Leather is one of the most popular products across globe and holds a significant place in the economy, while the pollution, associated to traditional leather industry, is far away on the “green chemistry” principles. In this sense, polyurethanes, which exhibit tunable chemical structures by selecting suitable precursors, can fit specific requirements, and the developments of green strategies make them important candidates for leather industry. This mini review briefly outlines the recent development of conventional (petrol-based) and sustainable polyurethanes in the leather industry, including their design and properties, in applications such as synthetic leather and surface-finishing (coatings/binders). Finally, outlooks of the future tendency, including more environmental-friendly strategies, bio-sourced/recycled materials and development of high-value multifunctional leather materials, are also here proposed.
The use of natural polysaccharide crosslinkers for decellularized matrices is an effective approach to prepare cardiovascular substitute materials. In this research, NaIO4 was applied to oxidize konjac glucomannan to prepare the polysaccharide crosslinker oxidized konjac glucomannan (OKGM). The as-prepared crosslinker was then used to stabilize collagen-rich decellularized porcine peritoneum (DPP) to construct a cardiovascular substitute material (OKGM-fixed DPP). The results demonstrated that compared with GA-fixed DPP and GNP-fixed DPP, 3.75% OKGM [1:1.5 (KGM: NaIO4)]-fixed DPP demonstrated suitable mechanical properties, as well as good hemocompatibility, excellent anti-calcification capability, and anti-enzymolysis in vitro. Furthermore, 3.75% OKGM [1:1.5 (KGM: NaIO4)]-fixed DPP was suitable for vascular endothelial cell adhesion and rapid proliferation, and a single layer of endothelial cells was formed on the fifth day of culture. The in vivo experimental results also showed excellent histocompatibility. The current results demonstrted that OKGM was a novel polysaccharide cross-linking reagent for crosslinking natural tissues featured with rich collagen content, and 3.75% OKGM [1:1.5 (KGM: NaIO4)]-fixed DPP was a potential cardiovascular substitute material.
Spider-capture-silk (SCS) can directionally capture and transport water from humid air relying on the unique geometrical structure. Although there have been adequate reports on the fabrication of artificial SCSs from petroleum-based materials, it remains a big challenge to innovate bio-based SCS mimicking fibers with high-performance fog collection ability and efficiency simultaneously. Herein, we report an eco-friendly and economical fiber system for water collection by coating gelatin on degummed silk. Compared to the previously reported fibers with the best fog collection ability (~ 13.10 μL), Gelatin on silk fiber 10 (GSF10) can collect larger water droplet (~ 16.70 μL in 330 s) with ~ 98% less mass. Meanwhile, the water collection efficiency of GSF10 demonstrates ~ 72% and ~ 48% enhancement to the existing best water collection polymer coated SCS fibers and spidroin eMaSp2 coated degummed silk respectively in terms of volume-to-TCL (vapor–liquid-solid three-phase contact line) index. The simultaneous function of superhydrophilicity, surface energy gradient, and ~ 65% water-induced volume swelling of the gelatin knots are the key factors in advancing the water collection performance. Abundant availability of feedstocks and ~ 75% improved space utilization guarantee the scalability and practical application of such bio-based fiber.
Supramolecular peptides exhibit obvious similarities with collagen fibers in terms of self-assembly characteristics, nanofibrous structure, and responsiveness to external stimuli. Here, a series of supramolecular peptides were developed by altering the amino acid sequence, enabling the self-assembly of three types of 4-biphenylacetic acid (BPAA)-tripeptides into fibrous hydrogel through hydrogen bonding and π–π stacking under the influence of ion induction. Transmission electron and scanning electron microscopies revealed that the diameter of the fiber within nanofibrous hydrogels was ~ 10 and ~ 40 nm, respectively, which was similar with the self-assembled collagen fibers. For this reason, these hydrogels could be considered as a biomimetic extracellular substitute. Meanwhile, the gelation concentration induced by ions was even lower than 0.66 wt%, with an elastic modulus of ~ 0.27 kPa, corresponding to a water content of 99.34 wt%. In addition, the three supramolecular hydrogels were found to be good substrates for L929 cell adhesion and MC-3T3 cell proliferation. The overall results implied that BPAA-based hydrogels have a lucrative application potential as cell carriers.
