Ferritin, a protein that is present in the human body for a controlled iron storage and release, consists of a ferrihydrite core and a protein shell. Apoferritin, the empty shell of ferritin, can be modified to carry tailored properties exploitable for targeted and direct drug delivery. This protein shell has the ability to dis- and reassemble depending on the pH value of the liquid environment and can thus be filled with the desired substance. Here we observed the dis- and reassembly process of the protein shell of ferritin and apoferritin in situ and in real space using atomic force microscopy. Ferritin and apoferritin nanoparticles adsorbed on a mica substrate exhibited a change in their size by varying the pH value of the surrounding medium. Lowering the pH value of the solution led to a decrease in size of the nanoparticles whereas a successive increase of the pH value increased the particle size again. The pH dependent change in size could be related to the dis- and reassembling of the protein shell of ferritin and apoferritin. Supplementary imaging by bimodal magnetic force microscopy of ferritin molecules accomplished in air revealed a polygonal shape of the core and a three-fold symmetry of the protein shell providing valuable information about the substructure of the nanoparticles.

Polymer coatings on cellulosic fibres are widely used to enhance the natural fibre properties by improving, for example, the hydrophobicity and wet strength. Here, we investigate the effects of a terpolymer P(S-co-MABP-co-PyMA) coating on cotton linters and eucalyptus fibres to improve the resistance of cellulose fibres against wetness. Coated and uncoated fibres were characterised by using scanning electron microscopy, contact angle measurements, Raman spectroscopy and atomic force microscopy with the objective of correlating macroscopic properties such as the hydrophobicity of the fleece with microscopic properties such as the coating distribution and local nanomechanics. The scanning electron and fluorescence microscopy results revealed the distribution of the coating on the paper fleeces and fibres. Contact angle measurements proved the hydrophobic character of the coated fleece, which was also confirmed by Raman spectroscopy measurements that investigated the water uptake in single fibres. The water uptake also induced a change in the local mechanical properties, as measured by atomic force microscopy. These results verify the basic functionality of the hydrophobic coating on fibres and paper fleeces but call into question the homogeneity of the coating. Graphic abstract

Paper materials are well-known to be hydrophilic unless chemical and mechanical processing treatments are undertaken. The relative humidity impacts the fiber elasticity, the interfiber joint behavior and the failure mechanism. In this work, we present a comprehensive experimental and computational study on mechanical properties of the fiber and the fiber network under humidity influence. The manually extracted cellulose fiber is exposed to different levels of humidity, and then mechanically characterized using atomic force microscopy, which delivers the humidity dependent longitudinal Young’s modulus. We describe the relation and calibrate the data into an exponential function, and the obtained relationship allows calculation of fiber elastic modulus at any humidity level. Moreover, by using confoncal laser scanning microscopy, the coefficient of hygroscopic expansion of the fibers is determined. We further present a finite element model to simulate the deformation and the failure of the fiber network. The model includes the fiber anisotropy and the hygroscopic expansion using the experimentally determined constants, and further considers interfiber behavior and debonding by using a humidity dependent cohesive zone interface model. Simulations on exemplary fiber network samples are performed to demonstrate the influence of different aspects including relative humidity and fiber-fiber bonding parameters on the mechanical features, such as force-elongation curve, strength and extensibility. Finally, we provide computational insights for interfiber bond damage pattern with respect to different humidity level as further outlook.

Modelling of single cellulose fibres is usually performed by assuming homogenous properties, such as strength and Young’s modulus, for the whole fibre. Additionally, the inhomogeneity in size and swelling behaviour along the fibre is often disregarded. For better numerical models, a more detailed characterisation of the fibre is required. Herein, we report a method based on atomic force microscopy to map these properties along the fibre. A fibre was mechanically characterised by static colloidal probe AFM measurements along the longitudinal direction of the fibre. Thus, the contact stress and strain at each loading point could be extracted. Stress–strain curves were be obtained along the fibre. Additionally, mechanical properties such as adhesion or dissipation were mapped. Local variations of the effective fibre radius were recorded via confocal laser scanning microscopy. Scanning electron microscopy measurements revealed the local macroscopic fibril orientation and provided an overview of the fibre topography. By combining these data, regions along the fibre with higher adhesion, dissipation, bending ability and strain or differences in the contact stress when increasing the relative humidity could be identified. This combined approach allows for one to obtain a detailed picture of the mechanical properties of single fibres. Graphic abstract

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