Martin W. M. Fijten

Fast Surface Modification by Microwave Assisted Click Reactions on Silicon Substrates

Microwave irradiation has been used for the chemical modification of functional monolayers on silicon surfaces. The thermal and chemical stability of these layers was tested under microwave irradiation to investigate the possibility to use this alternative heating process for the surface functionalization of self-assembled monolayers. The quality and morphology of the monolayers before and after microwave irradiation was analyzed by surface-sensitive techniques, such as Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), and contact angle measurements. As a model reaction, the 1,3-dipolar cycloaddition of organic azides and terminal acetylenes was tested for the chemical modification of functional azide monolayers. Low and high molar mass compounds modified with an acetylene group were successfully clicked onto the surfaces as confirmed by FTIR spectroscopy and AFM investigations. It could be verified that the reaction can be performed in reaction times of 5 min, and a comparison to conventional heating mechanisms allowed us to conclude that the elevated reaction temperatures result in the fast reaction process.

Star-shaped polyacrylates: Highly functionalized architectures via CuAAC click conjugation

Well-defined functional star-shaped polymer structures with up to 29 arms have been successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and click chemistry. First, azide end-functionalized poly(isobornyl acrylate) (PiBA) star-shaped polymers were prepared by successive ATRP and bromine substitution. Subsequently, alkyne end-functionalized molecules and polymers were introduced onto the star-shaped PiBA bearing pendant azide moieties by copper-catalyzed azide-alkyne cycloaddition (CuAAC). The possibilities and limits for the CuAAC on such highly branched polyacrylates are described.

Synthesis and crystal structures of multifunctional tosylates as basis for star-shaped poly(2-ethyl-2-oxazoline)s

Summary The synthesis of well-defined polymer architectures is of major importance for the development of complex functional materials. In this contribution, we discuss the synthesis of a range of multifunctional star-shaped tosylates as potential initiators for the living cationic ring-opening polymerization (CROP) of 2-oxazolines resulting in star-shaped polymers. The synthesis of the tosylates was performed by esterification of the corresponding alcohols with tosyl chloride. Recrystallization of these tosylate compounds afforded single crystals, and the X-ray crystal structures of di-, tetra- and hexa-tosylates are reported. The use of tetra- and hexa-tosylates, based on (di)pentaerythritol as initiators for the CROP of 2-ethyl-2-oxazoline, resulted in very slow initiation and ill-defined polymers, which is most likely caused by steric hindrance in these initiators. As a consequence, a porphyrin-cored tetra-tosylate initiator was prepared, which yielded a well-defined star-shaped poly(2-ethyl-2-oxazoline) by CROP as demonstrated by SEC with RI, UV and diode-array detectors, as well as by 1H NMR spectroscopy.

Enhanced Selectivity for the Hydrolysis of Block Copoly(2-oxazoline)s in Ethanol–Water Resulting in Linear Poly(ethylene imine) Copolymers

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.