Abstract
Lignin has a UV-blocking ability because it contains phenolic and ketone functional groups. However, the lignin produced in the paper industry undergoes extreme polycondensation, resulting in an extremely dark color, which impedes its value-added application in the field of UV-blocking cosmetics. In this study, maleic acid (MA) was used as a green and recyclable reagent to pretreat an agricultural waste lignocellulosic biomass, Kenaf stalk. Lignin underwent a carboxyl esterification reaction with MA to produce light-colored dissolved lignin (DL), which was further prepared into lignin nanospheres and used in lignin-based sunscreens. The results showed that when adding 5 wt% DL-lignin nanospheres (DL-LNPs) to a sunscreen with an actual measured sun protection factor (SPF) of 7.05, the SPF of the lignin-based sunscreen increased to 63.82 far exceeding the commercially available SPF 50 sunscreens. The prepared lignin-based sunscreen had good biocompatibility when applied to human skin and did not stain the skin. The remaining neutral solid after pretreatment was made into Kenaf fibers by PFI milling for papermaking. The ring crush strength index of the paper increased from 2.81 N m/g to 3.14 N m/g when 15 wt% Kenaf fibers was added to the softwood pulp. When the additions Kenaf fibers was 5 wt%, the tensile index and tearing index of the paper increased from 8.57 N m/g and 4.68 mN m2/g to 9.22 N m/g and 5.48 mN m2/g, respectively. Therefore, this study provides a new way for the value-added utilization of Kenaf stalk lignocellulosic biomass.
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References
Bhatnagar P, Law JX, Ng SF (2021) Chitosan reinforced with Kenaf nanocrystalline cellulose as an effective carrier for the delivery of platelet lysate in the acceleration of wound healing. Polymers 13:4392. https://doi.org/10.3390/polym13244392
Cai C, Hirth K, Gleisner R, Lou H, Qiu X, Zhu JY (2020) Maleic acid as a dicarboxylic acid hydrotrope for sustainable fractionation of wood at atmospheric pressure and ≤ 100°C: mode and utility of lignin esterification. Green Chem 22:1605–1617. https://doi.org/10.1039/c9gc04267a
Cen Q, Chen S, Yang D, Zheng D, Qiu X (2023) Full bio-based aerogel incorporating lignin for excellent flame retardancy, mechanical resistance, and thermal insulation. ACS Sustain Chem Eng 11:4473–4484. https://doi.org/10.1021/acssuschemeng.2c07652
Chen WJ, Zhao BC, Cao XF, Yuan TQ, Shi Q, Wang SF, Sun RC (2019) Structural features of alkaline dioxane lignin and residual lignin from Eucalyptus grandis x E. urophylla. J Agric Food Chem 67:968–974. https://doi.org/10.1021/acs.jafc.8b05760
Constant S, Wienk HLJ, Frissen AE, de Peinder P, Boelens R, van Es DS, Grisel RJH, Weckhuysen BM, Huijgen WJJ, Gosselink RJA, Bruijnincx PCA (2016) New insights into the structure and composition of technical lignins: a comparative characterisation study. Green Chem 18:2651–2665. https://doi.org/10.1039/c5gc03043a
del Río JC, Lino AG, Colodette JL, Lima CF, Gutiérrez A, Martínez ÁT, Lu F, Ralph J, Rencoret J (2015) Differences in the chemical structure of the lignins from sugarcane bagasse and straw. Biomass Bioenergy 81:322–338. https://doi.org/10.1016/j.biombioe.2015.07.006
Fatriansyah JF, Surip SN, Wan Jaafar WNR, Phasa A, Uyup MKA, Suhariadi I (2022) Isothermal crystallization kinetics and mechanical properties of PLA/Kenaf biocomposite: comparison between alkaline treated kenaf core and bast reinforcement. Mater Lett 319:132294. https://doi.org/10.1016/j.matlet.2022.132294
Ji HR, Song YL, Zhang X, Tan TW (2017) Using a combined hydrolysis factor to balance enzymatic saccharification and the structural characteristics of lignin during pretreatment of hybrid poplar with a fully recyclable solid acid. Bioresour Technol 238:575–581. https://doi.org/10.1016/j.biortech.2017.04.092
Ji H, Dong C, Yang G, Pang Z (2018) Valorization of lignocellulosic biomass toward multipurpose fractionation: furfural, phenolic compounds, and ethanol. ACS Sustain Chem Eng 6:15306–15315. https://doi.org/10.1021/acssuschemeng.8b03766
