Optoelectronic Supramolecular Block-Copolymer Assemblies Aided by Donor-Acceptor Interactions Alexander Sidorenko, University of the Sciences in Philadelphia,

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Optoelectronic Supramolecular Block-Copolymer Assemblies Aided by Donor-Acceptor Interactions Alexander Sidorenko, University of the Sciences in Philadelphia, DMR The goal of this EAGER project is the design, synthesis and functional characterization of a new class of nanostructured materials – donor-acceptor SupraMolecular Assemblies (SMA). During the last year we focused our research on the following aspects of the SMAs: Molecular aspects of the interaction of the additive and host polymer units, including quantum-mechanical aspects and NMR. In particular, we have interpreted the changes in the NMR spectra in terms of formation of unstable assemblies based on weak interactions (donor-acceptor, dipole-dipole, and π-stacking ). The most possible geometry of assembly of model molecules (EDOT and 4-ethyl pyridine) is shown in the Figure 1. We found that the additives can change preferential interactions with different blocks of the parent block copolymer depending on the solvent vapors. As a result, we can control the distribution of the additive and tune the morphology of the SMA from spherical (leftmost AFM image) to cylindrical (central) to gyroidal (image on right).* One of the most important findings of this year is direct in-situ oxidative polymerization of the additive in the pores of the SMA, as evidenced by AFM.** The results obtained in the frames of the project are very encouraging and can be of significant fundamental interest as well as find technical applications in optoelectronics, organic electronics, etc. Figure 1. The concept of SMA and results of molecular simulations of a donor-acceptor assembly for the model compounds Figure 2. Evolution of the SMA morphology upon exposure to vapors of different solvents: spheres – cylinders – gyroids (AFM images from left to right, bars show the scale) Figure 3. Depending on the parent block copolymer, either planar morphology (left), multilayers (center), or toroids (right) of the polymeric additive were observed with AFM (bars show the scale).

On June 22, 2011 the Department of Chemistry & Biochemistry hosted approximately 25 summer campers (ages 5-9) and their chaperones from Zhang Sah, a local nonprofit organization. The organization asked USciences to be a part of their summer camp kick-off week focusing on science. The group toured chemistry labs and were treated to some interesting discussions and demonstrations by the USciences faculty. The PI Alexander Sidorenko hosted the young campers and demonstrated them the “beauty” of chemistry (Photo on top). One of the major local outreach activities was Philadelphia Science Festival. It took place on April 15-28, 2011 ( USciences co-sponsored the PSF and the PI presented a series of images obtained in his lab at the Art and Science Gallery. On the photo at bottom Timothy Enright, the PI’s graduate student, represents the objet d'art: AFM image of live cell attached to the responsive substrate. The PI has established formal granted collaboration with Bristol- Myers Squibb, a local big-pharma company. Infrastructural improvement: due to the kind support of the Department of Chemistry & Biochemistry and the NSF grant, the PI has extended his research space by opening a new lab dedicated to AFM. The research group led by the PI has grown from 4 students (one graduate, three undergrads) in 2010 to 7 persons (three undergrads, 4 graduate students) in Optoelectronic Supramolecular Block-Copolymer Assemblies Aided by Donor- Acceptor Interactions Alexander Sidorenko, University of the Sciences in Philadelphia, DMR