In the general global rise of attention and research to seek greener attitudes, the field of cultural heritage (CH) makes no exception. In the last decades, an increasing number of sustainable and biologically based solutions have been proposed for the protection and care of artworks. Additionally, the safety of the target artwork and the operator must be kept as core goals. Within this scenario, new products and treatments should be explored and implemented in the common conservation praxes. Therefore, this review addressing metal heritage is aimed to report biologically derived gel formulations already proposed for this specific area as reliable tools for cleaning. Promising bio-gel-based protocols, still to be implemented in metal conservation, are also presented to promote their investigation by stakeholders in metal conservation. After an opening overview on the common practices for cleaning metallic surfaces in CH, the focus will be moved onto the potentialities of gel-alternatives and in particular of ones with a biological origin. In more detail, we displayed water-gels (i.e., hydrogels) and solvent-gels (i.e., organogels) together with particular attention to bio-solvents. The discussion is closed in light of the state-of-the-art and future perspectives.

In the field of cultural heritage, the use of natural gels is rising for the application of active agents. Here, two natural polymers are assessed: agar, a pioneer hydrogel for conservation treatments, and chitosan, a rather novel and metal-binding gel. For chitosan, a state-of-the-art based formulation (CS–ItA–LCys) is evaluated as it was reported for silver-complexing properties. It is evaluated whether these polymers can withstand the addition of the chelating compound deferoxamine, which is a bacterial siderophore. This allows for the obtainment of completely bio-sourced gel systems. A Fourier-transformed (FT) infrared spectroscopy characterization is performed, completed with rheological measurements and Cryo-Scanning Electron Microscopy (cryo–SEM) to investigate the physico–chemical properties of the gels, as well as their interaction with deferoxamine. Both polymers are also tested for their inherent complexing ability on silver ions using FT–Raman spectroscopy. A multi-analytical comparison shows different microstructures, in particular, the presence of a thick membrane for chitosan and different mechanical behaviors, with agar being more brittle. Neither hydrogel seems affected by the addition of deferoxamine; this is shown by similar rheological behavior and molecular structures in the presence or absence of the chelator. The intrinsic abilities of the chitosan formulation to make silver complex are demonstrated with the observation of two peaks characteristic of Ag–S and Ag–O bonds. Agar and chitosan are both proven to be reliable gels to act as carriers for bio-based active agents. This paper confirms the potential asset of the chitosan formulation CS–ItA–LCys as a promising gel for the complexation of soluble silver.

Bioderived alternatives to commonly used complexing agents for the cleaning of iron artworks are sought for their natural origin and better biodegradability. Indeed, complexing agents currently used for the removal of undesired corrosion products from iron artworks can be difficult to control and their environmental impact is often overlooked. This paper studies the use of siderophores, focusing on the ability of one of them, deferoxamine, to be employed as an active agent loaded in polysaccharides hydrogels, on corrosion phases. Preliminary tests were conducted on artificially aged steel samples and further studies were performed on naturally corroded steel to assess the most performing application parameters. Long-term behavior of cleaned surface was assessed. Cleaning outcomes were compared with those obtainable with disodium ethylenediaminetetraacetic acid using optical microscopy, colorimetry and atomic absorption spectroscopy as well as Infrared and Raman micro-spectroscopies. Among the different gelling agents evaluated, agar applied when hot and gellan gum prepared at room temperature were the most effective gel formulations and agar left few residues over the treated surfaces. The protocol was then tested on altered steel artifacts belonging to heritage institutions in France. Encouraging outcomes in the removal of iron corrosion phases with green approaches are here presented. Graphical abstract

Lacquered brass objects are widely present in scientific and technical heritage collections. Localized atmospheric corrosion occurs on the metal when the coating fails to play its protective role. Although lacquered brass objects are not necessarily endangered by this phenomenon, the presence of dark, unpleasant corrosion spots alters the surface appearance, affecting the readability of the objects. Conservators are therefore frequently asked to clean these surfaces. We hereby present the results of a study conducted in the framework of the CleanLaB (Cleaning of Lacquered Brass) project at the Haute Ecole Arc of Neuchâtel for the cleaning of lacquered brass. This work investigates the effects of several gelled cleaning systems applied on artificially aged, lacquered brass samples to remove the corrosion products without affecting the integrity of the coating. The performance of complexing agents commonly used in conservation was compared on lacquered brass mock-ups coated with shellac resin by means of multiple non-invasive characterization and imaging techniques. The tests included conventional complexing agents like sodium citrate and disodium ethylenediaminetetraacetic acid, as well as a bio-originated system based on deferoxamine, a microbial metal chelator investigated as a green alternative in cleaning formulations.

The biocatalytic production of nicotinic acid using nitrilases has emerged as a promising alternative to conventional chemical synthesis, offering improved selectivity and environmental sustainability. In this study, we developed a continuous‐flow millireactor system employing Escherichia coli cells expressing a nitrilase from Paraburkholderia phymatum (Nit _Phym ) for the continuous production of nicotinic acid. To enhance catalytic efficiency and stability, whole cells were immobilized using two different strategies: covalent attachment to the reactor walls and encapsulation in alginate microbeads. The performance of these immobilization techniques was evaluated in millireactors with two different geometries: pillar and zigzag configurations. Encapsulation of Nit _Phym ‐expressing E. coli cells in alginate microbeads was achieved through a centrifuge‐assisted microencapsulation method, yielding beads with diameters of up to 350 µm. Continuous‐flow reactions demonstrated that the microencapsulated cells maintained their activity over at least 7 days, achieving stable conversion rates of approximately 30% in both pillar and zigzag millireactors. Compared to direct covalent immobilization, microencapsulation significantly reduced cell leaching and contamination of the reaction product. These findings highlight the potential of whole‐cell microencapsulation for enhancing the stability and efficiency of biocatalytic processes in continuous‐flow millireactors.