The production of high-valued organonitrogen chemicals, especially N-heterocycles, requires artificial N2 fixation accompanied by the consumption of fossil resources. To avoid the use of these energy- and resource-intensive processes, we develop a sustainable strategy to convert nitrogen-rich animal biomass into N-heterocycles through a thermochemical conversion process (TCP) under atmospheric pressure. A high percentage of N-heterocycles (87.51%) were obtained after the TCP of bovine skin due to the abundance of nitrogen-containing amino acids (e.g., glycine, proline, and l-hydroxyproline). Animal biomass with more diverse amino acid composition (e.g., muscles) yielded higher concentrations of amines/amides and nitriles after TCP. In addition, by introducing catalysts (KOH for pyrrole and Al2O3 for cyclo-Gly–Pro) to TCP, the production quantities of pyrrole and cyclo-Gly–Pro increased to 30.79 mg g−1 and 38.88 mg g−1, respectively. This approach can be used to convert the significant animal biomass waste generated annually from animal culls into valued organonitrogen chemicals while circumventing NH3-dependent and petrochemical-dependent synthesis routes.
Restrictions on heavy metals, especially chromium, have encouraged alternative tanning systems that can reduce environmental and human health risks from conventional chrome-based tanning. In this work, metal-free combination tanning was developed by using vegetable tannins and a triazine-based syntan containing active chlorine groups (SACC). Specifically, the relationship between leather performance (e.g., hydrothermal stability and organoleptic properties) and technical protocols (e.g., types and dose of tannins) was systematically established. The optimized protocol involving a unique procedure (i.e., 10% SACC pre-tanning, shaving, and 25% wattle tanning) endowed the leather with high shrinkage temperature (~ 92 °C) and met the Chinese standards for shoe upper leather (QB/T 1873-2010). Our method not only produces zero chrome-containing solid wastes, but also uses ~ 75% less tannin for leather manufacture. The excellent leather performance was ascribed to the synergistic effects, where SACC and wattle diffused into collagen fibrils and may bind to collagen via covalent, hydrogen and ionic bonding, locking the hierarchical structure of collagen from microfibrils to fiber bundles. Moreover, we summarized these findings and proposed a diffusion-binding-locking mechanism, providing new insights for current tanning theory. Together with the biodegradable spent tanning liquor, this approach will underpin the development of sustainable leather manufacture.
Wet-salted skin, as a special artificial high-salt environment, is rich in protein, fat, collagen and other nutrient substrates, and is a rich resource of halotolerant and halophilic microorganisms. However, knowledge gaps regarding the microbial community structure and inter taxa associations of wet-salted skin are large. In this study, the spatiotemporal dynamics and community structure of microorganisms present on wet-salted goatskins were investigated using 16S rRNA gene amplicon sequencing and culturable technique. Alpha diversity analysis based on Sobs, Chao, Ace and Shannon indices revealed that microbial diversity on the wet-salted goatskins exhibited a trend of ‘down → up → down → flat’ with time. During preservation, genera belonging to the bacteria domain such as Acinetobacter, Weissella and Streptococcus were slowly dying out, whereas those belonging to halophilic archaea such as Natrialba and Haloterrigena were gradually flourishing. Moreover, to resist high-salt stress, microorganisms on the wet-salted goatskin gradually migrated from the outside to the inside, eventually leading to the microbial diversity inside the skin being the same as or even higher than that on the skin surface. Venn diagram analysis revealed that the strains of some genera, including Psychrobacter, Salimicrobium, Salinicola, Ornithinibacillus, Halomonas, Bacillus and Chromohalobacter, were distributed throughout the interior and exterior of the wet-salted goatskin and existed during various periods. Accordingly, 45 protease-producing halophilic or halotolerant microorganisms were isolated and screened from the wet-salted goatskin using the gradient dilution plate method. Importantly, 16S rRNA genes of some bacteria exhibited less than 99.5% similarity to valid published species, indicating that they likely are novel species and have a good potential for application.
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