image: 1,8,13-Trip is a triptycene molecule that can self-assemble into 2D hexagonal arrays, which then stack on top of each other to form a periodic polymer structure, shown in middle of the figure. Can silicone (PDMS) chains with the ends substituted with triptycene molecules self-assemble in a similar fashion? view more
Credit: Fumitaka Ishiwari
Scientists at Tokyo Institute of Technology, RIKEN and Tohoku University have developed a silicone polymer chain that can self-assemble into a 3D periodic structure. They achieved this by using their recently reported self-assembling triptycene molecules to modify the ends of the polymer chains.
The development of novel soft materials for various optical, mechanical, heat/charge transportation and nanotechnological applications would greatly benefit from techniques to create polymer assemblies in periodically ordered structures. Such ordered structures are created using molecular scaffolds or by modifying certain parts of the polymers used so that they self-assemble into the desired shape.
However, researchers nowadays consider that terminal functionalization (modifying both ends of a polymer chain) is not very effective for creating periodically ordered structures. That's why scientists from Tokyo Institute of Technology (Tokyo Tech), led by Fumitaka Ishiwari, were interested in revisiting one of their recently developed triptycene molecules, called 1,8,13-Trip. The team had already demonstrated that this molecule can reliably self-assemble into a periodic 3D structure made of parallel 2D sheets separated from each other by a fixed distance (see Fig. 1). "We were interested in investigating whether the powerful self-assembling ability of this triptycene motif would also operate in polymer systems," explains Ishiwari.
Therefore, the team designed polydimethylsiloxane (PDMS) chains with the ends replaced by a triptycene molecule. They hoped that these modified silicone chains would also exhibit the promising self-assembling behavior observed for 1,8,13-Trip alone, and thus had to run many different experiments to prove it, including Synchrotron-Radiation X-ray diffraction/scattering using the BL45XU beamline at SPring-8 (Hyogo, Japan), differential scanning calorimetry and spectroscopy measurements. Fortunately, all results seemed to indicate that the modified PDMS chains had self-assembled into the 3D periodic structure shown in Fig. 2. This was also verified by analyzing the differences in the flow characteristics of the modified PDMS chains and regular PDMS chains.
The team's findings are very promising because the triptycene motif used is simple and easy to synthesize via short steps, and may provide a powerful tool for organizing polymers and reinforcing their structural and physical properties. "The present finding will update the general notion that terminal functionalization is not effective for achieving the controlled assembly of polymers into a periodically ordered structure," concludes Ishiwari. The team will carry on investigating the self-organization of polymers, and it is hoped that the results will lead to the development of novel materials and synthesis techniques.
Professor Masaki Takata of Tohoku University attributed the success of the study to the collaborative efforts of the Network Joint Research Center for Materials and Devices and the large scale Synchrotron Radiation facility, SPring-8, managed by RIKEN. He added that "this would hopefully also trigger a big demand for further high quality materials, which can be developed at the next-generation 3GeV synchrotron facility, due to begin construction at Tohoku University next year."
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About Tokyo Institute of Technology
Tokyo Tech stands at the forefront of research and higher education as the leading university for science and technology in Japan. Tokyo Tech researchers excel in fields ranging from materials science to biology, computer science, and physics. Founded in 1881, Tokyo Tech hosts over 10,000 undergraduate and graduate students per year, who develop into scientific leaders and some of the most sought-after engineers in industry. Embodying the Japanese philosophy of "monotsukuri," meaning "technical ingenuity and innovation," the Tokyo Tech community strives to contribute to society through high-impact research. Website: http://www.titech.ac.jp/english/
About RIKEN
RIKEN is Japan's largest research institute for basic and applied research. Over 2500 papers by RIKEN researchers are published every year in leading scientific and technology journals covering a broad spectrum of disciplines including physics, chemistry, biology, engineering, and medical science. RIKEN's research environment and strong emphasis on interdisciplinary collaboration and globalization has earned a worldwide reputation for scientific excellence.
Website: http://www.riken.jp/en/
Facebook: http://www.facebook.com/RIKEN.english
Twitter: @riken_en
About Tohoku University
Tohoku University was established in 1907 as Japan's third national university, and is proud to be ranked No.2 on the 2017 Times Higher Education list of top universities in Japan. Tohoku University has a history of innovation and continues to lead in traditional fields of research, is committed to contributing to its local and global communities, and encourages academic-industry-government cooperation to help strengthen and develop new areas of research.
Website:https://www.tohoku.ac.jp/en/
Journal
Journal of the American Chemical Society