Search

The synthesis of well‐defined propargyl‐functional aliphatic polycarbonates is achieved via the organocatalytic ring‐opening polymerization of prop‐2‐yn‐1‐yl 2‐oxo‐1,3,6‐dioxazocane‐6‐carboxylate (P‐8NC) using a wide variety of commercially available or readily made, shelf‐stable organocatalysts. The resulting homopolymers show low dispersities and end‐group fidelity, with the versatility of the system being demonstrated by the synthesis of telechelic copolymers and block copolymers with molar mass up to 40 kDa. [ABSTRACT FROM AUTHOR]

Regioregular poly(3-hexylthiophene) has been successfully incorporated into various poly( N, N-dimethylamino-2-ethyl methacrylate)-based block copolymers, i.e., P3HT- b-PDMAEMA, via Grignard metathesis (GRIM) method and atom transfer radical polymerization (ATRP) reactions. The structure of the diblock copolymers was fully confirmed by FT-IR, H NMR spectroscopy, gel permeation chromatography (GPC), and ultraviolet-visible spectroscopy (UV-vis). The recovered copolymers could be treated by protonation of the pending tertiary amine functions and depending on the relative content in PDMAEMA, the copolymers could be solubilized in more polar solvents where P3HT alone proved to be totally insoluble. [ABSTRACT FROM AUTHOR]

Abstract: In this paper, we describe the design and characterization of regioregular poly(3-hexylthiophene)-poly(ε-caprolactone) di- and tri-block copolymers (RRP3HT-b-PCL and PCL-b-RRP3HT-b-PCL). The well-controlled synthesis of (di)hydroxyl-terminated RRP3HT makes possible to design block copolymer structures with a narrow molecular weight distribution. The microscopic morphology is investigated by atomic force microscopy, which reveals self-assembled fibrillar structures with the RRP3HT nanoribbons separated by narrow domains of insulating PCL. The charge transport properties are characterized in thin films field-effect transistors, and comparison between the devices performances is carried out in view of the nanoscale morphology within the transistor channel. [Copyright &y& Elsevier]

Hydrophobic and amphiphilic derivatives of the biocompatible and biodegradable poly(dimethylmalic acid) (PdiMeMLA), varying by the nature of the lateral chains and the length of each block, respectively, have been synthesized by anionic ring-opening polymerization (aROP) of the corresponding monomers using an initiator/base system, which allowed for very good control over the (co)polymers' characteristics (molar masses, dispersity, nature of end-chains). Hydrophobic and core-shell nanoparticles (NPs) were then prepared by nanoprecipitation of hydrophobic homopolymers and amphiphilic block copolymers, respectively. Negatively charged NPs, showing hydrodynamic diameters (Dh) between 50 and 130 nm and narrow size distributions (0.08 < PDI < 0.22) depending on the (co)polymers nature, were obtained and characterized by dynamic light scattering (DLS), zetametry, and transmission electron microscopy (TEM). Finally, the cytotoxicity and cellular uptake of the obtained NPs were evaluated in vitro using the hepatoma HepaRG cell line. Our results showed that both cytotoxicity and cellular uptake were influenced by the nature of the (co)polymer constituting the NPs. [ABSTRACT FROM AUTHOR]

[Display omitted] • RGD-NanoStar micellar nanoassemblies loaded with Doxorubicin against osteosarcoma. • Impact of RGD on nanoparticles surface for osteosarcoma chemotherapy. • Dox released from RGD-NanoStar reach the nucleus unlike untargeted NanoStar. • Preserving Doxorubicin from degradation occurring under physiological conditions. • Sustained and prolonged Dox release from RGD-NanoStar@Dox. We developed cyclic RGD-tagged polymeric micellar nanoassemblies for sustained delivery of Doxorubicin (Dox) endowed with significant cytotoxic effect against MG63, SAOS-2, and U2-OS osteosarcoma cells without compromising the viability of healthy osteoblasts (hFOBs). Targeted polymeric micellar nanoassemblies (RGD-NanoStar@Dox) enabled Dox to reach the nucleus of MG63, SAOS-2, and U2-OS cells causing the same cytotoxic effect as free Dox, unlike untargeted micellar nanoassemblies (NanoStar@Dox) which failed to reach the nucleus and resulted ineffective, demonstrating the crucial role of cyclic RGD peptide in driving cellular uptake and accumulation mechanisms in osteosarcoma cells. Micellar nanoassemblies were obtained by nanoformulation of three-armed star PLA-PEG copolymers properly synthetized with and without decoration with the cyclic-RGDyK peptide (Arg-Gly-Asp-D-Tyr-Lys). The optimal RGD-NanoStar@Dox nanoformulation obtained by nanoprecipitation method (8 % drug loading; 35 % encapsulation efficiency) provided a prolonged and sustained drug release with a rate significantly lower than the free drug under the same experimental conditions. Moreover, the nanosystem preserved Dox from the natural degradation occurring under physiological conditions (i.e., dimerization and consequent precipitation) serving as a slow-release "drug reservoir" ensuring an extended biological activity over the time. [ABSTRACT FROM AUTHOR]

