Effects of Secondary Structures and pH on the Self-Assembly of Poly(ethylene glycol)--polytyrosine.

Different from conventional synthetic polymers, polypeptides exhibit a distinguishing characteristic of adopting specific secondary structures, including random coils, α-helixes, and β-sheets. The conformation determines the rigidity and solubility of polypeptide chains, which further direct the self-assembly and morphology of the nanostructures. We studied the effect of distinct secondary structures on the self-assembly behavior of polytyrosine (PTyr)-derived amphiphilic copolymers.

Helical Self-Assembly of Amphiphilic Chiral Azobenzene Alternating Copolymers.

Imposing chirality to supramolecular architectures is an important step forward toward understanding and utilization of chiral nanomaterials. This article reports the self-assembly of amphiphilic chiral alternating copolymers of poly(binaphthyl azobenzene--hexaethylene glycol) (P(BNPAzo--EG)) into helical supramolecular rods. Unlike conventional chiral assembly of copolymers largely through intermolecular organization, the intrachain stacking of chiral units along the main chain into single molecular micelles with amplified axial chirality of binaphthyl is key to the formation of helical supramolecular rods, which takes advantage of the particular chiral unit and soft unit alternating topological structure of the backbones.

An Inspection into Multifarious Ways to Synthesize Poly(Amino Acid)s.

Poly(α-amino acid)s (PAAs) attract growing attention due to their essential role in the application as biomaterials. To synthesize PAAs with desired structures and properties, scientists have developed various synthetic techniques with respective advantages. Here, different approaches to preparing PAAs are inspected.

Polymersomes with aggregation-induced emission based on amphiphilic block copolypeptoids.

Biocompatible polymersomes are prepared from amphiphilic block copolypeptoids with aggregation-induced emission, where the hydrophobic block P(TPE-NAG) is a tetraphenylethylene (TPE)-modified poly(N-allylglycine) and the hydrophilic block is polysarcosine. These nanoparticles are non-cytotoxic and show strong fluorescence emission in aqueous solution.

Oxidation-Sensitive Polymersomes Based on Amphiphilic Diblock Copolypeptoids.

Stimuli-responsive polymersomes formed by amphiphilic block copolymers have attracted substantial attention as smart and robust containers for drug delivery and nano/microreactors. Biosourced amphiphilic diblock copolypeptoids were developed that can self-assemble into oxidation-responsive unilamellar vesicles. These vesicles can burst under the action of reactive oxygen species which can be the hydrogen peroxide or the singlet oxygen produced by light-activation of a photosensitizer with spatiotemporal control.

Identifying the Hydrolysis of Carbonyl Sulfide as a Side Reaction Impeding the Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride.

Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization.

Fe@polyDOPA--polysarcosine, a T-Weighted MRI Contrast Agent via Controlled NTA Polymerization.

α-Amino acid -thiocarboxyanhydrides (NTAs) are promising cyclic monomers to synthesize polypeptides and polypeptoids via controlled ring-opening polymerizations. Superior to -carboxyanhydrides requiring protection on hydroxyl groups, NTAs are able to tolerate such nucleophiles. In this work, we report the synthesis of NTA monomers containing unprotected phenolic hydroxyl groups of 3,4-dihydroxy-l-phenylalanine (DOPA) and l-tyrosine (Tyr).

Polysarcosine brush stabilized gold nanorods for in vivo near-infrared photothermal tumor therapy.

Unlabelled: Gold nanorods (AuNRs) are suitable candidates for photothermal therapy in vivo, because of their excellent ability to transfer near-infrared (NIR) light into heat. However, appropriate surface should be generated on AuNRs before their in vivo application because of the low colloidal stability in complicate biological environment and relatively strong toxicity compared to their pristine stabilizer cetyltrimethylammonium bromide. In the current study, polysarcosine (PS), a non-ionic hydrophilic polypeptoid whose structure is similar to polypeptides, bearing repeating units of natural α-amino acid, was used to stabilize AuNRs due to its excellent hydrophilicity and biocompatibility.

Gold nanoparticles coated with polysarcosine brushes to enhance their colloidal stability and circulation time in vivo.

Polysarcosine (PS), a non-ionic hydrophilic polypeptoid whose structure is similar to polypeptides, bearing repeating units of natural α-amino acid, has been used to stabilize gold nanoparticles (AuNPs) due to its excellent hydrophilicity and biocompatibility. Disulfide functionalized polysarcosines with different molecular weight were synthesized and used to cap AuNPs by traditional ligand exchange. The grafting of PS on AuNPs was evidenced by Fourier transform infrared (FTIR) spectroscopy and the alternation of surface zeta potential.

Poly(ε-caprolactone)-block-polysarcosine by Ring-Opening Polymerization of Sarcosine N-Thiocarboxyanhydride: Synthesis and Thermoresponsive Self-Assembly.

Biocompatible amphiphilic block copolymers composed of polysarcosine (PSar) and poly(ε-caprolactone) (PCL) were synthesized using ring-opening polymerization of sarcosine N-thiocarboxyanhydride initiated by oxyamine-ended PCL and characterized by NMR, SEC, and DSC. Self-assembling of two triblock copolymers PSar8-b-PCL28-b-PSar8 (CS7) and PSar16-b-PCL40-b-PSar16 (CS10) in dilute solution was studied in detail toward polymersome formation using thin-film hydration and nanoprecipitation techniques. A few giant vesicles were obtained by thin-film hydration from both copolymers and visualized by confocal laser scanning microscope.

PEG-amine-initiated polymerization of sarcosine N-thiocarboxyanhydrides toward novel double-hydrophilic PEG-b-polysarcosine diblock copolymers.

Amino acid N-thiocarboxyanhydride (NTA), the thioanalog of N-carboxyanhydride (NCA), is much more stable than NCA against moisture and heat. The convenient monomer synthesis without rigorous anhydrous requirements makes the ring-opening polymerization of NTA a competitive alternative to prepare polypeptoid-containing materials with potential of large-scale production. Polysarcosines (PSars) with high yields (>90%) and low polydispersities (<1.