Narcissistic Self-Sorting of Amphiphilic Collagen-Inspired Peptides in Supramolecular Vesicular Assembly.

Herein, we describe the hierarchical self-assembly accompanying self-sorting of collagen-inspired peptides (CPs). The two amphiphilic CPs used in this study contained an azobenzene (Az) moiety at the -terminal, connected through a flexible spacer, but with different lengths of the (Gly-Pro-Hyp) triplet ( = 5 and 7). When the CP aqueous solution (60 °C) was cooled to 4 °C, both CPs formed a triple helix structure and the pre-organized helices subsequently self-assembled into highly ordered vesicles with a diameter of 50-200 nm.

Supramolecular Nanofibers from Collagen-Mimetic Peptides Bearing Various Aromatic Groups at N-Termini via Hierarchical Self-Assembly.

Self-assembly of artificial peptides has been widely studied for constructing nanostructured materials, with numerous potential applications in the nanobiotechnology field. Herein, we report the synthesis and hierarchical self-assembly of collagen-mimetic peptides (CMPs) bearing various aromatic groups at the -termini, including 2-naphthyl, 1-naphtyl, anthracenyl, and pyrenyl groups, into nanofibers. The CMPs (-(GPO): > 4) formed a triple helix structure in water at 4 °C, as confirmed via CD analyses, and their conformations were more stable with increasing hydrophobicity of the terminal aromatic group and peptide chain length.

Unique Self-Assembly of Sequence-Controlled Amino Acid Derived Vinyl Polymer with Gradient Thermoresponsiveness along a Chain.

A novel water-soluble amino acid derived vinyl polymer whose block sequence was designed to achieve a gradient thermoresponsiveness along a chain was accurately prepared through an ultrarapid reversible addition-fragmentation chain-transfer polymerization. The polymer exhibited unique temperature-regulated self-assembly in water, leading to multiple nanostructural transformations including disassembly-to-ordered and ordered-to-ordered transitions. The morphologies were drastically changed by heating the solution from 4 °C (soluble form) to 20 °C (spherical micelle) to 70 °C (vesicle).

Photo-responsive azobenzene interactions promote hierarchical self-assembly of collagen triple-helical peptides to various higher-order structures.

Collagen is an essential structural protein in animal tissues and plays key roles in cellular modulation. We investigated methods to discover collagen model peptides (CMPs) that would self-assemble into triple helices and then grow into supramolecular organizations with diverse morphological features, which would be valuable as biomaterials. This challenging undertaking was achieved by placing azobenzene groups on the ends of the CMPs, (GPO) ( = 3-10), Azo-(GPO) .

Transparent, High-Strength, and Shape Memory Hydrogels from Thermo-Responsive Amino Acid-Derived Vinyl Polymer Networks.

Herein, the formation of unique shape-memory hydrogels that are composed of thermo-responsive amino-acid-derived vinyl polymer networks is reported; these are readily prepared by radical copolymerization of N-acryloyl glycinamide with commercially available cross-linkers, namely, methylenebis(acrylamide) and poly(ethylene glycol) diacrylate. These hydrogels are transparent (>90% transmittance at 600 nm) and are comprised of 97-70 wt% water. Furthermore, these contain both chemical and physical cross-linkages that are based on the multiple hydrogen bonds attained via amino acid units; this composition is aimed at generating opposing stimuli-responsive characters, namely, chemically stable and thermo-sensitive properties.

Precisely Synthesized Sequence-Controlled Amino Acid-Derived Vinyl Polymers: New Insights into Thermo-Responsive Polymer Design.

Thermo-responsive block copolymers are of great interest in biomedical and nanotechnological fields. These polymers achieve a versatile and complex responsiveness through a sophisticated and intricate combination of different thermo-responsive blocks. While their utility is clear, the fundamental design principles of such vinyl polymers are not yet thoroughly understood.

Spontaneous Formation of Nanoparticles from Peptide-Vinyl Polymer Diblock Hybrids Prepared by RAFT Polymerization and Their Interactions with Cells.

Novel polymeric nanoparticles (NPs) with uniform sizes were prepared from peptide-vinyl polymer diblock hybrids by the self-organized precipitation method. Hybrid polymers of polystyrene (PSt) and tetrapeptide (cell-binding epitope RGDS, reverse SDGR, cationic KKKK, and anionic DDDD) were successfully synthesized by combining solid-phase peptide synthesis and reversible addition fragmentation chain transfer polymerization methods. Narrowly dispersed hybrid polymers (polydispersity index < 1.

Photocleavable Peptide-Poly(2-hydroxyethyl methacrylate) Hybrid Graft Copolymer via Postpolymerization Modification by Click Chemistry To Modulate the Cell Affinities of 2D and 3D Materials.

