Abstract:The monomers 2-methyl-2-oxazine (MeOZI), 2-ethyl-2-oxazine (EtOZI), and 2-n-propyl-2-oxazine (nPropOZI) were synthesized and polymerized via the living cationic ring-opening polymerization (CROP) under microwave-assisted conditions. pEtOZI and pnPropOZI were found to be thermoresponsive, exhibiting LCST behavior in water and their cloud point temperatures (T(CP)) are lower than for poly(2-oxazoline)s with similar side chains. However, comparison of poly(2-oxazine) and poly(2-oxazoline)s isomers reveals that po… Show more
“…The potential of POx for biomedical applications has been reviewed extensively elsewhere. 1,5,6 Most studies focus on POx in suspension [7][8][9] while reports on their grafting to surfaces and organization in thin films are sparse. This is most likely due to the fact that the immobilization of POx onto surfaces is a tedious process, in which the polymer has to be initially synthesized in solution before being somehow grafted onto a compatible substrate in subsequent steps.…”
Polyoxazolines arise as a promising new class of polymers for biomedical applications, but creating oxzoline-based coatings via conventional methods is challenging. Herein, nanoscale polyoxazoline coatings were generated via a single step plasma deposition process. The effects of plasma deposition conditions on the film stability, structure and chemical group density were investigated. Detailed examination of the physical and chemical properties of plasma deposited polyoxazoline via XPS, FTIR, contact angle and ellipsometry unravels the complex functionality of the films. Partial retention of the oxazoline ring facilitates covalent reaction with the carboxylic acid groups present on nanoparticulates and biomolecules. Surface bound proteins effectively retain their bioactivity, therefore a vast range of potential applications unlocks for plasma deposited polyoxazoline coatings in the field of biosensing, medical arrays and diagnosis. 20 Graphical abstract Nanoscale polyoxazoline coatings generated via a single step plasma deposition process are investigated. The complex functionality of the film can be controlled by varying the deposition conditions. Partial retention of the oxazoline ring facilitates covalent binding of nanoparticules and biomolecules.
“…The potential of POx for biomedical applications has been reviewed extensively elsewhere. 1,5,6 Most studies focus on POx in suspension [7][8][9] while reports on their grafting to surfaces and organization in thin films are sparse. This is most likely due to the fact that the immobilization of POx onto surfaces is a tedious process, in which the polymer has to be initially synthesized in solution before being somehow grafted onto a compatible substrate in subsequent steps.…”
Polyoxazolines arise as a promising new class of polymers for biomedical applications, but creating oxzoline-based coatings via conventional methods is challenging. Herein, nanoscale polyoxazoline coatings were generated via a single step plasma deposition process. The effects of plasma deposition conditions on the film stability, structure and chemical group density were investigated. Detailed examination of the physical and chemical properties of plasma deposited polyoxazoline via XPS, FTIR, contact angle and ellipsometry unravels the complex functionality of the films. Partial retention of the oxazoline ring facilitates covalent reaction with the carboxylic acid groups present on nanoparticulates and biomolecules. Surface bound proteins effectively retain their bioactivity, therefore a vast range of potential applications unlocks for plasma deposited polyoxazoline coatings in the field of biosensing, medical arrays and diagnosis. 20 Graphical abstract Nanoscale polyoxazoline coatings generated via a single step plasma deposition process are investigated. The complex functionality of the film can be controlled by varying the deposition conditions. Partial retention of the oxazoline ring facilitates covalent binding of nanoparticules and biomolecules.
“…One of the best-characterized thermoresponsive polymers is poly(N-isopropyl acrylamide) (PNIPAAm), which displays a lower critical solution temperature (LCST) of 32˝C, just below body temperature [2][3][4][5]. Other classes of thermoresponsive polymers that have emerged in recent years are for example poly(oligo ethylene glycol acrylate)s [2,6], polyisocyanopeptides grafted with oligo(ethylene glycol) side chains [7][8][9], poly(2-oxazine)s [10] and poly(2-oxazoline)s [3,5,[11][12][13][14][15][16][17].…”
This paper describes the synthesis and thermal properties in solution and bulk of poly(2-alkyl-oxazoline)s (PAOx) containing a methyl ester side chain.Homopolymers of 2-methoxycarbonylethyl-2-oxazoline (MestOx) and 2-methoxycarbonylpropyl-2-oxazoline (C3MestOx), as well as copolymers with 2-ethyl-2-oxazoline (EtOx) and 2-n-propyl-2-oxazoline (nPropOx), with systematic variations in composition were prepared. The investigation of the solution properties of these polymers revealed that the cloud point temperatures (T CP s) could be tuned in between 24˝C and 108˝C by variation of the PAOx composition. To the best of our knowledge, the T CP s of PMestOx and PC3MestOx are reported for the first time and they closely resemble the T CP s of PEtOx and PnPropOx, respectively, indicating similar hydrophilicity of the methyl ester and alkyl side chains. Furthermore, the thermal transitions and thermal stability of these polymers were investigated by DSC and TGA measurements, respectively, revealing amorphous polymers with glass transition temperatures between´1˝C and 54˝C that are thermally stable up to >300˝C.
“…The living cationic ring‐opening polymerization (CROP) of 2‐oxazolines enables the synthesis of a wide range of polymer architectures with a variety of end groups. The versatility of this living polymerization method allows the preparation of well‐defined polyamides with tunable properties 1–5. Furthermore, poly(2‐oxazoline)s (POx) can be hydrolyzed yielding linear, well‐defined poly(ethylene imine) (L‐PEI),6 which exhibits interesting solubility properties due to its crystallinity and pH responsiveness 7.…”
The ability of merging the properties of poly(2-oxazoline)s and poly(ethylene imine) is of high interest for various biomedical applications, including gene delivery, biosensors, and switchable surfaces and nanoparticles. In the present research, a methodology for the controlled and selective hydrolysis of (co)poly(2-oxazoline)s is developed in an ethanol-water solvent mixture, opening the path toward a wide range of block poly(2-oxazoline-co-ethylene imine) (POx-PEI) copolymers with tunable properties. The unexpected influence of the selected ethanol-water binary solvent mixture on the hydrolysis kinetics and selectivity is highlighted in the pursue of well-defined POx-PEI block copolymers.
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