木质素纳米粒子的功能化应用研究进展

doi:10.3969/j.issn.1001-1803.2023.01.013

摘要/Abstract

摘要：

木质素是植物中含量仅次于纤维素的第二大天然有机高分子化合物，具有优异的耐腐蚀、耐热、抗菌和抗氧化性能。木质素资源的高效利用对解决化石资源的日益紧缺及环境污染等问题具有重要意义。木质素纳米粒子（LNPs）的出现为木素基高附加值产品的开发与应用开辟了一条新途径，其兼具纳米材料的小尺寸效应、表面效应、界面效应等特性和木质素自身的优异特性，在众多领域都表现出了广泛的潜在应用价值。本文对LNPs的6种制备方法包括：自组装法、界面聚合/交联法、高剪切均质法、超声波法、微生物法和酶解法的特点及原理进行了概述，并对每种方法的产物组成、最终产物状态进行了梳理。随后综述了LNPs在吸附剂、比色探针和复合材料（复合薄膜、复合水凝胶）中的功能化应用研究进展，并对其发展前景进行了展望，以期为LNPs的功能化开发提供思路。

关键词: 木质素, 纳米粒子, 生物质, 应用

Abstract:

Lignin is the second largest natural organic polymer compound in plants after cellulose, which has excellent corrosion resistance, heat resistance, and antibacterial and antioxidative properties. The efficient utilization of lignin resources is of great significance to solve the problems of increasing shortage of fossil resources and environmental pollution. The emergence of lignin nanoparticles （LNPs） has opened up a new way for the development and application of high value-added lignin-based products, which combines the small size effect, surface effect and interface effect of nanomaterials with the excellent characteristics of lignin itself. LNPs have shown potential applications in many fields. Herein, the characteristics and principles of six preparation methods of LNPs were summarized, including self-assembly method, interfacial polymerization/crosslinking method, high shear homogenization method, ultrasonic method, microbial method and enzymatic method. The product composition and final product state of each method were also introduced. Then, the research progress on functional applications of LNPs in adsorbents, colorimetric probes and composite materials （composite films and composite hydrogels） was reviewed, and the development trend of LNPs was prospected to provide ideas for functional development of LNPs.

Key words: lignin, nanoparticle, biomass, application

中图分类号:

TQ351

王春玉, 王惠娟, 范世强, 刘杨. 木质素纳米粒子的功能化应用研究进展[J]. 日用化学工业（中英文）, 2023, 53(1): 92-99.

Wang Chunyu, Wang Huijuan, Fan Shiqiang, Liu Yang. Research progress on functional application of lignin nanoparticles[J]. China Surfactant Detergent & Cosmetics, 2023, 53(1): 92-99.

