PMID- 29506382 OWN - NLM STAT- PubMed-not-MEDLINE DCOM- 20180608 LR - 20180608 IS - 1520-5126 (Electronic) IS - 0002-7863 (Linking) VI - 140 IP - 11 DP - 2018 Mar 21 TI - Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers. PG - 4100-4109 LID - 10.1021/jacs.8b00461 [doi] AB - A series of amphiphilic ionic peptoid block copolymers where the total number (1 or 3) and position of ionic monomers along the polymer chain are precisely controlled have been synthesized by the submonomer method. Upon dissolution in water at pH = 9, the amphiphilic peptoids self-assemble into small spherical micelles having hydrodynamic radius in approximately 5-10 nm range and critical micellar concentration (CMC) in the 0.034-0.094 mg/mL range. Small-angle neutron scattering (SANS) analysis of the micellar solutions revealed unprecedented dependence of the micellar structure on the number and position of ionic monomers along the chain. It was found that the micellar aggregation number ( N(agg)) and the micellar radius ( R(m)) both increase as the ionic monomer is positioned progressively away from the junction of the hydrophilic and hydrophobic segments along the polymer chain. By defining an ionic monomer position number ( n) as the number of monomers between the junction and the ionic monomer, N(agg) exhibited a power law dependence on n with an exponent of approximately 1/3 and approximately 3/10 for the respective singly and triply charged series. By contrast, R(m) exhibited a weaker dependence on the ionic monomer position by a power law relationship with an exponent of approximately 1/10 and approximately 1/20 for the respective singly and triply charged series. Furthermore, R(m) was found to scale with N(agg) in a power-law relationship with an exponent of 0.32 for the singly charged series, consistent with a weakly charged ionic star-like polymer model in the unscreened regime. This study demonstrated a unique method to precisely tailor the structure of small spherical micelles based on ionic block copolymers by controlling the sequence and position of the ionic monomer. FAU - Sternhagen, Garrett L AU - Sternhagen GL AD - Department of Chemistry and Macromolecular Studies Group , Louisiana State University , Baton Rouge , Louisiana 70803 , United States. FAU - Gupta, Sudipta AU - Gupta S AUID- ORCID: 0000-0001-6642-3776 AD - Department of Chemistry and Macromolecular Studies Group , Louisiana State University , Baton Rouge , Louisiana 70803 , United States. FAU - Zhang, Yueheng AU - Zhang Y AD - Department of Chemical and Biomolecular Engineering , Tulane University , New Orleans , Louisiana 70118 , United States. FAU - John, Vijay AU - John V AUID- ORCID: 0000-0001-5426-7585 AD - Department of Chemical and Biomolecular Engineering , Tulane University , New Orleans , Louisiana 70118 , United States. FAU - Schneider, Gerald J AU - Schneider GJ AD - Department of Chemistry and Macromolecular Studies Group , Louisiana State University , Baton Rouge , Louisiana 70803 , United States. AD - Department of Physics , Louisiana State University , Baton Rouge , Louisiana 70803 , United States. FAU - Zhang, Donghui AU - Zhang D AUID- ORCID: 0000-0003-0779-6438 AD - Department of Chemistry and Macromolecular Studies Group , Louisiana State University , Baton Rouge , Louisiana 70803 , United States. LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't PT - Research Support, U.S. Gov't, Non-P.H.S. DEP - 20180313 PL - United States TA - J Am Chem Soc JT - Journal of the American Chemical Society JID - 7503056 EDAT- 2018/03/07 06:00 MHDA- 2018/03/07 06:01 CRDT- 2018/03/07 06:00 PHST- 2018/03/07 06:00 [pubmed] PHST- 2018/03/07 06:01 [medline] PHST- 2018/03/07 06:00 [entrez] AID - 10.1021/jacs.8b00461 [doi] PST - ppublish SO - J Am Chem Soc. 2018 Mar 21;140(11):4100-4109. doi: 10.1021/jacs.8b00461. Epub 2018 Mar 13.