Langmuir p. 11375 - 11385 (2014)
Update date:2022-08-02
Topics:
Wall, Brian D.
Zhou, Yuecheng
Mei, Shao
Ardoa, Herdeline Ann M.
Ferguson, Andrew L.
Tovar, John D.
This photophysical study characterizes the generality of intermolecular electronic interactions present within nanomaterials derived from self-assembling oligopeptides with embedded π-conjugated oligophenylenevinylene (OPV) subunits stilbene and distyrylbenzene that in principle present two distinct β-sheet motifs. Two different synthetic approaches led to oligopeptides that upon self-assembly are expected to self-assemble into multimeric aggregates stabilized by β-sheet-like secondary structures. The target molecules express either two C-termini linked to the central OPV core (symmetric peptides) or the more common N-termini to C-termini polarity typical of natural oligopeptides (nonsymmetric peptides). Both peptide secondary structures were shown to form extended 1-D peptide aggregates with intimate intermolecular π-electron interactions. Differences in length of the π-conjugated OPV segments resulted in differing extents of intermolecular interactions and the resulting photophysics. The peptides containing the shorter stilbene (OPV2) units showed little ground state interactions and resulted in excimeric emission, while the longer distyrylbenzene (OPV3) peptides had different ground state interactions between adjacent π-conjugated subunits resulting in either perturbed electronic properties arising from exciton coupling or excimer-like excited states. Molecular dynamics simulations of nascent aggregate formation predict peptide dimerization to be a spontaneous process, possessing thermodynamic driving potentials in the range 2-6 kcal/mol for the four molecules considered. Antiparallel stacking of the peptides containing an OPV3 subunit is thermodynamically favored over the parallel orientation, whereas both arrangements are equally favored for the peptides containing an OPV2 subunit. This study validates the generality of peptide-π-peptide self-assembly to provide electronically delocalized supramolecular structures and suggests flexibility in peptide sequence design as a way to tune the material properties of π-conjugated supramolecular polymers.
View MoreGuangxi Bonger Pharmaceutical Co., Ltd
website:http://napo.lookchem.com/
Contact:+86-18817331185
Address:Donghai Industrial Zone, Tiandong Country,Guangxi,China
Yicheng Goto Pharmaceuticals Co.,Ltd.
Contact:+86 710 3423122
Address:5th Floor,East Gate of Building #2,Servo-Industrial Park,1st Qilin Road,Xiangyang,Hubei,China
Wuxi Forest Biological Co.,Ltd
Contact:+86-510-81602300
Address:Room 317,Building D, No.159 middle Chengjiang Road,Jiangyin Wuxi city.
Shangyu Sanhechemicals Co.,LTD.
Contact:86-0571-56696839
Address:Num.2952,Nanhuan Road,Binjiang District,Hangzhou,China
Fusilin chemical science & technology co., ltd.
Contact:532-80698166/86057573, +86-400-669-7885
Address:School of Material Science & Engineering, Shandong Uinversity of Science & Technology, Huangdao Zone, Qindao, Shandong
Doi:10.1021/om00038a024
(1992)Doi:10.1021/jo01362a029
(1957)Doi:10.1021/acs.jmedchem.9b01852
(2020)Doi:10.1080/10426507.2014.974751
(2015)Doi:10.1080/07328300008544065
(2000)Doi:10.1055/s-1986-31701
(1986)