A substrate protection approach to applying the calcium ion for improving the proteolysis resistance of the collagen.

Enzymatic dehairing, as a crucial part of cleaner leather processing, has reached processive advancement with potentially replacing the traditional hair removal due to increasing pressure from environmental demand. However, this cleaner technology based on proteases has a problem that the hide grain (collagen-rich structure) is susceptible to be hydrolyzed, decreasing the quality of finished leather. From the perspective of improving the stability of collagen fibers and their resistance to proteolysis, a method for protecting the hide grain during the enzymatic dehairing process was developed. The results showed that calcium ions had a swelling effect on collagen fibers under near-neutral conditions (pH 6.0-10.0), decreasing the thermal stability of collagen and the proteolysis resistance of collagen significantly. The alkaline environment (pH 10.0-12.0) will promote the dissociation of carboxyl groups in hide collagen, promoting the combination of calcium ions and carboxyl groups. This strategy can change the surface charge of collagen fibers and strengthen the connection between collagen fibers, thus improving protease resistance and the thermal stability of collagen. However, collagen fibers could swell violently once the alkalinity of the solution environment was extreme. Despite the above situation, calcium ion was still conducive to maintain the structural stability of collagen fibers. At pH 10.0-12.0, pretreating animal hide with a solution containing calcium ions can improve the protease resistance of hide grain, making the hide grain well-protected. This method provided an effective way to establish a safer enzymatic unhairing technology based on substrate protection. KEY POINTS: • A collagen protection method for hair removal of animal hide was developed. • This method applied calcium ions to collagen at alkaline conditions (pH 10.0-12.0). • Pretreatment results of calcium ions at different pH values on animal hide were compared.