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Crosslinked macroporous hydrophilic poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated poly(GMA-co-EGDMA)] with identical chemical structure (60% of glycidyl methacrylate) but with varied average pore sizes (from 30 to 560 nm), specific surface areas (from 13.2 to 106.0 m2/g), specific volumes (from 0.755 to 1.191 cm3/g) and particle sizes (

The successful synthesis of amylose brushes via enzymatic ‘‘grafting from’’ polymerization and the detailed characterization of all synthetic steps by X-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry measurements are reported. Au and Si surfaces are amino-functionalized with self-assembled monolayers (SAMs) of cystamine and 3-aminopropyldimethyethoxysilane (APDMES), respectively. Maltoheptaose is covalently attached to the amino-functionalized Au and Si surfaces via reductive amination. Amylose brushes are grown from maltoheptaose modified Au and Si surfaces with enzymatic polymerization using potato phosphorylase and Rabbit Muscle phosphorylase, as evidenced by spectroscopic ellipsometry and XPS measurements.

Densely packed polysaccharide brushes consisting of alpha-D-glucose residues were grafted from modified silicon substrates. Potato phosphorylase was herein used to grow linear polysaccharide chains from silicon tethered maltoheptaose oligosaccharides using glucose-1-phosphate as donor substrate. The combined use of potato phosphorylase and Deinococcus geothermalis branching enzyme resulted in a hyperbranched brush coating as the latter one redistributes short oligosaccharides from the alpha(1-4)-linked position to the alpha(1-6)-linked position in the polysaccharide brush. The obtained grafting density of the brushes was estimated on 1.89 nm(-2) while the thickness was measured with ellipsometric techniques and, determined to be between 12.2 and 20.2 nm.

A series of poly(GMA-co-EGDMA) resins with identical composition but varying particle sizes, pore radii, specific surface areas and specific volumes are studied to assess how Candida antarctica lipase B immobilization affects the porosity of the copolymer particles. Mercury porosimetry reveals a significant change in the average pore size (up to 6.1-fold), the specific surface area (up to 3.2-fold) and the specific volume (up to 2.1-fold) of the epoxy resin. A similar behaviour is observed for glutaraldehyde-modified epoxy resins. The influences of the resin porosity properties on the loading of Candida antarctica lipase B during immobilization and on the hydrolytic activity (hydrolysis of p-nitrophenyl acetate) of the immobilized lipase are studied.

Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP) complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating.

Following concerns dealing with the finite nature of fossil resources and environmental pollution, interest in sustainable polymer alternatives and their production is rising. Enzymatic polymerization represents a promising solution to overcome these problems. The green nature and robustness of this type of polymerization gives rise to a multitude of biobased polymer. Within a large variety of biobased building blocks, furan derivatives and furan chemistry occupy a special position in polymer chemistry. The similarity between furan and phenyl rings opens an opportunity to a biobased alternative for phenyl-based polymers. For instance, polyethylene furanoate (PEF) is one successful example of biobased alternatives to polyethylene terephthalate (PET), which is widely used as packaging material. Interestingly, even though many studies reported the use of enzymatic routes in the synthesis of aliphatic polymers, there is a limited amount of reports on enzymatic synthesis of furan polymers. The work described in this thesis is focused on the further development of enzymatic routes for the production of various novel furan polymers with versatile properties. The obtained findings pave the way towards a transition from fossil- to bio-based polymers, as well as more environmentally friendly synthetic routes.