图/表 5

参考文献 58

[1]	Richter A P, Brown J S, Bharti B, et al. An environmentally benign antimicrobial nanoparticle based on a silver-infused lignin core[J]. Nature Nanotechnology, 2015, 10 (9) : 817-823. doi: 10.1038/nnano.2015.141 pmid: 26167765
[2]	Wang Huan, Yang Dongjie, Qian Yong, et al. Recent progress in the preparation and application of lignin-based functional materials[J]. Chemical Industry and Engineering Progress, 2019, 38 (1) : 441-455.
[3]	Kai D, Tan M J, Chee P L, et al. Towards lignin-based functional materials in a sustainable world[J]. Green Chemistry, 2016, 18 (5) : 1175-1200. doi: 10.1039/C5GC02616D
[4]	Lievonen M, Valle-Delgado J J, Mattinen M-L, et al. A simple process for lignin nanoparticle preparation[J]. Green Chemistry, 2016, 18 (5) : 1416-1422. doi: 10.1039/C5GC01436K
[5]	Chen K, Wang S, Qi Y, et al. State-of-the-art: applications and industrialization of lignin micro/nano particles[J]. ChemSusChem, 2021, 14 (5) : 1284-1294. doi: 10.1002/cssc.202002441 pmid: 33403798
[6]	Li H, Deng Y, Wu H, et al. Self-assembly of kraft lignin into nanospheres in dioxane-water mixture[J]. Holzforschung, 2016, 70 (8) : 725-731. doi: 10.1515/hf-2015-0238
[7]	Richter A P, Bharti B, Armstrong H B, et al. Synthesis and characterization of biodegradable lignin nanoparticles with tunable surface properties[J]. Langmuir, 2016, 32 (25) : 6468-6477. doi: 10.1021/acs.langmuir.6b01088 pmid: 27268077
[8]	Cui Shaobo, Lu Zhongyuan, Liu Dechun, et al. Interfacial polymerization and its applications[J]. Chemical Industry and Engineering Progress, 2006, 25 (1) : 47-50.
[9]	Yiamsawas D, Beckers S J, Lu H, et al. Morphology-controlled synthesis of lignin nanocarriers for drug delivery and carbon materials[J]. ACS Biomaterials Science & Engineering, 2017, 3 (10) : 2375-2383.
[10]	Nypelö T E, Carrillo C A, Rojas O J. Lignin supracolloids synthesized from (W/O) microemulsions: use in the interfacial stabilization of Pickering systems and organic carriers for silver metal[J]. Soft Matter, 2015, 11 (10) : 2046-2054. doi: 10.1039/c4sm02851a pmid: 25629687
[11]	Chen N, Dempere L A, Tong Z. Synthesis of pH-responsive lignin-based nanocapsules for controlled release of hydrophobic molecules[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (10) : 5204-5211.
[12]	Henn A, Mattinen M L. Chemo-enzymatically prepared lignin nanoparticles for value-added applications[J]. World Journal of Microbiology and Biotechnology, 2019, 35 (8) : 1-9. doi: 10.1007/s11274-018-2566-9
[13]	Chen Kai, Qi Yungeng, Guo Yanzhu, et al. Progress on preparation and application of small-scale lignin particles[J]. Chemical Industry and Engineering Progress, 2020, 39 (8) : 3157-3173.
[14]	Juikar S J, Vigneshwaran N. Extraction of nanolignin from coconut fibers by controlled microbial hydrolysis[J]. Industrial Crops and Products, 2017, 109: 420-425. doi: 10.1016/j.indcrop.2017.08.067
[15]	Rangan A, Manchiganti M V, Thilaividankan R M, et al. Novel method for the preparation of lignin-rich nanoparticles from lignocellulosic fibers[J]. Industrial Crops & Products, 2017, 103: 152-160.
[16]	Mishra P K, Wimmer R. Aerosol assisted self-assembly as a route to synthesize solid and hollow spherical lignin colloids and its utilization in layer by layer deposition[J]. Ultrasonics Sonochemistry, 2017, 35: 45-50. doi: S1350-4177(16)30312-1 pmid: 27614582
[17]	Myint A A, Lee H W, Seo B, et al. One pot synthesis of environmentally friendly lignin nanoparticles with compressed liquid carbon dioxide as an antisolvent[J]. Green Chemistry, 2016, 18 (7) : 2129-2146. doi: 10.1039/C5GC02398J
[18]	Qi L, Zhu M, Zu Y, et al. Comparative antioxidant activity of nanoscale lignin prepared by a supercritical antisolvent (SAS) process with non-nanoscale lignin[J]. Food Chemistry, 2012, 135 (1) : 63-67. doi: 10.1016/j.foodchem.2012.04.070
[19]	Tortora M, Cavalieri F, Mosesso P, et al. Ultrasound driven assembly of lignin into microcapsules for storage and delivery of hydrophobic molecules[J]. Biomacromolecules, 2014, 15 (5) : 1634-1643. doi: 10.1021/bm500015j pmid: 24720505
[20]	Ago M, Huan S, Borghei M, et al. High-throughput synthesis of lignin particles (-30 nm to -2 μm) via aerosol flow reactor: size fractionation and utilization in pickering emulsions[J]. ACS Applied Materials & Interfaces, 2016, 8 (35) : 23302-23310.
