Herein, we investigated the effect of the support modification (Sibunit carbon) with diazonium salts of Pd and Pd-Au catalysts on furfural hydrogenation under 5 bars of H2 and 50 °C. To this end, the surface of Sibunit (Cp) was modified with butyl (Cp-Butyl), carboxyl (Cp-COOH) and amino groups (Cp-NH2) using corresponding diazonium salts. The catalysts were synthesized by the sol immobilization method. The catalysts as well as the corresponding supports were characterized by Fourier transform infrared spectroscopy, N2 adsorption-desorption, inductively coupled plasma atomic emission spectroscopy, high resolution transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Hammet indicator method and X-ray photoelectron spectroscopy. The analysis of the results allowed us to determine the crucial influence of surface chemistry on the catalytic behavior of the studied catalysts, especially regarding selectivity. At the same time, the structural, textural, electronic and acid–base properties of the catalysts were practically unaffected. Thus, it can be assumed that the modification of Sibunit with various functional groups leads to changes in the hydrophobic/hydrophilic and/or electrostatic properties of the surface, which influenced the selectivity of the process.
The surface hydrophobicity of poly(ε-caprolactone) electrospun scaffolds prevents their interactions with cells and tissue integration. Although plasma treatment of scaffolds enhances their hydrophilicity, this effect is temporary, and the hydrophobicity of the scaffolds is restored in about 30 days. In this communication, we report a method for hydrophilization of poly(ε-caprolactone) electrospun scaffolds for more than 6 months. To that end, diamond-like coating was deposited on the surface of the scaffolds in a nitrogen atmosphere using pulsed vacuum arc deposition with sputtering of graphite target. This approach allows for a single-side hydrophilization of the scaffold (water contact angle of 22 ± 3° vs. 126 ± 2° for pristine PCL scaffold) and preserves its structure. With increased nitrogen pressure in the chamber, sp3-hybridized carbon content decreased twice (sp2/sp3 ratio decreased from 1.06 to 0.52), which demonstrates the possibility of tailoring the content of carbon in sp2 and sp3 hybridization state. Nitrogen content in the deposited coatings was found at 16.1 ± 0.9 at.%. In vitro tests with fibroblast cell culture did not reveal any cytotoxic compounds in sample extracts.
Electrospun poly(ε-caprolactone) (PCL)-based scaffolds are widely used in tissue engineering. However, low cell adhesion remains the key drawback of PCL scaffolds. It is well known that nitrogen-doped diamond-like carbon (N-DLC) coatings deposited on the surface of various implants are able to enhance their biocompatibility and functional properties. Herein, we report the utilization of the pulsed vacuum arc deposition (PVAD) technique for the fabrication of thin N-DLC coatings on the surface of electrospun PCL scaffolds. The effect of N-DLC coating deposition under various nitrogen pressures on the morphological, mechanical, physico-chemical, and biological properties of PCL scaffolds was investigated. It was established that an increase in nitrogen pressure in the range from 5 × 10−3 to 5 × 10−1 Pa results in up to a 10-fold increase in the nitrogen content and a 2-fold increase in the roughness of the PCL fiber surface. These factors provided the conditions for the enhanced adhesion and proliferation of human mesenchymal stem cells (MMSCs) on the surface of the modified PCL scaffolds. Importantly, the preservation of N-DLC coating properties determines the shelf life of a coated medical device. The elemental composition, tensile strength, and surface human MMSC adhesion were studied immediately after fabrication and after 6 months of storage under normal conditions. The enhanced MMSC adhesion was preserved after 6 months of storage of the modified PCL-based scaffolds under normal conditions.