The present work describes the development and the evaluation of cryogel-poly-ε-caprolactone combinatory scaffolds for bone tissue engineering. Gelatin was selected as cell-interactive biopolymer to enable the adhesion and the proliferation of mouse calvaria pre-osteoblasts while poly-ε-caprolactone was applied for its mechanical strength required for the envisaged application. In order to real...

Thermo-responsive diblock copolymers composed of hydrophilic methoxy poly(ethylene glycol) (MPEG) and hydrophobic biodegradable polyesters were prepared for application as injectable drug delivery systems, because they show a thermo-responsive sol-to-gel transition, especially around body temperature, when dispersed in aqueous solutions. The thermogelling hydrogels formed by hydrophobic aggrega...

Thermosensitive nanoparticles were prepared via the self-assembly of two different poly(ε-caprolactone)-based block copolymers of poly(N-isopropylacrylamide)-b-poly(ε-caprolactone) (PNPCL) and poly(ethylene glycol)-b-poly(ε-caprolactone) (PEGCL). The self-aggregation and thermosensitive behaviors of the mixed nanoparticles were investigated using 1H-NMR, turbidimetry, differential scanning micr...

Rare-earth complexes are attractive catalyst systems due to their low cost, low toxicity and high reactivity. Modular ligand sets are ideal for complex formation since the steric and electronic properties of the resultant metal complexes can be easily varied. This thesis explores the structure and reactivity of new yttrium amidate complexes, which combine the highly reactive metal with the modu...

The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be...

A novel well-defined linear poly(ε-caprolactone) (P1) containing terminal azobenzene and ethyne groups was successfully synthesized through tin-catalyzed ring-opening polymerization of ε-caprolactone in the presence of N,N′-bis(2-hydroxyethyl)-4-(3ethynylphenylazo)aniline (BHA) in bulk. Subsequent reactions allowed the synthesis of the corresponding bromoester end-functionalized polymer (P2), w...

In order to expand the properties and applications of aliphatic absorbable polyesters, a new biodegradable block copolymer family, poly(ester amide)-b-poly(ε-caprolactone) (PEA-b-PCL), was synthesized and characterized. These copolymers were synthesized by first preparing l-phenylalanine-based poly(ester amide) macroinitiators (Phe-PEAs) with free amine end groups via a solution polycondensatio...

Slowly degradable copolymers of L-lactide and ε-caprolactone can provide long-term delivery and may be interesting as alternative release systems of cyclosporine A (CyA) and rapamycin (sirolimus), in which available dosage forms cause a lot of side effects. The aim of this study was to obtain slowly degradable matrices containing immunosuppressive drug from PLACL initiated by nontoxic Zr[Acac]₄...

Aiming to produce high-quality bio-based 3D printed products, in this work, coconut fibers were chemical modified using caprolactone. Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic reasonance (NMR) confirmed the grafting of hydroxyl groups present on surface with caprolactone units. Furthermore, from contact angle (CA) analyses, higher hydrophobicity after treatment was con...

We demonstrate, for the first time, in the Baeyer-Villiger oxidation of cyclohexanone with aqueous hydrogen peroxide under conditions aimed at obtaining ε-caprolactone, that a thermally activated radical reaction leads to the concurrent formation of adipic acid, even when a stoichiometric amount of the oxidant is used. In fact, ε-caprolactone is the primary reaction product, but it is more reac...