[21]	Alqahtani M S, Alqahtani A, Al-Thabit A, et al. Novel lignin nanoparticles for oral drug delivery[J]. Journal of Materials Chemistry B, 2019, 7 (28) : 4461-4473. doi: 10.1039/c9tb00594c
[22]	Lintinen K, Xiao Y, Ashok R B, et al. Closed cycle production of concentrated and dry redispersible colloidal lignin particles with a three solvent polarity exchange method[J]. Green Chemistry, 2018, 20 (4) : 843-850. doi: 10.1039/C7GC03465B
[23]	Dai L, Li Y, Liu R, et al. Green mussel-inspired lignin magnetic nanoparticles with high adsorptive capacity and environmental friendliness for chromium (Ⅲ) removal[J]. International Journal of Biological Macromolecules, 2019, 132: 478-486. doi: 10.1016/j.ijbiomac.2019.03.222
[24]	Rivière G N, Korpi A, Sipponen M H, et al. Agglomeration of viruses by cationic lignin particles for facilitated water purification[J]. ACS Sustainable Chemistry & Engineering, 2020, 8 (10) : 4167-4177.
[25]	Leskinen T, Witos J, Delgado J, et al. Adsorption of proteins on colloidal lignin particles for advanced biomaterials[J]. Biomacromolecules, 2017, 18 (9) : 2767-2776. doi: 10.1021/acs.biomac.7b00676 pmid: 28724292
[26]	Nishio M, Umezawa Y, Fantini J, et al. CH-π hydrogen bonds in biological macromolecules[J]. Physical Chemistry Chemical Physics, 2014, 16 (25) : 12648-12683. doi: 10.1039/c4cp00099d pmid: 24836323
[27]	Penna M J, Mijajlovic M, Biggs M J. Molecular-level understanding of protein adsorption at the interface between water and a strongly interacting uncharged solid surface[J]. Journal of the American Chemical Society, 2014, 136 (14) : 5323-5331. doi: 10.1021/ja411796e pmid: 24506166
[28]	Zong E, Huang G, Liu X, et al. A lignin-based nano-adsorbent for superfast and highly selective removal of phosphate[J]. Journal of Materials Chemistry A, 2018, 6 (21) : 9971-9983. doi: 10.1039/C8TA01449C
[29]	Liu X, He X, Zhang J, et al. Cerium oxide nanoparticle functionalized lignin as a nano-biosorbent for efficient phosphate removal[J]. RSC Advances, 2020, 10 (3) : 1249-1260. doi: 10.1039/c9ra09986g pmid: 35494677
[30]	Sohni S, Hashima R, Nidaullah H, et al. Chitosan/nano-lignin based composite as a new sorbent for enhanced removal of dye pollution from aqueous solutions[J]. International journal of biological macromolecules, 2019, 132: 1304-1317. doi: S0141-8130(19)30667-1 pmid: 30922916
[31]	Azimvand J, Didehban K, Mirshokraie S A. Preparation and characterization of nano-lignin biomaterial to remove basic red 2 dye from aqueous solutions[J]. Pollution, 2018, 4 (3) : 395-415.
[32]	Dong R J, Zheng D F, Yang D J, et al. pH-responsive lignin-based magnetic nanoparticles for recovery of cellulose[J]. Bioresource Technology, 2019, 294: 122133-122139. doi: 10.1016/j.biortech.2019.122133
[33]	Chen Yihui, Liu Yan, Zhou Jianli, et al. Determination of peroxides in food samples by high performance liquid chromatography with variable wavelength detector[J]. Chinese Journal of Spectroscopy Laboratory, 2009, 26 (2) : 414-417.
[34]	Muralikrishna S, Cheunkar S, Lertanantawong B, et al. Graphene oxide-Cu(Ⅱ) composite electrode for non-enzymatic determination of hydrogen peroxide[J]. Journal of Electroanalytical Chemistry, 2016, 776: 59-65. doi: 10.1016/j.jelechem.2016.06.034
[35]	Sheng Y, Yang H, Wang Y, et al. Silver nanoclusters-catalyzed luminol chemiluminescence for hydrogen peroxide and uric acid detection[J]. Talanta, 2017, 166: 268-274. doi: S0039-9140(17)30176-5 pmid: 28213233
[36]	Nasir M, Nawaz M H, Latif U, et al. An overview on enzyme-mimicking nanomaterials for use in electrochemical and optical assays[J]. Microchimica Acta, 2017, 184 (2) : 323-342. doi: 10.1007/s00604-016-2036-8
[37]	Aadil K R, Barapatre A, Meena A S, et al. Hydrogen peroxide sensing and cytotoxicity activity of Acacia lignin stabilized silver nanoparticles[J]. International Journal of Biological Macromolecules, 2016, 82: 39-47. doi: 10.1016/j.ijbiomac.2015.09.072 pmid: 26434518
[38]	Wang B, Gu S, Ding Y, et al. A novel route to prepare LaNiO₃ perovskite-type oxide nanofibers by electrospinning for glucose and hydrogen peroxide sensing[J]. Analyst, 2013, 138 (1) : 362-367. doi: 10.1039/C2AN35989H
[39]	Zhang Q, Li M, Guo C, et al. Fe₃O₄nanoparticles loaded on lignin nanoparticles applied as a peroxidase mimic for the sensitively colorimetric detection of H₂O₂[J]. Nanomaterials, 2019, 9 (2) : 210-224. doi: 10.3390/nano9020210
