Department of Chemistry

Polymers, Materials, and Nanoscience

Research ImageMany challenging problems in the modern science and technology are related to preparation, properties, and utilization of novel functional materials. The polymer chemistry and the chemical microelectronics programs represent parts of the multidisciplinary effort in this field. The many-pronged approach includes: synthesis and molecular characterization of well-defined block and graft copolymers; preparation of new engineering thermoplastics and liquid crystalline materials; synthesis, modification and processing of polymers in super-critical carbon dioxide; chemical design of hybrid polymers for catalysis and photoredox activity, polymers for microelectronics applications including 193 nm and 157 nm photoresists and low-k dielectrics, and defined microstructures.

Chemical microelectronics is focused on preparation of organic and inorganic electronic materials; microscopic patterning of thin films using novel techniques, plasma, ion beam, laser beam, etc.; kinetics of etching and film formation; characterization of mechanical, electronic, and optical properties; spatially resolved chemical analysis of surfaces, interfaces, and thin films and microstructures. A broad variety of expertise includes visualization and probing of submicrometer surface structures by scanning probe microscopy, characterization of polymer dynamics by NMR techniques and light scattering, measurement of molecular conductivity, and analytical as well as computational and numerical methods in polymers.

 

Recent Research Highlights

Shapeshifting

Biological systems have the ability to program reversible shape changes in response to cues from their environment. While a variety of adaptive and stimuli-responsive materials like hydrogels, liquid crystalline elastomers, and shape memory materials have been developed, mimicking programmable behavior in a reversible way remains elusive.

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Work published in Macromolecules by the Sheiko and Ashby groups, in collaboration with the University of Connecticut, Brookhaven and Oak Ridge National Labs, has shown that semi-crystalline elastomers may undergo reversible switching between well-defined shapes without applying any external forces. This behavior stems from the correlated interplay between a crystalline scaffold and a network of chemical crosslinks, each capable of encoding a distinct shape. The universal mechanism of reversible shapeshifting affords interesting opportunities for minimally invasive surgery, shape programmable biomedical implants, surgical sealants, and hands-free packaging.

 

Waveguide Scattering Microscopy

Dark-field microscopy, DFM, is widely used to optically image and spectroscopically analyze nanoscale objects. In a typical DFM configuration, a sample is illuminated at oblique angles and an objective lens collects light scattered by the sample at a range of lower angles. As demonstrated in an article published as the cover of ACS Photonics, researchers in the Cahoon Group have developed waveguide scattering microscopy, WSM, as an alternative technique to image and analyze photonic nanostructures. WSM uses an incoherent white-light source coupled to a dielectric slab waveguide to generate an evanescent field that illuminates objects located within several hundred nanometers of the waveguide surface.

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Using standard microscope slides or coverslips as the waveguide, the group demonstrate high-contrast dark-field imaging of nanophotonic and plasmonic structures such as Si nanowires, Au nanorods, and Ag nanoholes. Scattering spectra collected in the WSM configuration show excellent signal-to-noise with minimal background signal compared to conventional DFM. In addition, the polarization of the incident field is controlled by the direction of the propagating wave, providing a straightforward route to excite specific optical modes in anisotropic nanostructures by selecting the appropriate input wavevector. Considering the facile integration of WSM with standard microscopy equipment, the Cahoon Group scientists anticipate it will become a versatile tool for characterizing photonic nanostructures.

 

Representative Publications

Lubrication by Polyelectrolyte Brushes. Ekaterina B. Zhulina and Michael Rubinstein. Macromolecules, 2014, 47 (16), pp 5825–5838.

Shapeshifting: Reversible Shape Memory in Semicrystalline Elastomers. Jing Zhou, Sara A. Turner, Sarah M. Brosnan, Qiaoxi Li, Jan-Michael Y. Carrillo, Dmytro Nykypanchuk, Oleg Gang, Valerie S. Ashby, Andrey V. Dobrynin, and Sergei S. Sheiko. Nature Methods 11, 959–965 (2014).

Waveguide Scattering Microscopy for Dark-Field Imaging and Spectroscopy of Photonic Nanostructures. David J. Hill , Christopher W. Pinion , Joseph D. Christesen , and James F. Cahoon. ACS Photonics, 2014, 1 (8), pp 725–731.

Switchable Micropatterned Surface Topographies Mediated by Reversible Shape Memory. Sara A. Turner, Jing Zhou, Sergei S. Sheiko, and Valerie Sheares Ashby. ACS Appl. Mater. Interfaces, 2014, 6 (11), pp 8017–8021.

Particle Replication in Nonwetting Templates Nanoparticles with Tumor Selective Alkyl Silyl Ether Docetaxel Prodrug Reduces Toxicity. Kevin S. Chu, Mathew C. Finniss, Allison N. Schorzman, Jennifer L. Kuijer, J. Christopher Luft, Charles J. Bowerman, Mary E. Napier, Zishan A. Haroon, William C. Zamboni. Nano Lett., 2014, 14 (3), pp 1472–1476.

Controlling Molecular Weight of a High Efficiency Donor-Acceptor Conjugated Polymer and Understanding Its Significant Impact on Photovoltaic Properties. Wentao Li, Liqiang Yang, John R. Tumbleston, Liang Yan, Harald Ade, and Wei You. Adv. Mat., First published online, 14 MAR 2014, DOI: 10.1002/adma.201305251.

The Influence of Molecular Orientation on Organic Bulk Heterojunction Solar Cells. John R. Tumbleston, Brian A. Collins, Eliot Gann, Wei Ma and Harald Ade, Liqiang Yang, Andrew C. Stuart and Wei You. Nature Photonics (2014) doi:10.1038/nphoton.2014.55.

Copolymerization of Metal Nanoparticles: A Route to Colloidal Plasmonic Copolymers. Kun Liu, Ariella Lukach, Kouta Sugikawa, Siyon Chung, Jemma Vickery, Heloise Therien-Aubin, Bai Yang, Michael Rubinstein, and Eugenia Kumacheva. Angewandte Chemie International Edition, Volume 53, Issue 10, pages 2648–2653, March 3, 2014.

Storage of Electrical Information in Metal–Organic-Framework Memristors. Seok Min Yoon, Scott C. Warren, and Bartosz A. Grzybowski. Article first published online: 14 MAR 2014, DOI: 10.1002/anie.201309642.

Self-Healing of Unentangled Polymer Networks with Reversible Bonds. Evgeny B. Stukalin, Li-Heng Cai, N. Arun Kumar, Ludwik Leibler, and Michael Rubinstein. Macromolecules, 2013, 46 (18), pp 7525–7541.