microscopy. In addition, it was demonstrated that the pores produced by cold sintering are anisometric, which increases the anisotropy in the elastic properties. High attenuation regions (>300 Np/m) are present in all samples independent of relative density and correspond to defects identified in X‐ray computed tomography (XCT) which were as small as 38 µm in effective diameter. However, some high attenuation spots do not correspond to visible defects in XCT, which suggests the presence of features undetectable with XCT such as residual secondary phases at the grain boundaries.

     
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  3. An organic, x-ray radioluminescent colloid is fabricated by copolymerizing an organic scintillating monomer within a polystyrene basis. The intensity of emitted light from the radioluminescent colloidal particles can be manipulated by photonic means.

     
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  4. X-ray active, terpolymer nanospheres are fabricated by copolymerizing styrene, propargyl acrylate, and anthracene methyl methacrylate. The strong Coulombic forces between particles induce spontaneous self-assembly into a crystalline colloidal array.

     
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  5. Radioluminescent copolymer nanoparticles that self-assembled into a crystalline colloidal array due to electrostatic repulsion were encapsulated within hydrogels. The rejection wavelength of the gels was tuned through drying and swelling the system.

     
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  6. Due to Coulombic forces, X-ray active copolymer nanoparticles self-assembled into crystalline colloidal arrays which were stabilized through encapsulation in hydrogels. The system was able to emit blue light when pumped with an X-ray source. 
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  7. A high temperature reactor was developed to synthesize new scintillating nanoparticles that traditionally would sinter. Yttrium pyrosilicate nanoparticles were synthesized with optical properties suitable for x-ray biomedical applications. 
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  8. Core/shell nanoparticles composed of a silica core over which a propargyl methacrylate (PMA) shell was polymerized around were synthesized. To employ the shell coating, the surface of the silica nanoparticles (SiNPs) was modified with an alkene-terminated organometallic silane linker that allowed for the covalent attachment of a poly(propargyl methacrylate) (pPMA) shell. The alkyne groups resulting from the pPMA shell were utilized in copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reactions to attach azide-modified Förster resonance energy transfer (FRET) pairs of naphthalimide (azNap), rhodamine B (azRhod), and silicon phthalocyanine (azSiPc) derivatives to the shell surface. The luminescence of the system was manipulated by the covalent attachment of one, two, or three of the fluorophores resulting in no energy transfer, one energy transfer, or two energy transfers, respectively. When all three fluorophores were attached to the core/shell particles, an excitation of azNap with a wavelength of 400 nm resulted in the sequential energy transfer between two FRET pairs and the sole emission of azSiPc at 670 nm. These particles may have applications as bioimaging probes as their luminescence is easily detected using fluorescence microscopy.

     
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