Gustaaf Schoukens

Silkworm and spider silk scaffolds for chondrocyte support.

Objective To create scaffolds with silkworm cocoon, spider egg sac and spider dragline silk fibres and examine their use for chondrocyte attachment and support. Methods Three different kinds of scaffolds were developed with Bombyx mori cocoon, Araneus diadematus egg sac and dragline silk fibres. The attachment of human articular cartilage cells were investigated on these bioprotein matrices. The chondrocytes produced an extracellular matrix which was studied by immunostaining. Moreover, the compression behaviour in relation to the porosity was studied. Results The compression modulus of a silkworm silk scaffold was related to its porosity. Chondrocytes were able to attach and to grow on the different fibres and in the scaffolds for several weeks while producing extracellular matrix products. Conclusion Porous scaffolds can be made out of silkworm and spider silk for cartilage regeneration. Mechanical properties are related to porosity and pore size of the construct. Cell spreading and cell expression depended on the porosity and pore-size.

Quality and Statistical Classification of Brazilian Vegetable Oils Using Mid-Infrared and Raman Spectroscopy

Palm oil, soy oil, sunflower oil, corn oil, castor oil, and rapeseed oil were analyzed with Fourier transform infrared (FT-IR) and FT-Raman spectroscopy. The quality of different oils was evaluated and statistically classified by principal component analysis (PCA) and a partial least squares (PLS) regression model. First, a calibration set of spectra was selected from one sampling batch. The qualitative variations in spectra are discussed with a prediction of oil composition (saturated, mono- and polyunsaturated fatty acids) from mid-infrared analysis and iodine value from FT-Raman analysis, based on ratioing the intensity of bands at given wavenumbers. A more robust and convincing oil classification is obtained from two-parameter statistical models. The statistical analysis of FT-Raman spectra favorably distinguishes according to the iodine value, while the mid-infrared spectra are most sensitive to hydroxyl moieties. Second, the models are validated with a set of spectra from another sampling batch, including the same oil types as-received and after different aging times together with a hydrogenated castor oil and high-oleic sunflower oil. There is very good agreement between the model predictions and the Raman measurements, but the statistical significance is lower for mid-infrared spectra. In the future, this calibration model will be used to check vegetable oil qualities before using them in polymerization processes.

How Thermal Curing of an Organic Paper Coating Changes Topography, Chemistry, and Wettability

Celluloses are preferred renewable substrates, but hydrophilicity and porosity disfavor their water resistance. We present here an ecofriendly application of imidized nanoparticles and a method to flexibly tune the surface wettability of papers. The soft nanostructured coating is sensitive to thermal curing, which affects both the surface chemistry and morphology. The thermal stability of the coating is first investigated with conventional and modulated differential scanning calorimetry, revealing influences of the imide content and an endotherm reaction below the glass transition temperature at 120-150 °C. The latter is studied in detail for an appropriate selection of the copolymer precursors. According to diffuse reflection infrared spectroscopy, Raman spectroscopy, and UV/vis spectroscopy, the endotherm corresponds to an imidization reaction. The morphology of the coatings is followed at various scale levels by contactless roughness measurements and atomic force microscopy. Finally, the experimental values are fitted to the parameters of the Wenzel wetting model, and so-called calibration curves for the relation between contact angles, surface roughness, and surface chemistry are presented. They allow the prediction of the water contact angle of coated papers from the hydrophilic to the hydrophobic range, with a maximum in hydrophobicity after increasing the imide content at 120-150 °C curing.

New bioactive textile dressing materials from dibutyrylchitin

Purpose – Dibutyrylchitin (DBC) is an ester derivative of a natural polysaccharide – chitin. DBC is obtained by reaction of chitin with butyric anhydride in the presence of a catalyst. The production methods of DBC have been elaborated and optimized. DBC is easily soluble in common organic solvents and has film – and fibre forming properties. Such characteristics allow obtaining classical fibres from the polymer solutions. DBC is also a raw material for manufacturing yarn and for a broad range of textile dressing materials. Fibres with good mechanical properties are obtained by an optimized spinning process from the DBC solutions. The purpose of this paper is to present a further optimization of the mechanical properties of DBC‐fibres and yarns.Design/methodology/approach – The excellent biomedical properties of the DBC are confirmed by different experimental results which prove that DBC is a biocompatible and biodegradable polymer and stimulates regeneration of damaged tissues. Tests of these DBC dressin...

