New insight into lignin aggregation guiding efficient synthesis and functionalization of a lignin nanosphere with excellent performance
New insight into lignin aggregation guiding efficient synthesis and functionalization of a lignin nanosphere with excellent performance
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对木质素聚集的新见解指导具有优异性能的木质素纳米球的高效合成和功能化
DOI：
10.1039/d1gc03651c
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发表时间：
2021-12-09
期刊：
影响因子：
9.8
通讯作者：
Qiu, Xueqing
中科院分区：
文献类型：
--
作者：
Chen, Liheng;Luo, Si-Man;Qiu, Xueqing
了解木质素纳米颗粒形成的分子机理，将有助于更准确地指导其功能化，对生物质的价值评估具有重要意义。分子水平机械研究的试错方法极其困难且资源密集。本文通过分子模拟和实验相结合的方法揭示了木质素芳环分子内相互作用是木质素聚集成LNP的内在驱动力。此外，还建立了一个与木质素二聚体构型分布和LNP产率相关的定量芳烃相互作用模型，用于指导LNP的合成和功能化。然后筛选出一种纤维素衍生的溶剂，γ-戊内酯（GVL），以维持木质素分子的分子内堆积（~ 5.54 kJ mol（-1））成球形核，用于在溶剂转移期间生长均匀且稳定的木质素纳米球。在LNP形成机制的辅助下，木质素可以成功地稳定原位生成的金纳米颗粒，在GVL/水溶液中制备LNP期间具有优异的光热性能。该机理的提出将为木质素的绿色高效生物材料化提供重要的理论依据。
Understanding the molecular mechanism of lignin nanoparticle (LNP) formation will precisely instruct its functionalization, which is of importance for biomass valorization. Trial-and-error approaches for mechanistic research at the molecular level are extremely difficult and resource intensive. Here we have revealed that the intra-molecular interactions of lignin aromatic rings were the internal force driving the aggregation of lignin into LNPs by combining molecular simulation with experimental methods. A quantitative aromatic interaction correlated with the configuration distribution of lignin dimer and LNP yields was also developed for guiding the synthesis and functionalization of LNPs. A cellulose-derived solvent, gamma-valerolactone (GVL), was then screened out to sustain lignin molecules' intramolecular stacking (-5.54 kJ mol(-1)) into a spherical nucleus for the growth of a uniform and stable lignin nanosphere during solvent shifting. With the assistance of the LNP formation mechanism, lignin could successfully stabilize in situ generated gold nanoparticles with excellent photothermal performance during the production of LNPs in a GVL/water solution. The newly proposed mechanism will provide an important theoretical basis for upgrading lignin to value-added biomaterials in a green and facile pathway.