Oligo(p-phenylenevinylene)-peptide conjugates: synthesis and self-assembly in solution and at the solid-liquid interface.
Two oligo(p-phenylenevinylene)-peptide hybrid amphiphiles have been synthesized using solid- and liquid-phase strategies. The amphiliphiles are composed of a pi-conjugated oligo(p-phenylenevinylene) trimer (OPV) which is coupled at either a glycinyl-alanyl-glycinyl-alanyl-glycine (GAGAG) silk-inspired beta-sheet or a glycinyl-alanyl-asparagyl-prolyl-asparagy-alanyl-alanyl-glycine (GANPNAAG) beta-turn forming oligopeptide sequence. The solid-phase strategy enables one to use longer peptides if strong acidic conditions are avoided, whereas the solution-phase coupling gives better yields. The study of the two-dimensional (2D) self-assembly of OPV-GAGAG by scanning tunneling microscopy (STM) at the submolecular level demonstrated the formation of bilayers in which the molecules are lying antiparallel in a beta-sheet conformation. In the case of OPV-GANPNAAG self-assembled monolayers could not be observed. Absorption, fluorescence, and circular dichroism studies showed that OPV-GAGAG and OPV-GANPNAAG are aggregated in a variety of organic solvents. In water cryogenic temperature transmission electron microscopy (cryo-TEM), atomic force microscopy (AFM), light scattering, and optical studies reveal that self-assembled nanofibers are formed in which the helical organization of the OPV segments is dictated by the peptide sequence.
Matmour
Rachid
R
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
De Cat
Inge
I
George
Subi J
SJ
Adriaens
Wencke
W
Leclère
Philippe
P
Bomans
Paul H H
PH
Sommerdijk
Nico A J M
NA
Gielen
Jeroen C
JC
Christianen
Peter C M
PC
Heldens
Jeroen T
JT
van Hest
Jan C M
JC
Löwik
Dennis W P M
DW
De Feyter
Steven
S
Meijer
E W
EW
Schenning
Albertus P H J
AP
D000409:Alanine / Q000737:chemistry; D005998:Glycine / Q000737:chemistry; D016252:Microscopy, Scanning Tunneling; D019906:Nuclear Magnetic Resonance, Biomolecular; D009842:Oligopeptides / Q000138:chemical synthesis* / Q000737:chemistry; D011145:Polyvinyls / Q000138:chemical synthesis* / Q000737:chemistry; D017433:Protein Structure, Secondary; D012996:Solutions; D013050:Spectrometry, Fluorescence; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013056:Spectrophotometry, Ultraviolet; D013499:Surface Properties
D009842:Oligopeptides; D011145:Polyvinyls; D012996:Solutions; C470024:poly(4-phenylenevinylene); D000409:Alanine; D005998:Glycine