Discriminating Among Co‐monomer Sequence Distributions in Random Copolymers Using Interaction Chromatography

Han, Junwon; Jeon, Byung Ho; Ryu, Chang Y.; Semler, James J.; Jhon, Young K.; Genzer, Jan

doi:10.1002/marc.200900282

Cited by 16 publications

(18 citation statements)

References 28 publications

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“…The number of chains having 30 "red" and 70 "blue" segments within this population will then be equal to: Examining first the data corresponding to r-PBr 0.35 S it is apparent that the mother sample (i.e., as made copolymer) is not "truly" random because its FHWM exceeds that of the expected normal distribution. This is consistent with our earlier work, which established that the bromination reaction performed in 1-chlorodecane produced PBr x S copolymers that had a lower degree of randomness than those made in nitrobenzene [ 1 ]. However, the chemical heterogeneities of fractions F2-F5 (particularly those of F4 and F5) are close to "truly random".…”

Section: Determining the Chemical Composition Distribution Of Random Copolymerssupporting

confidence: 92%

Determining the Polydispersity in Chemical Composition and Monomer Sequence Distribution in Random Copolymers Prepared by Postpolymerization Modification of Homopolymers

et al. 2012

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We report on establishing the polydispersity in chemical composition (PCC) and polydispersity in monomer sequence distribution (PMSD) in random copolymers of poly(styrene-co-4-bromostyrene) (PBr x S), where x = (0.385 ± 0.035) is the mole fraction of the 4bromostyrene units (4-BrS), prepared by electrophilic substitution of bromine in the para-position of the phenyl ring of the parent polystyrene. Upon fixing the total number of repeating units, we tune the distribution of styrene and 4-BrS segments in PBr x S by carrying out the bromination reaction on polystyrene homopolymers in different solvents. While PBr x S with relatively random comonomer distribution is prepared in 1-chlorodecane, random-blocky sequences of 4-BrS in PBr x S are achieved by carrying out the bromination reaction in 1-chlorododecane. The PCC in both copolymers is established by fractionating both polymers using interaction chromatography (IC) and determining the chemical composition of the individual fractions by neutron activation analysis (NAA). The NAA data along with IC experiments reveal that the random-blocky sample possesses a narrowed PCC relative to a specimen with a more random comonomer sequence distribution. The full width at halfmaximum (fwhm) in the chemical composition profile from IC is used to quantify PCC; the random mother sample possessed a 25% fwhm, while the random blocky mother sample has a fwhm equal to 8.7%. The change in the adsorption enthalpy per brominated segment due to adsorption is determined to be ≈1.5 times greater for the random-blocky than the relatively random sample, proving that more pronounced cooperative adsorption occurs in the case of the random-blocky sample relative to the random copolymer sample. Computer simulation employing the discontinuous molecular dynamic scheme further reveals that the distribution of comonomer sequences, that is, PMSD, in the random-blocky copolymer is narrower than that in the copolymer with a random distribution of both monomers.

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Section: Determining the Chemical Composition Distribution Of Random Copolymerssupporting

confidence: 92%

Determining the Polydispersity in Chemical Composition and Monomer Sequence Distribution in Random Copolymers Prepared by Postpolymerization Modification of Homopolymers

et al. 2012

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“…[65][66][67] Different modification patterns can be achieved by performing the chemical modification on the polymer chains dissolved in solvents of different ''quality'' and correlated to the Kerr constant of the resulting modified polymer in solution. [68][69][70][71][72][73] In silico modeling provides full control over the distribution of modification groups, and represents an ideal modality for exploring the effect of modification pattern on the molecular architecture of hydrogels.…”

Section: Structure Of the Chitosan Hydrogelsmentioning

confidence: 99%

A multiscale coarse-grained model to predict the molecular architecture and drug transport properties of modified chitosan hydrogels

et al. 2020

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“…Typically, one hydrophobic and one hydrophilic monomer are used to understand how the transition from an extended coil to a compact globule is influenced by the monomer pattern. Prior to the development of controlled polymerizations, experimental studies were limited by the lack of synthetic strategies to access polymers with varying sequences but identical monomer content and length. − The first experimental study of the role of sequence in copolymer folding by Wu and co-workers examined AB copolymers of poly( N -isopropylacrylamide) (PNIPAM) and hydrophilic poly(vinylpyrrolidone) (PVP) . They exploited the lower critical solution temperature (LCST) of PNIPAM to control the distribution of the monomers while keeping the monomer composition and length constant.…”

Section: Controlling and Characterizing Self-assemblymentioning

confidence: 99%

Protein-Mimetic Self-Assembly with Synthetic Macromolecules

et al. 2021

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Protein-mimetic amphiphiles have significant promise as a platform to access the complex functions of natural biological materials and incorporate the tunability and environmental resilience of synthetic materials. The fields of polymer chemistry and chemical biology have concurrently approached the development of biomimetic amphiphiles with materials ranging from random amphiphilic copolymers to peptide–lipid conjugates. In this Perspective, we incorporate strategies from diverse chemical arenas for controlling assembled morphologies and dynamics of protein-mimetic synthetic macromolecules. An overview of significant advances in peptide amphiphiles and single-chain polymer nanoparticles provides the foundation for comparing recent advances in the implementation of multiple intermolecular interactions and computational strategies to fine-tune the assembled structures. We aim to bridge these fields, combining insights from multiple disciplines to inspire new approaches for the development of protein-mimetic materials, as these assemblies have far-reaching applications including in the development of new sensors, catalysts, and therapeutics.

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Discriminating Among Co‐monomer Sequence Distributions in Random Copolymers Using Interaction Chromatography

Cited by 16 publications

References 28 publications

Determining the Polydispersity in Chemical Composition and Monomer Sequence Distribution in Random Copolymers Prepared by Postpolymerization Modification of Homopolymers

Determining the Polydispersity in Chemical Composition and Monomer Sequence Distribution in Random Copolymers Prepared by Postpolymerization Modification of Homopolymers

A multiscale coarse-grained model to predict the molecular architecture and drug transport properties of modified chitosan hydrogels

Protein-Mimetic Self-Assembly with Synthetic Macromolecules

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