Simple blends of inorganic nanocrystals and organic (semiconducting) polymers usually lead to macroscopic segregation. Thus, such blends typically exhibit inferior properties than expected. To overcome the problem of segregation, polymer coated nanocrystals (nanocomposites) have been developed. Such nanocomposites are highly miscible within the polymer matrix. In this Review, a summary of synthetic approaches to achieve stable nanocomposites in a semiconducting polymer matrix is presented. Furthermore, a theoretical background as well as an overview concerning morphology control of inorganic NCs in polymer matrices are provided. In addition, the morphologic behavior of highly anisotropic nanoparticles (i.e. liquid crystalline phase formation of nanorod-composites) and branched nanoparticles (spatial orientation of tetrapods) is described. Finally, the morphology requirements for the application of inorganic/organic hybrid systems in light emitting diodes and solar cells are discussed, and potential solutions to achieve the required morphologies are provided.
Breast cancer cell invasion is influenced by growth factor concentration gradients in the tumor microenvironment. However, studying the influence of growth factor gradients on breast cancer cell invasion is challenging due to both the complexities of in vivo models and the difficulties in recapitulating the tumor microenvironment with defined gradients using in vitro models. A defined hyaluronic acid (HA)-based hydrogel crosslinked with matrix metalloproteinase (MMP) cleavable peptides and modified with multiphoton labile nitrodibenzofuran (NDBF) was synthesized to photochemically immobilize epidermal growth factor (EGF) gradients. We demonstrate that EGF gradients can differentially influence breast cancer cell invasion and drug response in cell lines with different EGF receptor (EGFR) expression levels. Photopatterned EGF gradients increase the invasion of moderate EGFR expressing MDA-MB-231 cells, reduce invasion of high EGFR expressing MDA-MB-468 cells, and have no effect on invasion of low EGFR-expressing MCF-7 cells. We evaluate MDA-MB-231 and MDA-MB-468 cell response to the clinically tested EGFR inhibitor, cetuximab. Interestingly, the cellular response to cetuximab is completely different on the EGF gradient hydrogels: cetuximab decreases MDA-MB-231 cell invasion but increases MDA-MB-468 cell invasion and cell number, thus demonstrating the importance of including cell-microenvironment interactions when evaluating drug targets.
We describe the synthesis of heterotelechelic polysarcosine polymers and their use as multidentate ligands in the preparation of stable water-soluble quantum dots (QDs). Orthogonally functionalized polysarcosine with amine and dibenzocyclooctyl (DBCO) end groups is obtained by ringopening polymerization of N-methylglycine N-carboxyanhydride with DBCO amine as initiator. In a first postpolymerization modification step, the future biological activity of the polymeric ligands is adjusted by modification of the amine terminus. Then, in a second postpolymerization modification step, azide functionalized di-and tridentate anchor compounds are introduced to the DBCO terminus of the polysarcosine via strain-promoted azide−alkyne cycloaddition (SPAAC). Through the separate synthesis of the anchor compounds, it is possible to ensure reproducible introduction of a well-defined number of multiple anchor groups to all polymers studied. Finally, the obtained multidentate polymeric ligands are successfully used in the ligand exchange procedures to yield stable, water-soluble QDs. As polysarcosine-based ligands can provide biocompatibility, prevent nonspecific interactions, and simultaneously enable specific targeting, the systems presented here are promising candidates to provide QDs well suitable for ex vivo analytics or bioimaging.
The influence of the morphology of quantum dot (QD)‐semiconducting polymer hybrid emission layers on the performance of quantum dot‐based light emitting diodes (QLEDs) is systematically investigated. Chemically grafted QD‐semiconducting polymer hybrids are fabricated by the ligand exchange procedure between CdSe/CdxZn1−xS QDs and a new block copolymer consisting of a carbazole‐based electroactive block with a low highest occupied molecular orbital level and a disulfide‐based anchor block. The performance of QLEDs with hybrid emission layers is compared with QLEDs utilizing QD‐only and physically mixed QD/polymer emission layers. It is shown that only in the emission layers formed by chemically grafted hybrids QDs are evenly distributed throughout the semiconducting polymer matrix. This leads to improved charge transport balance and suppressed photoluminescence quenching of QDs. As a result, hybrid QLEDs with the peak external quantum efficiency of 5.6% and the peak luminance of 21 707 cd m−2 which outperform the conventional devices with QD‐only emission layers are fabricated.
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