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.
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
Rachid
R
Matmour
Inge
I
De Cat
Subi J
SJ
George
Wencke
W
Adriaens
Philippe
P
Leclère
Paul H H
PH
Bomans
Nico A J M
NA
Sommerdijk
Jeroen C
JC
Gielen
Peter C M
PC
Christianen
Jeroen T
JT
Heldens
Jan C M
JC
van Hest
Dennis W P M
DW
Löwik
Steven
S
De Feyter
E W
EW
Meijer
Albertus P H J
AP
Schenning
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