Volume 9 Issue 4
Nov.  2024
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Yarong Li, Zhiguang Tang, Xiaohan Zhou, Junhua Zhang, Xueping Song, Kai Li, Wei Liu, Zhanying Zhang. Development of Methylene Bis-Benzotriazolyl Tetramethylbutylphenol-grafted lignin sub-microspheres loaded with TiO2 for sunscreen applications[J]. Journal of Bioresources and Bioproducts, 2024, 9(4): 534-547. doi: 10.1016/j.jobab.2024.09.003
Citation: Yarong Li, Zhiguang Tang, Xiaohan Zhou, Junhua Zhang, Xueping Song, Kai Li, Wei Liu, Zhanying Zhang. Development of Methylene Bis-Benzotriazolyl Tetramethylbutylphenol-grafted lignin sub-microspheres loaded with TiO2 for sunscreen applications[J]. Journal of Bioresources and Bioproducts, 2024, 9(4): 534-547. doi: 10.1016/j.jobab.2024.09.003

Development of Methylene Bis-Benzotriazolyl Tetramethylbutylphenol-grafted lignin sub-microspheres loaded with TiO2 for sunscreen applications

doi: 10.1016/j.jobab.2024.09.003
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  • Lignin serves as a promising Ultraviolet (UV) absorber within sunscreen industry. However, the commercial development of lignin-containing sunscreens faces challenges due to their low sun protection factor (SPF) and dark color in cosmetics industry. In this study, dual modifications on the chemical and physical structures of lignin were conducted to address these challenges. Initially, methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT) was grafted onto alkali lignin (AL) through an atom transfer radical polymerization reaction, resulting in a polymer of AL-graft-MBBT3 (AL-g-MBBT3). The sunscreen prepared with 10% AL-g-MBBT3 displays outstanding sun protection performance with a SPF of 42.93 and a light color with a color difference value (ΔE) of 45.6, in contrast to 10% AL with a SPF of 4.74 and a ΔE value of 49.5. Subsequently, AL-g-MBBT3 was transformed into normal submicron spheres (AL-g-MBBT3 N) and TiO2-loading submicron spheres (AL-g-MBBT3/TiO2). The sun protection performances of 10% AL-g-MBBT3 N@C and AL-g-MBBT3/TiO2@C sunscreens obviously surpass that of AL-g-MBBT3@C sunscreen, achieving SPFs of 60.38 and 66.20, respectively. Additionally, there is a considerable improvement in the color of these sunscreens, with ΔE values of 41.8 and 36.3, respectively. These results provide valuable insights into exploring lignin's high-value applications in sunscreen.

     

  • Declaration of competing interest
    The authors declare no conflict of interest.
    Supplementary materials
    Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.jobab.2024.09.003
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  • Baker, L.A., Marchetti, B., Karsili, T.N.V., Stavros, V.G., Ashfold, M.N.R., 2017. Photoprotection: extending lessons learned from studying natural sunscreens to the design of artificial sunscreen constituents. Chem. Soc. Rev. 46, 3770–3791. doi: 10.1039/C7CS00102A
    Bencherif, S.A., Gao, H.F., Srinivasan, A., Siegwart, D.J., Hollinger, J.O., Washburn, N.R., Matyjaszewski, K., 2009. Cell-adhesive star polymers prepared by ATRP. Biomacromolecules 10, 1795–1803. doi: 10.1021/bm900213u
    Chen, X. R, Han, X., Zhang, C.X., Ou, X., Liu, X.L., Zhang, J.H., Liu, W., Ragauskas, A.J., Song, X.P., Zhang, Z.Y., 2024. Synthesis of red, green, and blue carbon quantum dots and construction of multicolor cellulose-based light-emitting diodes. Small Struct 5, 2300449. doi: 10.1002/sstr.202300449
    Chen, K., Wang, S.Y., Qi, Y.G., Guo, H., Guo, Y.Z., Li, H.M., 2021. State-of-the-art: applications and industrialization of lignin micro/nano particles. ChemSusChem 14, 1284–1294. doi: 10.1002/cssc.202002441
