Hydrophobic-Sheath Segregated Macromolecular Fluorophores: Colloidal Nanoparticles of Polycaprolactone-Grafted Conjugated Polymers with Bright Far-Red/Near-Infrared Emission for Biological Imaging

This article describes molecular design, synthesis and characterization of colloidal nanoparticles containing polycaprolactone-grafted conjugated polymers that exhibit strong far red/near-infrared (FR/NIR) fluorescence for bioimaging. Specifically, we synthesized two kinds of conjugated polymer bottle brushes (PFTB^out-<i>g</i>-PCL and PFTBⁱⁿ-<i>g</i>-PCL) with different positions of the hexyl groups on the thiophene rings. A synthetic amphiphilic block copolymer PCL-<i>b</i>-POEGMA was employed as surfactants to encapsulate PFTB-<i>g</i>-PCL polymers into colloidal nanoparticles (denoted as “nanoREDs”) in aqueous media. The chain length of the PCL side chains in PFTB-<i>g</i>-PCL played a critical role in determining the fluorescence properties in both bulk solid states and the colloidal nanoparticles. Compared to semiconducting polymer dots (Pdots) composed of PFTB^out without grafted PCL, nanoRED^out showed at least four times higher fluorescence quantum yield (∼20%) and a broader emission band centered at 635 nm. We further demonstrated the application of this new class of nanoREDs for effective labeling of L929 cells and HeLa cancer cells with good biocompatibility. This strategy of hydrophobic-sheath segregated macromolecular fluorophores is expected to be applicable to a broad range of conjugated polymers with tunable optical properties for applications such as bioimaging

Monomer Symmetry-Regulated Defect Engineering: In Situ Preparation of Functionalized Covalent Organic Frameworks for Highly Efficient Capture and Separation of Carbon Dioxide

Developing crystalline porous materials with highly efficient CO2 selective adsorption capacity is one of the key challenges to carbon capture and storage (CCS). In current studies, much more attention has been paid to the crystalline and porous properties of crystalline porous materials for CCS, while the defects, which are unavoidable and ubiquitous, are relatively neglected. Herein, for the first time, we propose a monomer-symmetry regulation strategy for directional defect release to achieve in situ functionalization of COFs while exposing uniformly distributed defect-aldehyde groups as functionalization sites for selective CO2 capture. The regulated defective COFs possess high crystallinity, good structural stability, and a large number of organized and functionalized aldehyde sites, which exhibit one of the highest selective separation values of all COF sorbing materials in CO2/N2 selective adsorption (128.9 cm3/g at 273 K and 1 bar, selectivity: 45.8 from IAST). This work not only provides a new strategy for defect regulation and in situ functionalization of COFs but also provides a valuable approach in the design and preparation of new adsorbents for CO2 adsorption and CO2/N2 selective separation