Supramolecular triblock copolymers containing complementary nucleobase molecular recognition

Brian D. Mather; Margaux B. Baker; Frederick L. Beyer; Michael A.G. Berg; Matthew D. Greeny; Timothy Edward Long

doi:10.1021/ma070865y

Supramolecular triblock copolymers containing complementary nucleobase molecular recognition

Brian D. Mather, Margaux B. Baker, Frederick L. Beyer, Michael A.G. Berg, Matthew D. Greeny, Timothy Edward Long^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

112 Citations (Scopus)

Abstract

A novel difunctional alkoxyamine initiator, DEPN₂, was synthesized and utilized as an efficient initiator in nitroxide-mediated controlled radical polymerization of triblock copolymers. Complementary hydrogen-bonding triblock copolymers containing adenine (A) and thymine (T) nucleobase-functionalized outer blocks were synthesized. These thermoplastic elastomeric block copolymers contained short nucleobase-functionalized outer blocks (M_n ∼ 1K-4K) and n-butyl acrylate rubber blocks of variable length (M_n ∼ 14K-70K). Hydrogen-bonding interactions were observed for blends of the complementary nucleobase-functionalized block copolymers in terms of increased specific viscosity as well as higher scaling exponents for specific viscosity as a function of solution concentration. In the solid state, the blends exhibited evidence of a complementary A-T hard phase, which formed upon annealing, and dynamic mechanical analysis (DMA) revealed higher softening temperatures. Morphological development of the block copolymers was studied using SAXS and AFM, which revealed intermediate interdomain spacings and surface textures for the blends compared to the individual precursors. Hydrogen-bonding interactions enabled the compatibilization of complementary hydrogen-bonding guest molecules such as 9-octyladenine.

Original language	English
Pages (from-to)	6834-6845
Number of pages	12
Journal	Macromolecules
Volume	40
Issue number	19
DOIs	https://doi.org/10.1021/ma070865y
Publication status	Published - 2007 Sept 18
Externally published	Yes

ASJC Scopus subject areas

Materials Chemistry

Access to Document

10.1021/ma070865y

Cite this

@article{2b2c0ba70d6344cfa2a949dc5634a66b,

title = "Supramolecular triblock copolymers containing complementary nucleobase molecular recognition",

abstract = "A novel difunctional alkoxyamine initiator, DEPN2, was synthesized and utilized as an efficient initiator in nitroxide-mediated controlled radical polymerization of triblock copolymers. Complementary hydrogen-bonding triblock copolymers containing adenine (A) and thymine (T) nucleobase-functionalized outer blocks were synthesized. These thermoplastic elastomeric block copolymers contained short nucleobase-functionalized outer blocks (Mn ∼ 1K-4K) and n-butyl acrylate rubber blocks of variable length (Mn ∼ 14K-70K). Hydrogen-bonding interactions were observed for blends of the complementary nucleobase-functionalized block copolymers in terms of increased specific viscosity as well as higher scaling exponents for specific viscosity as a function of solution concentration. In the solid state, the blends exhibited evidence of a complementary A-T hard phase, which formed upon annealing, and dynamic mechanical analysis (DMA) revealed higher softening temperatures. Morphological development of the block copolymers was studied using SAXS and AFM, which revealed intermediate interdomain spacings and surface textures for the blends compared to the individual precursors. Hydrogen-bonding interactions enabled the compatibilization of complementary hydrogen-bonding guest molecules such as 9-octyladenine.",

author = "Mather, {Brian D.} and Baker, {Margaux B.} and Beyer, {Frederick L.} and Berg, {Michael A.G.} and Greeny, {Matthew D.} and Long, {Timothy Edward}",

year = "2007",

month = sep,

day = "18",

doi = "10.1021/ma070865y",

language = "English",

volume = "40",

pages = "6834--6845",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Supramolecular triblock copolymers containing complementary nucleobase molecular recognition

AU - Mather, Brian D.

AU - Baker, Margaux B.

AU - Beyer, Frederick L.

AU - Berg, Michael A.G.

AU - Greeny, Matthew D.

AU - Long, Timothy Edward

PY - 2007/9/18

Y1 - 2007/9/18

N2 - A novel difunctional alkoxyamine initiator, DEPN2, was synthesized and utilized as an efficient initiator in nitroxide-mediated controlled radical polymerization of triblock copolymers. Complementary hydrogen-bonding triblock copolymers containing adenine (A) and thymine (T) nucleobase-functionalized outer blocks were synthesized. These thermoplastic elastomeric block copolymers contained short nucleobase-functionalized outer blocks (Mn ∼ 1K-4K) and n-butyl acrylate rubber blocks of variable length (Mn ∼ 14K-70K). Hydrogen-bonding interactions were observed for blends of the complementary nucleobase-functionalized block copolymers in terms of increased specific viscosity as well as higher scaling exponents for specific viscosity as a function of solution concentration. In the solid state, the blends exhibited evidence of a complementary A-T hard phase, which formed upon annealing, and dynamic mechanical analysis (DMA) revealed higher softening temperatures. Morphological development of the block copolymers was studied using SAXS and AFM, which revealed intermediate interdomain spacings and surface textures for the blends compared to the individual precursors. Hydrogen-bonding interactions enabled the compatibilization of complementary hydrogen-bonding guest molecules such as 9-octyladenine.

AB - A novel difunctional alkoxyamine initiator, DEPN2, was synthesized and utilized as an efficient initiator in nitroxide-mediated controlled radical polymerization of triblock copolymers. Complementary hydrogen-bonding triblock copolymers containing adenine (A) and thymine (T) nucleobase-functionalized outer blocks were synthesized. These thermoplastic elastomeric block copolymers contained short nucleobase-functionalized outer blocks (Mn ∼ 1K-4K) and n-butyl acrylate rubber blocks of variable length (Mn ∼ 14K-70K). Hydrogen-bonding interactions were observed for blends of the complementary nucleobase-functionalized block copolymers in terms of increased specific viscosity as well as higher scaling exponents for specific viscosity as a function of solution concentration. In the solid state, the blends exhibited evidence of a complementary A-T hard phase, which formed upon annealing, and dynamic mechanical analysis (DMA) revealed higher softening temperatures. Morphological development of the block copolymers was studied using SAXS and AFM, which revealed intermediate interdomain spacings and surface textures for the blends compared to the individual precursors. Hydrogen-bonding interactions enabled the compatibilization of complementary hydrogen-bonding guest molecules such as 9-octyladenine.

UR - http://www.scopus.com/inward/record.url?scp=34948873704&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34948873704&partnerID=8YFLogxK

U2 - 10.1021/ma070865y

DO - 10.1021/ma070865y

M3 - Article

AN - SCOPUS:34948873704

SN - 0024-9297

VL - 40

SP - 6834

EP - 6845

JO - Macromolecules

JF - Macromolecules

IS - 19

ER -

Supramolecular triblock copolymers containing complementary nucleobase molecular recognition

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this