    Chen, K., Zhou, X.Y., Wang, D., Li, J.W., Qi, D.M., 2022. Synthesis and characterization of a broad-spectrum TiO2@lignin UV-protection agent with high antioxidant and emulsifying activity. Int. J. Biol. Macromol. 218, 33–43. doi: 10.1016/j.ijbiomac.2022.06.190
    Chio, C., Sain, M., Qin, W.S., 2019. Lignin utilization: a review of lignin depolymerization from various aspects. Renew. Sustain. Energy Rev. 107, 232–249. doi: 10.1016/j.rser.2019.03.008
    Cozzi, A.C., Perugini, P., Gourion-Arsiquaud, S., 2018. Comparative behavior between sunscreens based on free or encapsulated UV filters in term of skin penetration, retention and photo-stability. Eur. J. Pharm. Sci. 121, 309–318. doi: 10.1016/j.ejps.2018.06.001
    Darmawan, M.A., Ramadhani, N.H., Hubeis, N.A., Ramadhan, M.Y.A., Sahlan, M., Abd-Aziz, S., Gozan, M., 2022. Natural sunscreen formulation with a high Sun protection factor (SPF) from tengkawang butter and lignin. Ind. Crops Prod. 177, 114466. doi: 10.1016/j.indcrop.2021.114466
    Dou, J.Z., Sui, M.M., Malinen, K., Pesonen, T., Isohanni, T., Vuorinen, T., 2022. Spruce bark stilbenes as a nature-inspired Sun blocker for sunscreens. Green Chem. 24, 2962–2974. doi: 10.1039/d2gc00287f
    Erdem, B., Hunsicker, R.A., Simmons, G.W., Sudol, E.D., Dimonie, V.L., El-Aasser, M.S., 2001. XPS and FTIR surface characterization of TiO2 particles used in polymer encapsulation. Langmuir 17, 2664–2669. doi: 10.1021/la0015213
    Figueiredo, P., Lintinen, K., Hirvonen, J.T., Kostiainen, M.A., Santos, H.A., 2018. Properties and chemical modifications of lignin: towards lignin-based nanomaterials for biomedical applications. Prog. Mater. Sci. 93, 233–269. doi: 10.1504/IJPM.2018.10010239
    Kai, D., Chua, Y.K., Jiang, L., Owh, C., Chan, S.Y., Loh, X.J., 2016. Dual functional anti-oxidant and SPF enhancing lignin-based copolymers as additives for personal and healthcare products. RSC Adv. 6, 86420–86427. doi: 10.1039/C6RA21433A
    Lee, S.C., Tran, T.M.T., Choi, J.W., Won, K., 2019. Lignin for white natural sunscreens. Int. J. Biol. Macromol. 122, 549–554. doi: 10.1016/j.ijbiomac.2018.10.184
    Li, M.S., Reimers, J.R., Ford, M.J., Kobayashi, R., Amos, R.D., 2021. Accurate prediction of the properties of materials using the CAM-B3LYP density functional. J. Comput. Chem. 42, 1486–1497. doi: 10.1002/jcc.26558
    Li, Y.R., Zhao, S.Y., Hu, D.B., Ragauskas, A.J., Cao, D.Y., Liu, W.Q., Si, C.L., Xu, T., Zhao, P.T., Song, X.P., Li, K., 2022. Role evaluation of active groups in lignin on UV-shielding performance. ACS Sustain. Chem. Eng. 10, 11856–11866. doi: 10.1021/acssuschemeng.2c02714
    Li, Y.R., Zhao, S.Y., Li, Y.H., Ragauskas, A.J., Song, X.P., Li, K., 2022. Revealing the relationship between molecular weight of lignin and its color, UV-protecting property. Int. J. Biol. Macromol. 223, 1287–1296. doi: 10.1016/j.ijbiomac.2022.11.067
    Li, Y.R., Zhao, S.Y., Song, X.P., Cao, D.Y., Li, K., Hassanpour, M., Zhang, Z.Y., 2022. UV-shielding performance and color of lignin and its application to sunscreen. Macromol. Mater. Eng. 307, 2100628. doi: 10.1002/mame.202100628
    Liu, X.H., Wang, J.F., Yu, J., Zhang, M.M., Wang, C.P., Xu, Y.Z., Chu, F.X., 2013. Preparation and characterization of lignin based macromonomer and its copolymers with butyl methacrylate. Int. J. Biol. Macromol. 60, 309–315. doi: 10.1016/j.ijbiomac.2013.06.005
    Liu, Z.H., Hao, N.J., Wang, Y.Y., Dou, C., Lin, F.R., Shen, R.C., Bura, R., Hodge, D.B., Dale, B.E., Ragauskas, A.J., Yang, B., Yuan, J.S., 2021. Transforming biorefinery designs with 'Plug-in processes of lignin' to enable economic waste valorization. Nat. Commun. 12, 3912. doi: 10.1038/s41467-021-23920-4
    Liu, X.L., Zhao, S.Y., Chen, X.R., Han, X., Zhang, J.H., Wu, M., Song, X.P., Zhang, Z.Y., 2024. The effect of lignin molecular weight on the formation and properties of carbon quantum dots. Green Chem 26, 3190–3201. doi: 10.1039/d3gc04694j