Controlling the surface properties of engineered materials to enhance or reduce their cellular affinities remains a significant challenge in the field of biomaterials. We describe a universal technique for modulating the cytocompatibilities of two-dimensional (2D) and three-dimensional (3D) materials using a novel photocleavable peptide-grafted poly(2-hydroxyethyl methacrylate) (PHEMA) hybrid. The reversible addition-fragmentation chain transfer copolymerization of HEMA and propargyl acrylate was successfully controlled.

A novel thermo-responsive multiblock architecture composed of a sequential peptide and an amino acid-derived vinyl polymer: toward protein-mimicking single-chain folding.

A novel multiblock architecture composed of an alternating β-sheet forming oligopeptide and a thermo-responsive glycine-derived vinyl polymer was synthesized. The polymer exhibited lower critical solution temperature (LCST) behavior in water, unlike the behavior of a glycine-derived homopolymer, and formed nanoparticles through protein-mimicking folding driven by thermal cycle-induced β-sheet formation.

Stepwise Thermo-Responsive Amino Acid-Derived Triblock Vinyl Polymers: ATRP Synthesis of Polymers, Aggregation, and Gelation Properties via Flower-Like Micelle Formation.

Novel thermo-responsive ABA-type triblock copolymers (poly(NAAMe--NAGMe--NAAMe), = 18-72) composed of naturally occurring amino acid-based vinyl polymer blocks such as poly(-acryloyl-l-alanine methyl ester (poly(NAAMe)) as the A segment and poly(-acryloyl-glycine methylester)(poly(NAGMe)) as the B segment have been synthesized by the atom transfer radical polymerization (ATRP). Their thermal behaviors were analyzed in dilute aqueous solutions by turbidimetry. The turbidity curves provided two-step LCST transitions, and a flower-like micelle formation was confirmed at the temperature region between the first and second LCST transitions by dynamic light scattering, AFM and TEM.

Facile Synthesis of Multiblock Copolymers Containing Sequence-Controlled Peptides and Well-Defined Vinyl Polymers by Nitroxide-Mediated Polymerization.

Precisely incorporating a wide range of structural and functional multiblocks along a polymer backbone is a significant challenge in polymer chemistry and offers promising opportunities to design highly ordered materials, including controlled polymer folding. Herein, a facile and versatile strategy for preparing functional multiblock copolymers composed of sequential peptides and well-defined vinyl polymers with a narrow polydispersity is reported. Cyclic oligopeptides have been developed that contain an alkoxyamine bond in the framework.

Thermo-responsive polymer brushes on glass plate prepared from a new class of amino acid-derived vinyl monomers and their applications in cell-sheet engineering.

In this study, we present a novel thermo-responsive polymer platform that is based on the alanine methyl ester-containing homopolymer (PNAAMe) and the copolymer with glycine methyl ester-based vinyl monomer (P(NAAMe-co-NAGMe)) brushes prepared via surface-initiated atom transfer radical polymerization. Water contact angles for these brushes measured at different temperatures reveal that the polymer brushes collapse and dehydrate around 13°C and 25°C (Ts), respectively, upon elevating the temperature. At 37°C, seeded fibroblasts (NIH/3T3) adhere to and spread well onto these brush surfaces although the copolymer brush of P(NAAMe-co-NAGMe) depresses the number of adherent cells less than half of that for the homopolymer of PNAAMe after 24h of cell culture due to increment in hydrophilicity.

Temperature induced self-assembly of amino acid-derived vinyl block copolymers via dual phase transitions.

The unique thermoresponsive phase behaviors of diblock copolymers from amino acid-derived vinyl monomers have been demonstrated in view of variation in the aggregation state in water. Amino acid-based block copolymers composed of N-acryloyl-Ala-methylester (NAAMe) and N-acryloyl-βAla-methylester (NAβAMe) are successfully synthesized by RAFT polymerization. The resultant block copolymers poly(NAAMe-b-NAβAMe) contain a constant degree of polymerization (DP=48) of the poly(NAAMe) block, but the DP of the poly(NAβAMe) block varies (m=80-122).

Novel Self-Assembling Amino Acid-Derived Block Copolymer with Changeable Polymer Backbone Structure.

Block copolymers have attracted much attention as potentially interesting building blocks for the development of novel nanostructured materials in recent years. Herein, we report a new type of self-assembling block copolymer with changeable polymer backbone structure, poly(Fmoc-Ser)-b-PSt, which was synthesized by combining the polycondensation of 9-fluorenylmethoxycarbonyl-serine (Fmoc-Ser) with the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St). This block copolymer showed the direct conversion of the backbone structure from polyester to polypeptide through a multi O,N-acyl migration triggered by base-induced deprotection of Fmoc groups in organic solvent.

Preparation and self-assembly behavior of β-sheet peptide-inserted amphiphilic block copolymer as a useful polymeric surfactant.

