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Developing polymersomes for drug delivery purposes requires a deeper understanding of their behavior in physiological environment. We performed the self-assembly and in-situ loading of polybutadiene-block-polyethyleneoxide (PB-b-PEO) polymersomes in a continuous process using micromixers. Varying the length and end-groups of the starting block copolymer allows us to control the polymer membrane thickness and surface functionalities (hydroxyl or carboxylic acid), required to realize a further coupling with specific cell targeting ligands. To get a deeper understanding of these polymersomes in physiological environment, we studied the cellular response (HeLa cells) in presence of various polymersomes, and showed by cytotoxicity tests the relative biocompatibility of the systems. Flow cytometry experiments at 4?°C in PBS buffer showed a different behavior of hydroxyl-functionalized vesicles compared to carboxylic acid-functionalized vesicles. On the contrary cell binding in DMEM medium supplemented with 10% FCS was almost completely blocked with both kinds of polymersomes. Protein adsorption measurements by dynamic light scattering confirmed that protein binding occurs in all cases, which apparently influences the particle-cell interaction. This study contributes towards a deeper understanding of polymersomes in biological environment and further investigations will help us to design highly effective polymersomes for in vitro as well as in vivo applications.
Polylactide (PLA) and poly(methyl methacrylate) (PMMA) constitute, already for several decades, the gold standards for various biomedical applications due to their biocompatibility/inertness. Moreover, they have an additional property: they can form stereocomplexes (SCs) that have a more compact crystalline structure than the individual components. As a result, polymer SCs display improved thermal and mechanical properties, as well as delayed drug release and biodegradation rate in the case of drug delivery systems and biomaterials based on PLA, which is of prime importance in the biomedical field. In this article, the potential of SCs for biomedical applications in the areas of drug delivery, tissue engineering, and nanostructured surfaces is highlighted.
This review gives representative examples of the various types of synthetic cationic polymers or polyampholytes (chemical structure, architecture, etc) that can be used to complex DNA (forming polyplexes) for their application in gene delivery. In designing polycations for gene delivery, one has to take into account a balance between protection of DNA versus loss of efficiency for DNA condensation and efficient condensation versus hindering of DNA release. Indeed, if the polyplexes are not stable enough, premature dissociation will occur before delivery of the genetic material at the desired place, resulting in low transfection efficiency; on the other hand, a complex that is too stable will not release the DNA, also resulting in low gene expression. The techniques generally used to determine these properties are gel electrophoresis to test the DNA/polymer complexation, ethidium bromide or polyanion displacement to test the affinity of a polymer for DNA, and light scattering to determine the extent of DNA condensation. Moreover, with the development of more precise instruments for physico-chemical characterization and appropriate biochemical and biophysical techniques, a direct link between the physico-chemical characteristics of the polyplexes and their in vitro and in vivo properties can be drawn, thus allowing tremendous progress in the quest towards application of polyplexes for gene therapy, beyond the research laboratory.
Sequence-defined poly(amino phosphodiester)s containing main-chain tertiary amines were synthesized by automated solid-phase phosphoramidite chemistry. These polymers were prepared using four monomers with different substituents. The formed polymers were characterized by HPLC and mass spectrometry. These methods evidenced preparation of molecularly-defined polymers. Furthermore, the presence of tertiary amines in the polymer backbones facilitates sequencing by tandem mass spectrometry.
A rigid aromatic phosphorus-containing hyperbranched flame retardant structure is synthesized from 10-(2,5 dihydroxyphenyl)-10H-9-oxa-
10-phosphaphenanthrene-10-oxide (DOPO-HQ), tris(4-hydroxyphenyl)phosphine oxide (THPPO), and 1,4-terephthaloyl chloride (TPC). The resulting poly-(DOPO-HQ/THPPO-terephthalate) (PDTT) is implemented as a flame retardant into an epoxy resin (EP) at a 10 wt% loading. The effects on EP are compared with those of the monomer DOPO-HQ and triphenylphosphine oxide (OPPh3) as low molar mass flame retardants. The glass transition temperature, thermal decomposition, flammability (reaction to small flame), and burning behavior of the thermosets are investigated using differential scanning calorimetry, thermogravimetric analysis, pyrolysis combustion flow calorimetry, UL 94-burning chamber testing, and cone calorimeter measurements.
Although P-contents are low at only 0.6 wt%, the study aims not at attaining V-0, but at presenting a proof of principle: Epoxy resinswith PDTT show promising fire performance, exhibiting a 25% reduction in total heat evolved (THE), a 30% reduction in peak heat release rate (PHRR) due to flame inhibition (21% reduction in effective heat of combustion (EHC)), and an increase in Tg at the same time. This study indicates that rigid aromatic hyperbranched polymeric structures offer a promising route toward multifunctional flame retardancy.
Thermoresponsive polymers have shown great potential in applications such as bioseparation, drug delivery and diagnostic. Only few thermoresponsive polymers that present an upper critical solution temperature (UCST), i.e. phase separate from solution upon cooling, in a relevant temperature range have been reported so far. Moreover, the most studied UCST type polymers namely polybetaines are difficult to use under physiological conditions, which significantly restricts their potential applications. Therefore, UCST polymers with sharp and robust phase transition in physiological conditions (in the presence of salts, etc.) are highly needed in order to extend the range of applications of this class of polymers.
A robust UCST-type copolymer of acrylamide (AAm) and acrylonitrile (AN) (poly(AAm-co-AN)) was prepared by reversible addition fragmentation chain transfer (RAFT) polymerization and its thermo-induced aggregation behavior in aqueous media was studied by turbidimetry, dynamic and static light scattering. At temperature below the UCST, the poly(AAm-co-AN) copolymer chains were aggregated together. The aggregate size was found to be larger with increasing AN contents and became smaller upon dilution of the copolymer solutions. While above the UCST, the poly(AAm-co-AN) copolymer chains were expanded and weekly associated in solution. The association between the copolymer chains formed smaller aggregates with increasing the AN contents or the concentration of the solutions. A model is proposed to explain such association-aggregation behavior of the poly(AAm-co-AN) copolymer depending on the AN contents and concentration of the solutions.