Relationship between stress and orientation induced structures during uniaxial drawing of poly(ethylene 2,6-naphthalate)

Abstract Amorphous films of poly(ethylene 2,6-naphthalate) (PEN) were drawn isothermally at temperatures between 130°C and 160°C, more specially at 145°C up to the desired draw ratios, mainly to study structure formation during uniaxial drawing by differential scanning calorimetry. During drawing, a rigid phase structure was induced and the results were analyzed in comparison with stress–strain curves in order to relate the amount of induced rigid phase structure at the earlier-mentioned temperatures with the observed stretching behaviour. During the uniaxial drawing of PEN at temperatures between 130°C and 160°C, the amount of amorphous phase was linearly related to the square root of the extra first strain invariant. The stress–strain curves were characterized by a necking behaviour and the end of the yielding or necking was reached when the amount of induced rigid phase attained 50%. The rigid phase then acted as the continuous phase and the stress increased very strongly. The stretching behaviour of PEN was characterized more by the strain induced rigid phase formation than by the stress or strain induced crystallization.

Hybrid palm-oil/styrene-maleimide nanoparticles synthesized in aqueous dispersion under different conditions.

Abstract Poly(styrene-co-maleic anhydride) was imidized with ammonium hydroxide and palm oil, resulting in an aqueous dispersion of hybrid nanoparticles with diameters 85–180 nm (dispersed) or 20–50 nm (dried). The reaction conditions were optimized for different precursors by evaluating the relative amount ammonium hydroxide and maximizing the incorporated palm oil up to 70 wt.%. The interactions between palm oil and polymer phase have been studied by TEM, IR, Raman spectroscopy and thermal analysis (TGA, [TM] DSC). From Raman spectra, the amount of imide and reacted oil were quantified. Through concurring effects of imidization and coupling of fatty acids, the imidization needs a slight excess of NH3 relatively to maleic anhydride. The oxidative stability highly depends on oxidative crosslinking of free or non-reacted oil. Comparing the imide content from spectroscopic and thermal analysis suggests that a complex rigid imide phase without strong relaxation behavior has formed in combination with oil.

Hydrophobic waterborne coating for cellulose containing hybrid organic nanoparticle pigments with vegetable oils

Vegetable oils were combined with recent nanotechnology as a sustainable method for tuning the hydrophobicity of cellulose and paper surfaces. Different soy-, sunflower-, corn-, castor-, rapeseed- and hydrogenated oils were incorporated into an aqueous dispersion of hybrid styrene maleimide nanoparticles. Here, we investigate the formation of novel coatings from these dispersions and their performance on paper and paperboard, compared with model aluminum substrates. The coated papers are evaluated by static and dynamic contact angles, microscopy, atomic force microscopy, infrared and Raman spectroscopy. The nanoparticle pigments form a porous coating after drying, while the water repellence and hydrophobicity of paperboard and paper improved with contact angles of 90–99° after drying and 98–112° after ageing. The coatings with poly(unsaturated) oils have best hydrophobicity for dispersions with an optimum viscosity of 115–150 cp required for good coverage of the paper. While homogeneous coverage of the cellulose fibers is a primary requirement, thin coatings often provide higher contact angles on paper due to roughness of the underlaying fibrous surface. After ageing, the coatings are chemically stable without oil leakage and constant imide content, while an increase in contact angles is attributed to variations in coating morphology through local re-arrangements over the paper substrate.