A hybridization of structurally regulated biopolymers and conventional synthetic polymers offers promising opportunities to design novel polymeric nanomaterials. In this study, we newly prepared an amphiphilic triblock copolymer with β-sheet forming peptide as a central block, polystyrene-block-tetra(leucine)-block-poly(ethylene glycol) (PS-L4-PEG), by combining the solid phase peptide synthesis with the atom transfer radical polymerization (ATRP). On the basis of several morphological and structural analyses using atomic force microscopy, transmission electron microscopy, FTIR spectroscopy, and contact angle measurement, the PS-L4-PEG was found to form PEG-shell spherical and/or elliptical vesicles with a diameter of 30-100 nm in aqueous medium.

Novel peptide-shelled dendrimer with dramatically changeable thermo-responsive character.

The preparation of a novel peptide/dendrimer hybrid is reported in which an elastin-like oligopeptide is successfully assembled onto a poly(amidoamine) dendrimer surface (G4-ELP), and its unique thermo-responsive behavior is discussed. As a result, the G4-ELP is found to exhibit LCST behavior in the pH range 3-10 including physiological temperature range under neutral-pH conditions. Moreover, cooperative interplay between the folding state of the ELP shell and the ionization state of the dendrimer core enables the G4-ELP to control its LCST widely by pH variation.

Shape-specific nanofibers via self-assembly of three-branched peptide.

A novel amphiphilic branched peptide (1), in which three β-sheet formable peptides (L(4)K(8)L(4)) were connected by Lys residue, was newly prepared as a building block for self-assembly. A detailed analysis of the conformation and self-assembling property of 1 in water at various pH conditions was performed by using circular dichroism, FTIR, atomic force and transmission electron microscopies. The experimental results revealed that the branched peptide showed a pH-dependent conformation forming a shape-specific β-sheet-based nanofiber with morphologically kinked structures under specific pH conditions.

Fabrication of nucleobase-functionalized supramolecular nanofiber through peptide self-assembly.

In this study, we describe a novel molecular self-assembling system of a nucleobase-functionalized oligopeptide. An adenine-terminated amphiphilic triblock peptide (1), which consists of hydrophobic Leu and hydrophilic Lys, was newly synthesized as a building block for self-assembly. The conformational and self-assembling properties of 1 in water at various conditions were examined by means of circular dichroism, FTIR, UV, atomic force microscopy, and transmission electron microscopy measurements.

Enzymatically triggered self-assembly of poly(ethylene glycol)-attached oligopeptides into well-organized nanofibers.

A unique and programmable peptide self-assembling system has been fabricated by using poly(ethylene glycol)-attached amphiphilic oligopeptide, which shows rapid self-assembly into well-organized beta-sheet nanofibers in response to an enzymatic reaction.

Chain length effects of oligo(L-lysine)-shelled dendrimers on interaction with DNA.

The interaction of novel oligo(L-lysine)-shelled dendrimers (G3-PLL) with DNA was studied by means of circular dichroism spectroscopy, dynamic light scattering, and melting behavior of double-stranded DNA. G3-PLLs having various oligo(L-lysine) (PLL) segment (n = 5-40) were successfully synthesized by graft-polymerization of L-lysine NCA initiated with amino groups at the 3rd-generation poly(amidoamine) dendrimer surface. The ionization property of the newly prepared G3-PLLs were first examined.

pH-responsive, self-assembling nanoparticle from a fullerene-tagged poly(L-glutamic acid) and its superoxide dismutase mimetic property.

In this study, we describe the fabrication of novel fullerene-containing peptide-nanoparticles through self-assembly. A water-soluble, poly(l-glutamic acid)-attached fullerene was newly synthesized and the conformation and self-assembling property in water were examined by using circular dichroism, FTIR, UV, atomic force microscopy, and dynamic light scattering measurements. In the lower pH region (<6.

Structural control of self-assembled nanofibers by artificial beta-sheet peptides composed of D- or L-isomer.

A novel method for the control of peptide self-assembly has been developed by using synthetic triblock-type beta-sheet peptides composed of l- or d-amino acid, 1L and 1D, as building blocks. The peptides 1L and 1D self-assemble into beta-sheet nanofibers with left- and right-handed twists, respectively, under appropriate condition. On the other hand, the 1L/1D binary mixture was found to form only globular aggregates at the same condition.

Controlled self-assembly of amphiphilic oligopeptides into shape-specific nanoarchitectures.

Here, we report a novel, programmable, molecular self-assembling system to fabricate shape-specific, three-dimensional nanoarchitectures. Three types of simple 16-mer peptides consisting of hydrophobic Leu and hydrophilic Lys, LKL16, KLK16, and LK16, were prepared as building blocks for nanofabrications. A detailed analysis of the conformation and self-assembling mechanism was performed by using circular dichroism (CD), FTIR spectroscopy, and atomic force microscopy (AFM).