Award Abstract # 0847646
CAREER: Composite Materials of Functional Block-copolymers and Nanoparticles: Understanding the Assembly Processes and Structure-property Relationships

NSF Org: DMR
Division Of Materials Research
Recipient: TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA, THE
Initial Amendment Date: January 12, 2009
Latest Amendment Date: January 21, 2013
Award Number: 0847646
Award Instrument: Continuing Grant
Program Manager: Michael J. Scott
DMR
 Division Of Materials Research
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: January 1, 2009
End Date: December 31, 2013 (Estimated)
Total Intended Award Amount: $572,993.00
Total Awarded Amount to Date: $572,993.00
Funds Obligated to Date: FY 2009 = $112,993.00
FY 2010 = $115,000.00

FY 2011 = $115,000.00

FY 2012 = $115,000.00

FY 2013 = $115,000.00
History of Investigator:
  • So-Jung Park (Principal Investigator)
    sojungp@sas.upenn.edu
Recipient Sponsored Research Office: University of Pennsylvania
3451 WALNUT ST STE 440A
PHILADELPHIA
PA  US  19104-6205
(215)898-7293
Sponsor Congressional District: 03
Primary Place of Performance: University of Pennsylvania
3451 WALNUT ST STE 440A
PHILADELPHIA
PA  US  19104-6205
Primary Place of Performance
Congressional District:
03
Unique Entity Identifier (UEI): GM1XX56LEP58
Parent UEI: GM1XX56LEP58
NSF Program(s): SOLID STATE & MATERIALS CHEMIS
Primary Program Source: 01000910DB NSF RESEARCH & RELATED ACTIVIT
01001011DB NSF RESEARCH & RELATED ACTIVIT

01001112DB NSF RESEARCH & RELATED ACTIVIT

01001213DB NSF RESEARCH & RELATED ACTIVIT

01001314DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 1045, 1187, 7573, 9161, AMPP
Program Element Code(s): 176200
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

TECHNICAL SUMMARY:
The self-assembly of amphiphilic block-copolymers and nanoparticles offers a powerful route to create multifunctional nanostructures. However, the assembly behavior of the two components has not been vigorously studied, and researchers have been relying on the simple solubilization approach to encapsulate nanoparticles in polymer matrixes. The Park group has recently shown that the cooperative assembly of nanoparticles and block-copolymers can lead to ordered arrays of nanoparticles in discrete block-copolymer aggregates. The proposed research will further investigate what controls the co-assembly process of the two components in selective solvents and how nanoparticles affect the morphology and properties of block-copolymers. Such knowledge is key to the design of nanoparticle/polymer composite materials with preconceived architecture and properties. Furthermore, the Park group will extend the strategy to block-copolymers containing conjugated polymer segments, where block-copolymers not only act as structure-directing molecules but also provide an additional functionality to the composite system. This unique combination of materials and the self-assembly capability of block-copolymers will lead to advanced multifunctional nanometer to micrometer scale materials with controllable structure and properties.

