Enhanced Anticancer Efficacy of Chemotherapy by Amphiphilic Y-Shaped Polypeptide Micelles

Although the treatment modalities of cancers are developing rapidly, chemotherapy is still the primary treatment strategy for most solid cancers. The progress in nanotechnology provides an opportunity to upregulate the tumor suppression efficacy and decreases the systemic toxicities. As a promising nanoplatform, the polymer micelles are fascinating nanocarriers for the encapsulation and delivery of chemotherapeutic agents. The chemical and physical properties of amphiphilic co-polymers could significantly regulate the performances of the micellar self-assembly and affect the behaviors of controlled release of drugs. Herein, two amphiphilic Y-shaped polypeptides are prepared by the ring-opening polymerization of cyclic monomer l-leucine N-carboxyanhydride (l-Leu NCA) initiated by a dual-amino-ended macroinitiator poly(ethylene glycol) [mPEG-(NH2)2]. The block co-polypeptides with PLeu8 and PLeu16 segments could form spontaneously into micelles in an aqueous solution with hydrodynamic radii of 80.0 ± 6.0 and 69.1 ± 4.8 nm, respectively. The developed doxorubicin (DOX)-loaded micelles could release the payload in a sustained pattern and inhibit the growth of xenografted human HepG2 hepatocellular carcinoma with decreased systemic toxicity. The results demonstrated the great potential of polypeptide micellar formulations in cancer therapy clinically.

Ring-opening polymerization

Ring-opening polymerization is defined by IUPAC (Penczek, S., Moad, G. (2008). Glossary of the terms related to kinetics, thermodynamics, and mechanisms of polymerization. (IUPAC Recommendations 2008), Pure and Applied Chemistry, 80(10), 2163–2193) as (cit.) “Ring-opening polymerization (ROP): Polymerization in which a cyclic monomer yields a monomeric unit that is either acyclic or contains fewer rings than the cyclic monomer”. The large part of the resulting polymerizations is living/controlled; practically all belong to chain polymerizations. After the introduction, providing basic information on chain polymerizations, the paper presents the concise overview of major classes of monomers used in ROP, including cyclic ethers, esters, carbonates, and siloxanes as well as cyclic nitrogen, phosphorus, and sulfur containing monomers. There are discussed also thermodynamics, kinetic polymerizability, and major mechanisms of ROP. Special attention is concentrated on polymers prepared by ROP on industrial scale.

The synthesis of cyclic olefin copolymers (COCs) by ethylene copolymerisations with cyclooctene, cycloheptene, and with tricyclo[6.2.1.0(2,7)]undeca-4-ene: the effects of cyclic monomer structures on thermal properties

The synthesis of amorphous ethylene copolymers with cycloheptene, cis-cyclooctene, or tricyclo[6.2.1.0(2,7)]undeca-4-ene using half-titanocene catalysts and the effects of ring size and structure on the thermal properties have been demonstrated.

Polymers from sugars: cyclic monomer synthesis, ring-opening polymerisation, material properties and applications

This feature article gives an overview of sugar-based polymers that can be made by ring-opening-polymerisation and their applications.

Methylenelactide: vinyl polymerization and spatial reactivity effects

The first detailed study on free-radical polymerization, copolymerization and controlled radical polymerization of the cyclic push–pull-type monomer methylenelactide in comparison to the non-cyclic monomer α-acetoxyacrylate is described. The experimental results revealed that methylenelactide undergoes a self-initiated polymerization. The copolymerization parameters of methylenelactide and styrene as well as methyl methacrylate were determined. To predict the copolymerization behavior with other classes of monomers, Q and e values were calculated. Further, reversible addition fragmentation chain transfer (RAFT)-controlled homopolymerization of methylenelactide and copolymerization with N,N-dimethylacrylamide was performed at 70 °C in 1,4-dioxane using AIBN as initiator and 2-(((ethylthio)carbonothioyl)thio)-2-methylpropanoic acid as a transfer agent.

Remendable thermosetting polymers for isocyanate-free adhesives: a preliminary study

Based on a model study, a new bis-cyclic monomer bearing a Diels–Alder adduct was synthesized. This monomer was polymerized with a diamine to yield a thermoresponsive polyhydroxyurethane (PHU). This PHU is remendable at around 100 °C by retro Diels–Alder reaction.