An innovative consolidation strategy for degraded paper is presented based on the reversible application of cellulose nanocrystals as sustainable fillers to reinforce mechanical properties and resistance to further degradation. The compatibility and efficacy of the proposed consolidation treatment are assessed first on pure cellulose paper, used as a model, by reliable techniques such as field emission scanning electron microscopy, atomic force microscopy, tensile tests, X-ray powder diffraction, and Fourier transform infrared spectroscopy, evidencing the influence of the surface functionalization of nanocellulose on the consolidation and protection effects. Then, the consolidation technique is applied to real aged paper samples from Breviarium romanum ad usum Fratrum Minorum S.P. ( 1738), demonstrating the promising potential of the suggested approach. Amperometric measurements, carried out with a smart electrochemical tool developed in our laboratory, demonstrate the reversibility of the proposed treatment by removal of the nanocrystalline cellulose from the paper surface with a suitable cleaning hydrogel. This completely new feature of the consolidation treatment proposed here satisfies a pivotal requisite in cultural heritage conservation because the methodological requirement for the ″reversibility″ of any conservation measure is a fundamental goal for restorers. A paper artifact, in fact, is subject to a number of natural and man-made hazards, inducing continuous degradation. With time, monitoring and consolidation actions need to be often performed to ensure conservation, and this tends to modify the status quo and compromise the artifact integrity. Removable treatments can potentially avoid erosion of the artifact integrity.

Microgel particles have emerged in the past few years as a favorite model system for fundamental science and for innovative applications ranging from the industrial to biomedical fields. Despite their potentialities, no works so far have focused on the application of microgels for cultural heritage preservation. Here we show their first use for this purpose, focusing on wet paper cleaning. Exploiting their retentive properties, microgels are able to clean paper, ensuring more controlled water release from the gel matrix, in analogy to their macroscopic counterpart, i.e., hydrogels. However, differently from these, the reduced size of microgels makes them suitable to efficiently penetrate in the porous structure of the paper and to easily adapt to the irregular surfaces of the artifacts. To test their cleaning abilities, we prepare microgels made of Gellan gum, a natural and widespread material already used as a hydrogel for paper cleaning, and apply them to modern and ancient paper samples. Combining several diagnostic methods, we show that microgels performances in the removal of cellulose degradation byproducts for ancient samples are superior to commonly employed hydrogels and water bath treatments. This is due to the composition and morphology of ancient paper, which facilitates microgels penetration. For modern paper cleaning, performances are at least comparable to the other methods. In all cases, the application of microgels takes place on a time scale of a few minutes, opening the way for widespread use as a rapid and efficient cleaning protocol.

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Modern science is increasingly turning to nature for inspiration to design sustainable biomaterials in a smart and effective way. Herein, we describe biohybrid aerogels based on electrostatic complexation between cellulose and proteins—two of the most abundant natural polymers on Earth. The effects of both particle surface charge and particle size are investigated with respect to aerogel properties including the morphology, surface area, stability, and mechanical strength. Specifically, negatively charged nanocellulose (cellulose nanocrystals and cellulose nanofibers) and positively charged lysozyme amyloid fibers (full-length and shortened via sonication) are investigated in the preparation of fibrillar aerogels, whereby the nanocellulose component was found to have the largest effect on the resulting aerogel properties. Although electrostatic interactions between these two classes of charged nanoparticles allow us to avoid the use of any cross-linking agents, the resulting aerogels demonstrate a simple additive performance as compared to their respective single-component aerogels. This lack of synergy indicates that although electrostatic complexation certainly leads to the formation of local aggregates, these interactions alone may not be strong enough to synergistically improve bulk aerogel properties. Nevertheless, the results reported herein represent a critical step toward a broader understanding of biohybrid materials based on cellulose and proteins.