Yuanhang Xiao , Jiyu Liang , Minmin Liu , Jiajing Zhou , Chunhua Wang , Wei Lin
{"title":"多酚衍生物和铝可持续皮革制造的分层扩散-组装-交联策略(Ⅲ)","authors":"Yuanhang Xiao , Jiyu Liang , Minmin Liu , Jiajing Zhou , Chunhua Wang , Wei Lin","doi":"10.1016/j.polymer.2025.129099","DOIUrl":null,"url":null,"abstract":"<div><div>Chrome-free technologies based on vegetable polyphenols are critical for sustainable leather production, yet current strategies face the challenges of designing effective tanning system in achieving comparable tanning performances to that of Cr(Ⅲ). The key solution is to efficiently regulate the diffusion and crosslinking of chrome-free tanning agents in collagen matrix. Herein, a chrome-free tanning system was established based on 10 % polyphenol derivative (i.e., GACC) and 2 % Al(Ⅲ), which synergistically enables the enhanced diffusion and crosslinking within hierarchical structure of collagen. Molecular dynamics simulations and experiments showed that GACC and Al(Ⅲ) can diffuse into the hierarchy of fibrils and form intermolecular and intrafibrillar crosslinking within collagen matrix via coordination, covalent, and hydrogen bonds. Moreover, the carboxyl and hydroxyl groups of GACC coordinate with Al(Ⅲ) to form multi-scale GACC-Al coordination polymers (120−570 nm) via in-situ assembly, which bound with collagen to form multi-point crosslinking networks from elementary fibers to fibers levels. Thus, these findings are summarized as the hierarchical diffusion-assembly-crosslinking strategy for the first time. The unique tanning strategy endows leather with high porosity of collagen matrix (∼56.4 %), and remarkably enhanced hydrothermal stability (<em>T</em><sub>s</sub> ∼87 °C), excellent organoleptic (e.g., softness ∼6.3 mm) and physical properties (e.g., tear strength ∼64.3 N/mm, elongation at break ∼100.5 %) compared with commercial chrome-free tanning. The work provides valuable insights for developing tanning mechanisms and sustainable chrome-free tanning systems.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"338 ","pages":"Article 129099"},"PeriodicalIF":4.5000,"publicationDate":"2025-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hierarchical diffusion-assembly-crosslinking strategy for sustainable leather manufacturing by polyphenol derivatives and Al(Ⅲ)\",\"authors\":\"Yuanhang Xiao , Jiyu Liang , Minmin Liu , Jiajing Zhou , Chunhua Wang , Wei Lin\",\"doi\":\"10.1016/j.polymer.2025.129099\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Chrome-free technologies based on vegetable polyphenols are critical for sustainable leather production, yet current strategies face the challenges of designing effective tanning system in achieving comparable tanning performances to that of Cr(Ⅲ). The key solution is to efficiently regulate the diffusion and crosslinking of chrome-free tanning agents in collagen matrix. Herein, a chrome-free tanning system was established based on 10 % polyphenol derivative (i.e., GACC) and 2 % Al(Ⅲ), which synergistically enables the enhanced diffusion and crosslinking within hierarchical structure of collagen. Molecular dynamics simulations and experiments showed that GACC and Al(Ⅲ) can diffuse into the hierarchy of fibrils and form intermolecular and intrafibrillar crosslinking within collagen matrix via coordination, covalent, and hydrogen bonds. Moreover, the carboxyl and hydroxyl groups of GACC coordinate with Al(Ⅲ) to form multi-scale GACC-Al coordination polymers (120−570 nm) via in-situ assembly, which bound with collagen to form multi-point crosslinking networks from elementary fibers to fibers levels. Thus, these findings are summarized as the hierarchical diffusion-assembly-crosslinking strategy for the first time. The unique tanning strategy endows leather with high porosity of collagen matrix (∼56.4 %), and remarkably enhanced hydrothermal stability (<em>T</em><sub>s</sub> ∼87 °C), excellent organoleptic (e.g., softness ∼6.3 mm) and physical properties (e.g., tear strength ∼64.3 N/mm, elongation at break ∼100.5 %) compared with commercial chrome-free tanning. The work provides valuable insights for developing tanning mechanisms and sustainable chrome-free tanning systems.</div></div>\",\"PeriodicalId\":405,\"journal\":{\"name\":\"Polymer\",\"volume\":\"338 \",\"pages\":\"Article 129099\"},\"PeriodicalIF\":4.5000,\"publicationDate\":\"2025-09-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0032386125010857\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0032386125010857","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Hierarchical diffusion-assembly-crosslinking strategy for sustainable leather manufacturing by polyphenol derivatives and Al(Ⅲ)
Chrome-free technologies based on vegetable polyphenols are critical for sustainable leather production, yet current strategies face the challenges of designing effective tanning system in achieving comparable tanning performances to that of Cr(Ⅲ). The key solution is to efficiently regulate the diffusion and crosslinking of chrome-free tanning agents in collagen matrix. Herein, a chrome-free tanning system was established based on 10 % polyphenol derivative (i.e., GACC) and 2 % Al(Ⅲ), which synergistically enables the enhanced diffusion and crosslinking within hierarchical structure of collagen. Molecular dynamics simulations and experiments showed that GACC and Al(Ⅲ) can diffuse into the hierarchy of fibrils and form intermolecular and intrafibrillar crosslinking within collagen matrix via coordination, covalent, and hydrogen bonds. Moreover, the carboxyl and hydroxyl groups of GACC coordinate with Al(Ⅲ) to form multi-scale GACC-Al coordination polymers (120−570 nm) via in-situ assembly, which bound with collagen to form multi-point crosslinking networks from elementary fibers to fibers levels. Thus, these findings are summarized as the hierarchical diffusion-assembly-crosslinking strategy for the first time. The unique tanning strategy endows leather with high porosity of collagen matrix (∼56.4 %), and remarkably enhanced hydrothermal stability (Ts ∼87 °C), excellent organoleptic (e.g., softness ∼6.3 mm) and physical properties (e.g., tear strength ∼64.3 N/mm, elongation at break ∼100.5 %) compared with commercial chrome-free tanning. The work provides valuable insights for developing tanning mechanisms and sustainable chrome-free tanning systems.
期刊介绍:
Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics.
The main scope is covered but not limited to the following core areas:
Polymer Materials
Nanocomposites and hybrid nanomaterials
Polymer blends, films, fibres, networks and porous materials
Physical Characterization
Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films
Polymer Engineering
Advanced multiscale processing methods
Polymer Synthesis, Modification and Self-assembly
Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization
Technological Applications
Polymers for energy generation and storage
Polymer membranes for separation technology
Polymers for opto- and microelectronics.