Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

Sun, Jing; Jiang, Xi; Siegmund, Aaron; Connolly, Michael D.; Downing, Kenneth H.; Balsara, Nitash P.; Zuckermann, Ronald N.

doi:10.1021/acs.macromol.6b00353

Title: Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

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Abstract

Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this study, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (Φ_Npm) values ranging from 0.13 to 0.44 and dispersity (¯D) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with Φ_Npm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. Finally, we demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers.

Authors:

Sun, Jing ^[1]; Jiang, Xi; Siegmund, Aaron ^[2]; Connolly, Michael D.; Downing, Kenneth H.; Balsara, Nitash P. ^[3]; Zuckermann, Ronald N.

School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao, China 266042
Department of Medicinal Chemistry, Amgen Inc., One Amgen Center Drive, Thousand Oaks, California 91320-1799, United States
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States

Publication Date:: Mon Apr 04 00:00:00 EDT 2016

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States); National Natural Science Foundation of China (NSFC)

OSTI Identifier:: 1245326

Alternate Identifier(s):: OSTI ID: 1379302

Grant/Contract Number:: AC02-05CH11231; GM51487; 51503115

Resource Type:: Published Article

Journal Name:: Macromolecules

Additional Journal Information:: Journal Name: Macromolecules Journal Volume: 49 Journal Issue: 8; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Sun, Jing, Jiang, Xi, Siegmund, Aaron, Connolly, Michael D., Downing, Kenneth H., Balsara, Nitash P., and Zuckermann, Ronald N. Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.macromol.6b00353.

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                    Sun, Jing, Jiang, Xi, Siegmund, Aaron, Connolly, Michael D., Downing, Kenneth H., Balsara, Nitash P., & Zuckermann, Ronald N. Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers.  United States.  https://doi.org/10.1021/acs.macromol.6b00353

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                    Sun, Jing, Jiang, Xi, Siegmund, Aaron, Connolly, Michael D., Downing, Kenneth H., Balsara, Nitash P., and Zuckermann, Ronald N. Mon .  
"Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers".  United States.  https://doi.org/10.1021/acs.macromol.6b00353.

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@article{osti_1245326,

  title        = {Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers},

  author       = {Sun, Jing and Jiang, Xi and Siegmund, Aaron and Connolly, Michael D. and Downing, Kenneth H. and Balsara, Nitash P. and Zuckermann, Ronald N.},

  abstractNote = {Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this study, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (ΦNpm) values ranging from 0.13 to 0.44 and dispersity (¯D) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with ΦNpm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. Finally, we demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers.},

  doi          = {10.1021/acs.macromol.6b00353},

  journal      = {Macromolecules},

  number       = 8,

  volume       = 49,

  place        = {United States},

  year         = {Mon Apr 04 00:00:00 EDT 2016},

  month        = {Mon Apr 04 00:00:00 EDT 2016}

}

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