Ji HR, Wang L, Pang ZQ, Zhu WY, Yang GH, Dong CH (2020) Using a recyclable acid hydrotrope and subsequent short-term ultrasonic pretreatment to facilitate high-value lignin extraction and high-titer ethanol production. Cellulose 27:7561–7573. https://doi.org/10.1007/s10570-020-03285-5
Ji H, Wang L, Tao F, Yao Z, Li X, Dong C, Pang Z (2022) A hydrotrope pretreatment for stabilized lignin extraction and high titer ethanol production. Bioresour Bioprocess 9:1–11
Lee SC, Tran TMT, Choi JW, Won K (2019) Lignin for white natural sunscreens. Int J Biol Macromol 122:549–554. https://doi.org/10.1016/j.ijbiomac.2018.10.184
Li Y, Zhao S, Song X, Cao D, Li K, Hassanpour M, Zhang Z (2022) UV-shielding performance and color of lignin and its application to sunscreen. Macromol Mater Eng 307:2100628. https://doi.org/10.1002/mame.202100628
Lin M, Yang L, Zhang H, Xia Y, He Y, Lan W, Ren J, Yue F, Lu F (2021) Revealing the structure-activity relationship between lignin and anti-UV radiation. Ind Crops Prod. https://doi.org/10.1016/j.indcrop.2021.114212
Liu L, Qian M, Song P, Huang G, Yu Y, Fu S (2016) Fabrication of green lignin-based flame retardants for enhancing the thermal and fire retardancy properties of polypropylene/wood composites. ACS Sustain Chem Eng 4:2422–2431. https://doi.org/10.1021/acssuschemeng.6b00112
Liu ZH, Li BZ, Yuan JS, Yuan YJ (2022) Creative biological lignin conversion routes toward lignin valorization. Trends Biotechnol 40:1550–1566. https://doi.org/10.1016/j.tibtech.2022.09.014
Lu C, Xu J, Xie J, Zhu S, Wang B, Li J, Zhang F, Chen K (2022) Preparation, characterization of light-colored lignin from corn Stover by new ternary deep eutectic solvent extraction. Int J Biol Macromol 222:2512–2522. https://doi.org/10.1016/j.ijbiomac.2022.10.035
Ma S, Chen B, Zeng A, Li Z, Tang X, Sun Y, Lin L, Zeng X (2022) Chemical structure change of lignin extracted from bamboo biomass by maleic acid. Int J Biol Macromol 221:986–993. https://doi.org/10.1016/j.ijbiomac.2022.09.002
McKinlay AF, Diffey BL (1987) A reference spectrum for ultraviolet induced erythema in human skin. CIE J 6:21–27
Morsella M, d’Alessandro N, Lanterna AE, Scaiano JC (2016) Improving the sunscreen properties of TiO2 through an understanding of its catalytic properties. ACS Omega 1:464–469. https://doi.org/10.1021/acsomega.6b00177
Österberg M, Sipponen MH, Mattos BD, Rojas OJ (2020) Spherical lignin particles: a review on their sustainability and applications. Green Chem 22:2712–2733. https://doi.org/10.1039/d0gc00096e
Qian Y, Qiu XQ, Zhu SP (2015) Lignin: a nature-inspired sun blocker for broad-spectrum sunscreens. Green Chem 17:320–324. https://doi.org/10.1039/c4gc01333f
Qian Y, Qiu XQ, Zhu SP (2016) Sunscreen performance of lignin from different technical resources and their general synergistic effect with synthetic sunscreens. ACS Sustain Chem Eng 4:4029–4035. https://doi.org/10.1021/acssuschemeng.6b00934
Qian Y, Zhong XW, Li Y, Qiu XQ (2017) Fabrication of uniform lignin colloidal spheres for developing natural broad-spectrum sunscreens with high sun protection factor. Ind Crops Prod 101:54–60. https://doi.org/10.1016/j.indcrop.2017.03.001
Ratanasumarn N, Chitprasert P (2020) Cosmetic potential of lignin extracts from alkaline-treated sugarcane bagasse: optimization of extraction conditions using response surface methodology. Int J Biol Macromol 153:138–145. https://doi.org/10.1016/j.ijbiomac.2020.02.328
Rencoret J, Prinsen P, Gutierrez A, Martinez AT, Del Rio JC (2015) Isolation and structural characterization of the milled wood lignin, dioxane lignin, and cellulolytic lignin preparations from brewer’s spent grain. J Agric Food Chem 63:603–613. https://doi.org/10.1021/jf505808c
Saulnier BK, Siahkamari M, Singh SK, Nejad M, Hodge DB (2023) Effect of dilute acid pretreatment and lignin extraction conditions on lignin properties and suitability as a phenol replacement in phenol-formaldehyde wood adhesives. J Agric Food Chem 71:592–602. https://doi.org/10.1021/acs.jafc.2c07299
