Abstract:The helical and tubular structures self-assembled from proteins have inspired scientists to design synthetic building blocks that can be "polymerized" into supramolecular polymers through coordinated noncovalent interactions. However, cooperative supramolecular polymerization from large, synthetic macromolecules remains a challenge because of the difficulty of controlling the structure and interactions of macromolecular monomers. Herein we report the synthesis of polypeptide-grafted comb polymers and the use o… Show more
“…When pH decreases, carboxyl groups are protonated. The polymer then adopts a helical conformation and becomes insoluble in water [3,13,14] . This phase-transition could be adjusted by copolymerization Glu with hydrophobic amino acids [15] .…”
Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid (Glu) with L-leucine (Leu) [poly(Glu-r-Leu)s], as well as their block copolymers with polysarcosine (polySar). Well-defined poly(Glu-r-Leu)s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly(Glu-r-Leu) with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly(Glu-r-Leu)-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.
“…When pH decreases, carboxyl groups are protonated. The polymer then adopts a helical conformation and becomes insoluble in water [3,13,14] . This phase-transition could be adjusted by copolymerization Glu with hydrophobic amino acids [15] .…”
Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid (Glu) with L-leucine (Leu) [poly(Glu-r-Leu)s], as well as their block copolymers with polysarcosine (polySar). Well-defined poly(Glu-r-Leu)s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly(Glu-r-Leu) with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly(Glu-r-Leu)-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.
“…PGA can adopt different solution conformations depending on the degree of ionization, while pH represents a critical parameter for controlled supramolecular polymerization. 28,29 We performed circular dichroism studies of F3E10 at pH 7.5 (Fig. SI1 â ) and observed that PGA adopts a random coil conformation.…”
“…Wang et al have found conditions where polypeptidegrafted comblike polymers form tubular structures. [12] Moreover, they found that gold nanoparticles with grafted poly-(L-glutamic acid) can form tubules under certain circumstances. [12,13] In these systems, the monomer is effectively a single nanoparticle and the nanoparticle-nanoparticle interactions dictate the tubule formation.…”
The efficient and controlled assembly of complex structures from macromolecular building blocks is a critical open question in both biological systems and nanoscience. Using molecular dynamics simulations we study the self-assembly of tubular structures from model macromolecular monomers with multiple binding sites on their surfaces [Cheng et al., Soft Matter, 2012, 8, 5666-5678]. In this work we add chirality to the model monomer and a lock-and-key interaction. The self-assembly of free monomers into tubules yields a pitch value that often does not match the chirality of the monomer (including achiral monomers). We show that this mismatch occurs because of a twist deformation that brings the lateral interaction sites into alignment when the tubule pitch differs from the monomer chirality. The energy cost for this deformation is small as the energy distributions substantially overlap for small differences in the pitch and chirality. In order to control the tubule pitch by preventing the twist deformation, the interaction between the vertical surfaces must be increased without resulting in kinetically trapped structures. For this purpose, we employ lock-and-key interactions and obtain good control of the self-assembled tubule pitch. These results explain some fundamental features of microtubules. The vertical interaction strength is larger than the lateral in microtubules because this yields a controlled assembly of tubules with the proper pitch. We also generally find that the control of the assembly into tubules is difficult, which explains the wide range of pitch values and protofilament numbers observed in microtubule assembly.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citationsâcitations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.