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Creators/Authors contains: "Nosratabad, Neda Arabzadeh"

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  1. Magnetic resonance imaging, MRI, relying on 19F nuclei has attracted much attention, because the isotopes exhibit a high gyromagnetic ratio (comparable to that of protons) and have 100% natural abundance. Furthermore, due to the very low traces of intrinsic fluorine in biological tissues, fluorine labeling allows easy visualization in vivo using 19F-based MRI. However, one of the drawbacks of the available fluorine tracers is their very limited solubility in water. Here, we detail the design and preparation of a set of water-compatible fluorine-rich polymers as contrast agents that can enhance the effectiveness of 19F-based MRI. The agents are synthesized using the nucleophilic addition reaction between poly(isobutylene-alt-maleic anhydride) copolymer and a mixture of amine-appended fluorine groups and polyethylene glycol (PEG) blocks. This allows control over the polymer architecture and stoichiometry, resulting in good affinity to water solutions. We further investigate the effects of introducing additional segmental mobility to the fluorine moieties in the polymer, by inserting a PEG linker between the moieties and the polymer backbone. We find that controlling the polymer stoichiometry and introducing additional segmental mobility enhance the NMR signals and narrow the peak profile. In particular, we assess the impact of the PEG linker on T2* and T1 relaxation times, using a series of gradient-recalled echo images with varying echo times, TE, or recovery time, TR, respectively. We find that for equivalent concentrations, the PEG linker greatly increases T2*, while maintaining high T1 values, as compared to polymers without this linker. Phantom images collected from these compounds show bright signals over a background with high intensities. 
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  2. We designed a novel multicoordinating ligand based on the N-heterocyclic carbene (NHC) anchoring molecules and applied them for stabilizing luminescent quantum dots in aqueous media. The ligand is synthesized via nucleophilic addition reaction between amine-appended imidazole/poly(ethylene glycol) compounds and poly(isobutylene-alt-maleic anhydride) (PIMA), followed by carbene generation. We find that these NHC-based polymers exhibit fast and robust coordinating affinity to CdSe QDs overcoated with ZnS shells. The removal of hydrophobic coating and the generation of carbene are demonstrated by 1H NMR spectroscopy. 13C NMR spectroscopy confirms the existence of carbene-Zn complexes which is crucial for binding transition-metals on QD surfaces. These QDs exhibit absorption and emission features with little to no change before and after cap exchange, and their PL intensity is increased under light exposure. Excellent colloidal stability of these QD samples is observed in a wide range of competitive conditions over long period of time. Agarose gel electrophoresis indicates that the polymer coating imparts QDs with good compatibility in different aqueous buffers, and it prevents protein adsorption. 
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