Shen X-J, Wang B, Pan-li H, Wen J-L, Sun R-C (2016) Understanding the structural changes and depolymerization of eucalyptus lignin under mild conditions in aqueous AlCl3. RSC Adv 6:45315–45325. https://doi.org/10.1039/c6ra08945c
Sluiter A, Hames B, Ruiz R, Scarlata C, Crocker D (2008) Determination of Structural Carbohydrates and Lignin in Biomass—NREL/TP-510-42618
Su C, Hirth K, Liu Z, Cao Y, Zhu JY (2021) Acid hydrotropic fractionation of switchgrass at atmospheric pressure using maleic acid in comparison with p-TsOH: advantages of lignin esterification. Ind Crops Prod. https://doi.org/10.1016/j.indcrop.2020.113017
Tran MH, Phan D-P, Lee EY (2021) Review on lignin modifications toward natural UV protection ingredient for lignin-based sunscreens. Green Chem 23:4633–4646. https://doi.org/10.1039/d1gc01139a
Wang B, Sun D, Wang H-M, Yuan T-Q, Sun R-C (2018a) Green and facile preparation of regular lignin nanoparticles with high yield and their natural broad-spectrum sunscreens. ACS Sustain Chem Eng 7:2658–2666. https://doi.org/10.1021/acssuschemeng.8b05735
Wang G, Xia Y, Sui W, Si C (2018b) Lignin as a novel tyrosinase inhibitor: effects of sources and isolation processes. ACS Sustain Chem Eng 6:9510–9518. https://doi.org/10.1021/acssuschemeng.8b02234
Wu Y, Ji H, Ji X, Tian Z, Chen J (2020) Fibrillating wood chips to facilitate high-valued lignin extraction and high titer ethanol production. Ind Crops Prod. https://doi.org/10.1016/j.indcrop.2020.112153
Zhang Y, Naebe M (2021) Lignin: a review on structure, properties, and applications as a light-colored UV absorber. ACS Sustain Chem Eng 9:1427–1442. https://doi.org/10.1021/acssuschemeng.0c06998
Zhang H, Chen FG, Liu XX, Fu SY (2018) Micromorphology influence on the color performance of lignin and its application in guiding the preparation of light-colored lignin sunscreen. ACS Sustain Chem Eng 6:12532–12540. https://doi.org/10.1021/acssuschemeng.8b03464
Zhang H, Liu X, Fu S, Chen Y (2019a) High-value utilization of kraft lignin: color reduction and evaluation as sunscreen ingredient. Int J Biol Macromol 133:86–92. https://doi.org/10.1016/j.ijbiomac.2019.04.092
Zhang H, Liu XX, Fu SY, Chen YC (2019b) Fabrication of light-colored lignin microspheres for developing natural sunscreens with favorable UV absorbability and staining resistance. Ind Eng Chem Res 58:13858–13867. https://doi.org/10.1021/acs.iecr.9b02086
Zhou M, Shi H, Li C, Sheng X, Sun Y, Hou M, Niu M, Pan X (2020) Depolymerization and activation of alkali lignin by solid acid-catalyzed phenolation for preparation of lignin-based phenolic foams. Ind Eng Chem Res 59:14296–14305. https://doi.org/10.1021/acs.iecr.0c01753
Acknowledgments
The authors received supports from the National Key R&D Program of China (Grant No. 2019YFC1905900), the National Natural Science Foundation of China (Grant No. 32230070), Shandong Natural Science Foundation & Major Basic Research Project (Grant No. ZR2021ZD38), Jinan Innovation Team (Grant No. 2021GXRC023), the QUTJBZ Program (No. 2022JBZ01-05), the Taishan Industrial Experts Program, and Taishan Scholars Program.
Funding
National Key R&D Program of China (Grant No. 2019YFC1905900), the National Natural Science Foundation of China (Grant No. 32230070), Shandong Natural Science Foundation & Major Basic Research Project (Grant No. ZR2021ZD38), Jinan Innovation Team (Grant No. 2021GXRC023), the QUTJBZ Program (No. 2022JBZ01-05), the Taishan Industrial Experts Program, and Taishan Scholars Program.
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Yingren Lyu conducted all the experiment and wrote paper. Hairui Ji revised this paper. Xingxiang Ji funded acquisition and resources. Zhongjian Tian conceived the experiment. Fengshan Zhang provided guidance for experiment design.
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Lyu, Y., Ji, H., Ji, X. et al. A sustainable valorization of Kenaf stalk by maleic acid pretreatment towards lignin-based sunscreens preparation and papermaking. Cellulose 30, 9725–9739 (2023). https://doi.org/10.1007/s10570-023-05468-2
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DOI: https://doi.org/10.1007/s10570-023-05468-2