Shrinkage behaviour of uniaxially drawn poly(ethylene 2,6-naphthalate) films

Abstract Amorphous films of poly(ethylene 2,6-naphthalate) (PEN) were drawn isothermally at 145°C up to the desired draw ratios mainly to study structure formation during uniaxial drawing by differential scanning calorimetry and to characterise the shrinkage behaviour of the drawn films with or without heat treatment. During drawing, a rigid phase structure is induced and the amount of induced rigid phase structure is linearly related to the square root of the extra first strain invariant. The stress–strain curves are characterised by a necking behaviour and the end of the yielding or necking is reached when the amount of induced rigid phase is attaining 50%. The stretching behaviour of PEN is characterised more by the strain induced rigid phase formation (SIRP) than by the stress or strain induced crystallisation. The shrinkage behaviour is characterised by two regimes. A first one for draw ratios below the necking behaviour where the films shrink back to their original length for temperatures between 100 and 140°C with a mid-value of 120°C, corresponding to the glass transition temperature of the amorphous phase. The second regime, for draw ratios above the necking behaviour is characterised by a shrinkage behaviour for temperatures between 120 and 160°C, with a mid-value of 140°C, corresponding to the transition temperature of the induced rigid phase structure. In this regime, the films never shrink back below the draw ratio after necking and a linear relation between the initial draw ratio and the final draw ratio after shrinkage is obtained. A heat treatment of the oriented films with fixed ends stabilises the induced structures and the shrinkage of these heat-set films is zero for temperatures up to the heat-setting temperature.

Kaolinite Nanocomposite Platelets Synthesized by Intercalation and Imidization of Poly(styrene-co-maleic anhydride)

A synthesis route is presented for the subsequent intercalation, exfoliation and surface modification of kaolinite (Kln) by an imidization reaction of high-molecular weight poly(styrene-co-maleic anhydride) or SMA in the presence of ammonium hydroxide. In a first step, the intercalation of ammonolyzed SMA by guest displacement of intercalated dimethylsulfoxide has been proven. In a second step, the imidization of ammonolyzed SMA at 160 °C results in exfoliation of the kaolinite layers and deposition of poly(styrene-co-maleimide) or SMI nanoparticles onto the kaolinite surfaces. Compared with a physical mixture of Kln/SMI, the chemically reacted Kln/SMI provides more efficient exfoliation and hydrogen bonding between the nanoparticles and the kaolinite. The kaolinite nanocomposite particles are synthesized in aqueous dispersion with solid content of 65 wt %. The intercalation and exfoliation are optimized for a concentration ratio of Kln/SMI = 70:30, resulting in maximum intercalation and interlayer distance in combination with highest imide content. After thermal curing at 135 °C, the imidization proceeds towards a maximum conversion of the intermediate amic acid moieties. The changes in O–H stretching and kaolinite lattice vibrations have been illustrated by infrared and FT-Raman spectroscopy, which allow for a good quantification of concentration and imidization effects.

Bioactive dressings to promote wound healing

Abstract The role of bioactive dressings derived from natural resources in managing both acute and chronic wounds is discussed. Bioactive dressings contain bioactive substances who are active in wound healing. Wound healing is a dynamic and complex process which requires suitable environment to promote healing process. With the advancement in technology, bioactive dressings have been developed to treat different types of wounds by targeting various aspects of the healing process. These materials include hydrocolloids, hydrogels, alginates, collagens, honey dressings, chitosan, chitin, derivatives from chitosan or chitin and biotextiles. Chitosan, chitin and their derivatives have been studied widely as bioactive wound dressing materials. The application of dibutyryl chitin derived from chitin is extensively reviewed. The O-butyrylation of chitin or chitosan, and a little less the N-butyrylation, is an important modification of chitin and increases the biochemical activity of chitin or chitosan. Even, water-soluble derivatives of chitin or chitosan can be obtained by O-butyrylation. Future developments in bioactive wound dressing materials based on chitin, chitosan and their derivatives are indicated using the increased knowledge and understanding of the action of these dressings in wound healing. A better knowledge and understanding of the action of these dressings in wound healing will be the basis for future developments of more bioactive dressing materials.