NON-TECHNICAL SUMMARY:
The incorporation of nanoparticles in polymers offers an effective way to control the mechanical, optical, and electrical properties of soft materials for applications ranging from flexible, low-cost solar cells to biological imaging and medicine. The proposed research aims to elucidate how the interactions between nanoparticles and block-copolymers affect the morphology of polymer/nanoparticle composite particles. This study will provide a guide for selecting suitable block-copolymer/nanoparticle pairs and assembly conditions to create composite materials with desirable architectures and properties. The broader impact of the proposed activity seeks to exploit highly visible nanoscience to better engage pre-college and undergraduate students in science. Educating graduate students and postdoctoral fellows in an interdisciplinary field of chemistry is another important outcome of the proposed study. The proposed research uses concepts and tools in several different areas including materials science, surface chemistry, and spectroscopy. Students will discover opportunities at the interfaces between seemingly unrelated fields and learn how to solve problems at those boundaries.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 15)
Chen, Xi-Jun;Sanchez-Gaytan, Brenda L.;Hayik, Sara E. N.;Fryd, Michael;Wayland, Bradford B.;Park, So-Jung; "Self-Assembled Hybrid Structures of DNA Block-Copolymers and Nanoparticles with Enhanced DNA Binding Properties" Small , v.6 , 2010 , p.2256-2260
Chen, Xi-Jun;Sanchez-Gaytan, Brenda L.;Qian, Zhaoxia;Park, So-Jung; "Noble metal nanoparticles in DNA detection and delivery" WIREs: Nanomedicine and Nanobiotechnology , v.4 , 2012 , p.273-290
Hickey, R.; Haynes, A; Kikkawa, J; Park, S. -J. "Controlling the Morphology of Nanoparticle-Encapsulating Block-copolymer Assemblies: from Micelles to Vesicles" Journal of American Chemical Society , v.133 , 2010 , p.1517
Hickey, Robert J.;Haynes, Alyssa S.;Kikkawa, James M.;Park, So-Jung; "Controlling the Self-Assembly Structure of Magnetic Nanoparticles and Amphiphilic Block-Copolymers: From Micelles to Vesicles" Journal of the American Chemical Society , v.133 , 2011 , p.1517-1525
Hickey, Robert J.; Luo, Qingjie; Park, So-Jung "Polymersomes and Multicompartment Polymersomes Formed by the Interfacial Self-Assembly of Gold Nanoparticles and Amphiphilic Polymers" ACS MACRO LETTERS , v.2 , 2013
Hickey, Robert J.; Meng, Xin; Zhang, Peijun; Park, So-Jung "Low-Dimensional Nanoparticle Clustering in Polymer Micelles and Their Transverse Relaxivity Rates" ACS NANO , v.7 , 2013 10.1021/nn400824b
Hickey, Robert J.;Sanchez-Gaytan, Brenda L.;Cui, Weihong;Composto, Russell J.;Fryd, Mike;Wayland, Bradford B.;Park, So-Jung; "Morphological Transitions of Block-Copolymer Bilayers via Nanoparticle Clustering" Small , v.6 , 2010 , p.48-51
Jung, Yeongri;Hickey, Robert J.;Park, So-Jung; "Encapsulating Light-Emitting Polymers in Block Copolymer Micelles" Langmuir , v.26 , 2010 , p.7540-7543
Kamps, Amanda C.;Sanchez-Gaytan, Brenda L.;Hickey, Robert J.;Clarke, Nigel;Fryd, Michael;Park, So-Jung; "Nanoparticle-Directed Self-Assembly of Amphiphilic Block Copolymers" Langmuir , v.26 , 2010 , p.14345-143
Luo, Qingjie; Hickey, Robert J.; Park, So-Jung "Controlling the Location of Nanoparticles in Colloidal Assemblies of Amphiphilic Polymers by Tuning Nanoparticle Surface Chemistry" ACS MACRO LETTERS , v.2 , 2013 10.1021/mz3006044
Park, Sang-Jae;Kang, Seung-Gu;Fryd, Michael;Saven, Jeffery G.;Park, So-Jung; "Highly Tunable Photoluminescent Properties of Amphiphilic Conjugated Block Copolymers" Journal of the American Chemical Society , v.132 , 2010 , p.9931-9933
(Showing: 1 - 10 of 15)

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.



The combination of nanoparticles and polymers offers a powerful route to generate soft materials possessing the unique optical, electrical, and magnetic properties of nanoparticles as well as the excellent processibility of polymers.  Inspired by the way Nature forms functional supramolecular assemblies using lipid bilayers as architectural skeletons, this project utilized the self-assembly of amphiphilic block-copolymers to control the organization of nanoparticles.  Based on this strategy, we have assembled various types of nanoparticles (e.g., CdSe, Fe3O4, Au) into a unique hierarchical self-assembly structure of nanoparticles.  This work demonstrated for the first time that ordered arrays of nanoparticles can be formed through the cooperative self-assembly of nanoparticles and amphiphilic polymers in solution phase.  Moreover, we discovered that the incorporation of nanoparticles can significantly impact the self-assembly behavior of amphiphilic block-copolymers, and identified key factors that affect the co-assembly structure.  Based on these discoveries, we fabricated various types of well-defined hybrid assemblies, including polymer vesicles packed with magnetic nanoparticles (superparamagnetic polymersomes).  To the best of our knowledge, our report was the first to describe well-defined polymersomes densely packed with nanoparticles.  The superparamagnetic polymersomes exhibited an unusually high transverse relaxation rate, showing promise in MRI applications.  We believe that our superparamagnetic polymersomes will likely lead to exciting opportunities in the field of nanomedicine owing to their ability to load both hydrophilic and hydrophobic substances, their controllable nanoparticle density and unusually high magnetic relaxation rates. 


Last Modified: 04/08/2014
Modified by: So-Jung Park

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