Co-assembly of cyclic peptide nanotubes and block copolymers in thin films: controlling the kinetic pathway.

Published on Sep 21, 2015in Nanoscale7.79
路 DOI :10.1039/C5NR03915K
Chen Zhang2
Estimated H-index: 2
(University of California, Berkeley),
Ting Xu42
Estimated H-index: 42
(University of California, Berkeley)
Sources
Abstract
Directed co-assembly of polymer-conjugated cyclic peptide nanotubes (CPNs) and block copolymers in thin films is a viable approach to fabricate sub-nanometer porous membranes without synthesizing nanotubes with identical length and vertical alignment. Here we show that the process is pathway dependent and successful co-assembly requires eliminating CPNs larger than 100 nm in solution. Optimizing polymer鈥搒olvent interactions can improve conjugate dispersion to a certain extent, but this limits thin film fabrication. Introduction of a trace amount of hydrogen-bond blockers, such as trifluoroacetic acid by vapor absorption, is more effective to reduce CPN aggregation in solution and circumvents issues of solvent immiscibility. This study provides critical insights into guided assemblies within nanoscopic frameworks toward sub-nanometer porous membranes.
馃摉 Papers frequently viewed together
2015
1 Author (Chen Zhang)
201115.88ACS Nano
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References33
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#1Robert Chapman (USYD: University of Sydney)H-Index: 30
#2Ming Liang Koh (USYD: University of Sydney)H-Index: 7
Last. S茅bastien Perrier (USYD: University of Sydney)H-Index: 69
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We describe the solution assembly of polymer鈥揷yclic peptide conjugates into nanotubes, by direct in situ measurements. The conjugates were assembled by exploiting the 尾-sheet assembly of the alt(D,L) cyclic octapeptide core. The conjugated polymer permits solubilization of the peptide and the resulting nanotubes, thus allowing for the first time the direct study of the assembly mechanism of this system. The resulting materials present unique properties for a wide range of applications. We find t...
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#1Robert Chapman (USYD: University of Sydney)H-Index: 30
#2Katrina A. Jolliffe (USYD: University of Sydney)H-Index: 45
Last. S茅bastien Perrier (USYD: University of Sydney)H-Index: 69
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#1Rami Hourani (University of California, Berkeley)H-Index: 10
#2Chen Zhang (University of California, Berkeley)H-Index: 2
Last. Ting Xu (University of California, Berkeley)H-Index: 42
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A facile route to generate cyclic peptide nanotubes with tunable interiors is presented. By incorporating 3-amino-2-methylbenzoic acid in the d,l-alternating primary sequence of a cyclic peptide, a functional group can be presented in the interior of the nanotubes without compromising the formation of high aspect ratio nanotubes. The new design of such a cyclic peptide also enables one to modulate the nanotube growth process to be compatible with the polymer processing window without compromisin...
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#1Yong Wang (Nanjing Tech University)H-Index: 62
#2Fengbin Li (Nanjing Tech University)H-Index: 6
Block copolymers (BCPs) composed of two or more thermodynamically incompatible homopolymers self-assemble into periodic microdomains. Exposing self-assembled BCPs with solvents selective to one block causes a swelling of the domains composed of this block. Strong swelling in the confinement imposed by the matrix of the other glassy block leads to well-defined porous structures via morphology reconstruction. This confined swelling-induced pore-making process has emerged recently as a new strategy...
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#1Douglas L. Gin (CU: University of Colorado Boulder)H-Index: 63
#2Richard D. Noble (CU: University of Colorado Boulder)H-Index: 96
Synthetic membranes are used in many separation processes, from industrial-scale ones鈥攕uch as separating atmospheric gases for medical and industrial use, and removing salt from seawater鈥攖o smaller-scale processes in chemical synthesis and purification. Membranes are commonly solid materials, such as polymers, that have good mechanical stability and can be readily processed into high鈥搒urface area, defect-free, thin films. These features are critical for obtaining not only good chemical separatio...
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#1Ting Xu (University of California, Berkeley)H-Index: 42
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Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation and protective coatings. While molecularly defined nanoporous inorganic and organic materials abound, generating flexible nanoporous thin films with highly aligned channels over large areas has been elusive. Here, we developed a new approach where the growth of cyclic peptide nanotubes can be directed in a structu...
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Self-assembling cyclic peptide-polymer conjugates were prepared by 鈥榗licking鈥 polymers (prepared by RAFT polymerization) to an azide functionalized d-alt-l cyclic octapeptide via the Huisgen 1,3-dipolar cycloaddition reaction. Due to the high graft density, the efficiency of the click chemistry conjugation reaction was found to be highly dependent on the size of the polymer. At relatively low molecular weights, as many as four polymer chains could be grafted to each 8 residue cyclic peptide ring...
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With nanoscale pores, high porosity, narrow pore size distributions, and tunable chemical and mechanical properties, block copolymers hold tremendous potential as robust, efficient, and highly selective separation membranes. Recent work by Yang et al. illustrates how block copolymers can be employed in the preparation of membranes for use in controlled, long-term, protein-delivery devices. Their work demonstrates that highly efficient and tunable separations are possible with block copolymer mem...
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#1Julien Couet (University of Freiburg)H-Index: 7
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: The external structure of polymer-wrapped nanotubes resembles that of small nanorods with a core/shell morphology, where the core consists of a self-assembled peptide nanotube surrounded by a soft polymeric coat. The length and the diameter of the nanorods are investigated as a function of the molar mass of the peptide-grafted macromolecules by statistical atomic force microscopy cross-section analysis of dry nanorods adsorbed to a solid substrate. With increasing molar mass of the grafted pol...
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#1Mark A. Shannon (UIUC: University of Illinois at Urbana鈥揅hampaign)H-Index: 45
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