Optimization of the activation and nucleation steps in the precipitation of a calcium phosphate primer layer on electrospun poly(ɛ-caprolactone).

The present study aimed to optimize the procedure for coating electrospun poly(ε-caprolactone) (PCL) fibers with a calcium phosphate (CP) layer in order to improve their potential as bone tissue engineering scaffold. In particular, attention was paid to the reproducibility of the procedure, the morphology of the coating, and the preservation of the porous structure of the scaffold. Ethanol dipping followed by an ultrasonic assisted hydrolysis of the fiber surface with sodium hydroxide solution efficiently activated the surface. The resulting reactive groups served as nucleation points for CP precipitation, induced by alternate dipping of the samples in calcium and phosphate rich solutions. By controlling the deposition, a reproducible thin layer of CP was grown onto the fiber surface. The deposited CP was identified as calcium-deficient apatite (CDHAp). Analysis of the cell viability, adhesion, and proliferation of MC3T3-E1 cells on untreated and CDHAp coated PCL scaffolds showed that the CDHAp coating enhanced the cell response, as the number of attached cells was higher in comparison to the untreated PCL and cells on the CDHAp coated samples showed similar morphologies as the ones found in the positive control.

Polycaprolactone and polycaprolactone/chitosan nanofibres functionalised with the pH-sensitive dye Nitrazine Yellow.

Nanofibres functionalised with pH-sensitive dyes could greatly contribute to the development of stimuli-responsive materials. However, the application of biocompatible polymers is vital to allow for their use in (bio)medical applications. Therefore, this paper focuses on the development and characterisation of pH-sensitive polycaprolactone (PCL) nanofibrous structures and PCL/chitosan nanofibrous blends with 20% chitosan. Electrospinning with added Nitrazine Yellow molecules proved to be an excellent method resulting in pH-responsive non-wovens. Unlike the slow and broad response of PCL nanofibres (time lag of more than 3h), the use of blends with chitosan led to an increased sensitivity and significantly reduced response time (time lag of 5 min). These important effects are attributed to the increased hydrophilic nature of the nanofibres containing chitosan. Computational calculations indicated stronger interactions, mainly based on electrostatic interactions, of the dye with chitosan (ΔG of -132.3 kJ/mol) compared to the long-range interactions with PCL (ΔG of -35.6 kJ/mol), thus underpinning our experimental observations. In conclusion, because of the unique characteristics of chitosan, the use of PCL/chitosan blends in pH-sensitive biocompatible nanofibrous sensors is crucial.

Investigating the halochromic properties of azo dyes in an aqueous environment by using a combined experimental and theoretical approach.

The halochromism in solution of a prototypical example of an azo dye, ethyl orange, was investigated by using a combined theoretical and experimental approach. Experimental UV/Vis and Raman spectroscopy pointed towards a structural change of the azo dye with changing pH value (in the range pH 5-3). The pH-sensitive behavior was modeled through a series of ab initio computations on the neutral and various singly and doubly protonated structures. For this purpose, contemporary DFT functionals (B3LYP, CAM-B3LYP, and M06) were used in combination with implicit modeling of the water solvent environment. Static calculations were successful in assigning the most-probable protonation site. However, to fully understand the origin of the main absorption peaks, a molecular dynamics simulation study in a water molecular environment was used in combination with time-dependent DFT (TD-DFT) calculations to deduce average UV/Vis spectra that take into account the flexibility of the dye and the explicit interactions with the surrounding water molecules. This procedure allowed us to achieve a remarkable agreement between the theoretical and experimental UV/Vis spectrum and enabled us to fully unravel the pH-sensitive behavior of ethyl orange in aqueous environment.