[40]	Jiang B, Duan D, Gao L, et al. Standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes[J]. Nature Protocols, 2018, 13 (7) : 1506-1520. doi: 10.1038/s41596-018-0001-1 pmid: 29967547
[41]	Xue Y, Qiu X, Liu Z, et al. Facile and efficient synthesis of silver nanoparticles based on biorefinery wood lignin and its application as the optical sensor[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (6) : 7695-7703.
[42]	Feldman D. Lignin nanocomposites[J]. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 2016, 53 (6) : 382-387. doi: 10.1080/10601325.2016.1166006
[43]	Grossman A, Wilfred V. Lignin-based polymers and nanomaterials[J]. Current Opinion in Biotechnology, 2019, 56: 112-120. doi: S0958-1669(18)30061-2 pmid: 30458357
[44]	Du Lulu, Meng Weixiao, Xie Yanlin, et al. Research progress on PLA toughening[J]. New Chemical Materials, 2021, 49 (2) : 48-51.
[45]	Yang W, Dominici F, Fortunati E, et al. Effect of lignin nanoparticles and masterbatch procedures on the final properties of glycidyl methacrylate-g-poly(lactic acid) films before and after accelerated UV weathering[J]. Industrial Crops & Products, 2015, 77: 833-844.
[46]	Yang W, Fortunati E, Dominici F, et al. Effect of processing conditions and lignin content on thermal, mechanical and degradative behavior of lignin nanoparticles/polylactic(acid) bionanocomposites prepared by melt extrusion and solvent casting[J]. European Polymer Journal, 2015, 71: 126-139. doi: 10.1016/j.eurpolymj.2015.07.051
[47]	Li X, Hegyesi N, Zhang Y, et al. Poly(lactic acid)/lignin blends prepared with the pickering emulsion template method[J]. European Polymer Journal, 2019, 110: 378-384. doi: 10.1016/j.eurpolymj.2018.12.001
[48]	Gordobil O, Delucis R, Egüés I, et al. Kraft lignin as filler in PLA to improve ductility and thermal properties[J]. Industrial Crops and Products, 2015, 72: 46-53. doi: 10.1016/j.indcrop.2015.01.055
[49]	Anwer M, Naguib H, Celzard A, et al. Comparison of the thermal, dynamic mechanical and morphological properties of PLA-lignin & PLA-tannin particulate green composites[J]. Composites Part B, 2015, 82: 92-99. doi: 10.1016/j.compositesb.2015.08.028
[50]	Bertini F, Canetti M, Cacciamani A, et al. Effect of ligno-derivatives on thermal properties and degradation behavior of poly(3-hydroxybutyrate)-based biocomposites[J]. Polymer Degradation and Stability, 2012, 97: 1979-1987. doi: 10.1016/j.polymdegradstab.2012.03.009
[51]	Liu D, Zhong T, Chang P R, et al. Starch composites reinforced by bamboo cellulosic crystals[J]. Bioresource Technology, 2010, 101 (7) : 2529-2536. doi: 10.1016/j.biortech.2009.11.058 pmid: 20015636
[52]	Lizundia E, Armentano I, Luzi F, et al. Synergic effect of nanolignin and metal oxide nanoparticles into poly(L-lactide) bionanocomposites: material properties, antioxidant activity and antibacterial performance[J]. ACS Applied Bio Materials, 2020, 3 (8) : 5263-5274. doi: 10.1021/acsabm.0c00637 pmid: 35021701
[53]	Nguyen K T, West J L. Photopolymerizable hydrogels for tissue engineering applications[J]. Biomaterials, 2002, 23 (22) : 4307-4314. pmid: 12219820
[54]	Chen Y, Zheng K, Niu L, et al. Highly mechanical properties nanocomposite hydrogels with biorenewable lignin nanoparticles[J]. International Journal of Biological Macromolecules, 2019, 128: 414-420. doi: S0141-8130(18)35437-0 pmid: 30682469
[55]	Yang W, Fortunati E, Bertoglio F, et al. Polyvinyl alcohol/chitosan hydrogels with enhanced antioxidant and antibacterial properties induced by lignin nanoparticles[J]. Carbohydrate Polymers, 2018, 181: 275-284. doi: S0144-8617(17)31240-7 pmid: 29253973
[56]	Hu X, Ye D, Tang J, et al. From waste to functional additives: thermal stabilization and toughening of PVA with lignin[J]. RSC Advances, 2016, 6 (17) : 13797-13802. doi: 10.1039/C5RA26385A
[57]	Ye D, Jiang L, Hu X, et al. Lignosulfonate as reinforcement in polyvinyl alcohol film: mechanical properties and interaction analysis[J]. International journal of biological macromolecules, 2016, 83: 209-215. doi: 10.1016/j.ijbiomac.2015.11.064 pmid: 26631636
[58]	Bian H, Jiao L, Wang R, et al. Lignin nanoparticles as nano-spacers for tuning the viscoelasticity of cellulose nanofibril reinforced polyvinyl alcohol-borax hydrogel[J]. European Polymer Journal, 2018, 107: 267-274. doi: 10.1016/j.eurpolymj.2018.08.028