Abstract: Novel synthetic transfection vectors with linear triblock and star-shaped diblock copolymer architectures have been synthesized by atom transfer radical polymerization (ATRP). Based on 2-(dimethylamino)ethyl methacrylate (DMAEMA) and copolymerization with poly(ethyleneglycol) α-methoxy, ω-methacrylate (MAPEG), the synthesis was realized using CuBr ligated with 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as catalytic complex and either ethyl 2-bromoisobutyrate (EBiB) or bis(α-bromoisobutyryl) N-methyl diethanolamine (DEA) or tris(α-bromoisobutyryl) triethanolamine (TEA) as (multifunctional)initiator. The polymers were characterized by GPC and NMR. The solution properties of these homopolymers and palm-tree-like copolymers were investigated by viscometry either in pure water or in buffered aqueous solutions. Interestingly, all the synthesized polymers show polyelectrolyte effect in Millipore water (25°C) and in Hepes (20mM) buffer solution (pH 7.4, NaCl 155mM, 25°C). Fitting of these viscometric data according to either Fuoss or Fedors equation allows for calculating the intrinsic viscosity of the polymers. These results are compared with dynamic light scattering (DLS) experiments to determine absolute masses. Finally, DEA based palm-tree-like copolymer is investigated to AFM measurement and micelles were observed at pH 8. [Copyright &y& Elsevier]

Highlights: [•] Assessment of end-group functionality in ATRP of NiPAm. [•] Synthesis of well-defined “smart” amphiphilic block copolymers. [•] Relevance of side reactions and diffusional limitations in ATRP of NiPAm. [ABSTRACT FROM AUTHOR]

Polyelectrolytes are promising electronicallyinsulating layers for low-voltage organic field effect transistors.However, the polyelectrolyte–semiconductor interface is difficultto manufacture due to challenges in wettability. We introduce an amphiphilicsemiconducting copolymer which, when spread as a thin film, can changeits surface from hydrophobic to hydrophilic upon exposure to water.This peculiar wettability is exploited in the fabrication of polyelectrolyte-gatedfield-effect transistors operating below 0.5 V. The prepared amphiphilicsemiconducting copolymer is based on a hydrophobic regioregular poly(3-hexylthiophene)(P3HT) covalently linked to a hydrophilic poly(sulfonated)-based randomblock. Such a copolymer is obtained in a three-step strategy combiningGrignard metathesis (GRIM), atom transfer radical polymerization (ATRP)processes, and a postmodification method. The structure of the diblockcopolymer was characterized using FT-IR, 1H NMR spectroscopy,and gel permeation chromatography (GPC). [ABSTRACT FROM AUTHOR]

Abstract: We report a method for inkjet-printing an organic semiconductor layer on top of the electrolyte insulator layer in polyelectrolyte-gated OFETs by using a surface modification treatment to overcome the underlying wettability problem at this interface. The method includes depositing an amphiphilic diblock copolymer (P3HT-b-PDMAEMA). This material is designed to have one set of blocks that mimics the hydrophobic properties of the semiconductor (poly(3-hexylthiophene) or P3HT), while the other set of blocks include polar components that improve adhesion to the polyelectrolyte insulator. Contact angle measurements, atomic force microscopy, and X-ray photoelectron spectroscopy confirm formation of the desired surface modification film. Successful inkjet printing of a smooth semiconductor layer allows us to manufacture complete transistor structures that exhibit low-voltage operation in the range of 1V. [Copyright &y& Elsevier]

Abstract: The synthesis of amphiphilic and adaptative block copolymers has been envisioned following a commutative two-step strategy involving atom transfer radical polymerization (ATRP) and the Huisgen-1,3-dipolar cycloaddition techniques. The reliability of this strategy is based on the use of an azido-containing ATRP initiator, the 2-(2-azidoethoxy)ethylbromoisobutyrate (N3E i BBr), able to be “clicked” to an alkyne-terminated derivative and to promote the ATRP polymerization from the active site. In the context of this work, an alkyne-terminated poly(ε-caprolactone) produced by ring-opening polymerization (ROP) of CL was employed as hydrophobic “clickable” segment. The N3E i BBr initiator was obtained by nucleophilic substitution of the chloride atom from 2-(2-chloroethoxy)ethanol by an azide function and followed by the esterification of the hydroxy function by bromoisobutyryl bromide. This initiator was employed in polymerization of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA) monomer by ATRP in THF at 60°C using CuBr complexed by 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as catalytic complex. Low initiation efficiencies were obtained and they were ascribed to intramolecular cyclization during the polymerization as evidenced by ESI-MS and 2D NMR spectroscopy. The “Click” coupling reaction was performed in THF at r.t. and was found to be efficient when using CuBr complexed by 2,2′-bipyridine ligand. To circumvent the low initiation efficiency, the N3E i BBr could be “clicked” in a first step to PCL precursors before initiating the polymerization of DMAEMA monomer by ATRP. In this context, various catalytic complexes in different composition ratio were employed to optimize the “click” coupling step. Moreover, this strategy was found to be suitable to produce well-defined PCL-b-PDMAEMA block copolymers, characterized by narrow polydispersity indices. Since ATRP and the Huisgen-1,3-dipolar cycloaddition both require the use of a copper(I)-based catalyst, the two first strategies were merged in a “one-pot” process in order to obtain in one step a well-defined block copolymer characterized by a narrow polydispersity index and predictable composition and block lengths. [Copyright &y& Elsevier]