    Mennucci, B., Tomasi, J., Cammi, R., Cheeseman, J.R., Frisch, M.J., Devlin, F.J., Gabriel, S., Stephens, P.J., 2002. Polarizable continuum model (PCM) calculations of solvent effects on optical rotations of chiral molecules. J. Phys. Chem. A 106, 6102–6113. doi: 10.1021/jp020124t
    Mondal, S., Jatrana, A., Maan, S., Sharma, P., 2023. Lignin modification and valorization in medicine, cosmetics, environmental remediation and agriculture: a review. Environ. Chem. Lett. 21, 2171–2197. doi: 10.1007/s10311-023-01585-3
    Muzata, T.S., Gebrekrstos, A., Orasugh, J.T., Ray, S.S., 2023. An overview of recent advances in polymer composites with improved UV-shielding properties. J. Appl. Polym. Sci. 140, e53693. doi: 10.1002/app.53693
    Österberg, M., Sipponen, M.H., Mattos, B.D., Rojas, O.J., 2020. Spherical lignin particles: a review on their sustainability and applications. Green Chem. 22, 2712–2733. doi: 10.1039/d0gc00096e
    Pan, X.J., Kadla, J.F., Ehara, K., Gilkes, N., Saddler, J.N., 2006. Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationship between lignin structure, extraction conditions, and antioxidant activity. J. Agric. Food Chem. 54, 5806–5813. doi: 10.1021/jf0605392
    Qian, Y., Qiu, X.Q., Zhu, S.P., 2015. Lignin: a nature-inspired Sun blocker for broad-spectrum sunscreens. Green Chem. 17, 320–324. doi: 10.1039/C4GC01333F
    Qian, Y., Qiu, X.Q., Zhu, S.P., 2016. Sunscreen performance of lignin from different technical resources and their general synergistic effect with synthetic sunscreens. ACS Sustain. Chem. Eng. 4, 4029–4035. doi: 10.1021/acssuschemeng.6b00934
    Qian, Y., Zhong, X.W., Li, Y., Qiu, X.Q., 2017. Fabrication of uniform lignin colloidal spheres for developing natural broad-spectrum sunscreens with high Sun protection factor. Ind. Crops Prod. 101, 54–60. doi: 10.1016/j.indcrop.2017.03.001
    Schneider, W.D.H., Dillon, A.J.P., Camassola, M., 2021. Lignin nanoparticles enter the scene: a promising versatile green tool for multiple applications. Biotechnol. Adv. 47, 107685. doi: 10.1016/j.biotechadv.2020.107685
    Tejado, A., Peña, C., Labidi, J., Echeverria, J.M., Mondragon, I., 2007. Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis. Bioresour. Technol. 98, 1655–1663. doi: 10.1016/j.biortech.2006.05.042
    Tirado-Rives, J., Jorgensen, W.L., 2008. Performance of B3LYP density functional methods for a large set of organic molecules. J. Chem. Theory Comput. 4, 297–306. doi: 10.1021/ct700248k
    Tortora, M., Cavalieri, F., Mosesso, P., Ciaffardini, F., Melone, F., Crestini, C., 2014. Ultrasound driven assembly of lignin into microcapsules for storage and delivery of hydrophobic molecules. Biomacromolecules 15, 1634–1643. doi: 10.1021/bm500015j
    Tran, M.H., Phan, D.P., Lee, E.Y., 2021. Review on lignin modifications toward natural UV protection ingredient for lignin-based sunscreens. Green Chem. 23, 4633–4646. doi: 10.1039/d1gc01139a
    Tsuzuki, S., Uchimaru, T., 2020. Accuracy of intermolecular interaction energies, particularly those of hetero-atom containing molecules obtained by DFT calculations with Grimme's D2, D3 and D3BJ dispersion corrections. Phys. Chem. Chem. Phys. 22, 22508–22519. doi: 10.1039/d0cp03679j
    Ugartondo, V., Mitjans, M., Vinardell, M.P., 2008. Comparative antioxidant and cytotoxic effects of lignins from different sources. Bioresour. Technol. 99, 6683–6687. doi: 10.1016/j.biortech.2007.11.038
    Wang, J.Y., Chen, W.H., Yang, D.J., Fang, Z.Q., Liu, W.F., Xiang, T., Qiu, X.Q., 2022. Photonic lignin with tunable and stimuli-responsive structural color. ACS Nano 16, 20705–20713. doi: 10.1021/acsnano.2c07756
    Wang, T.Y., Zhao, J.Y., Yang, Z., Xiong, L.D., Li, L., Gu, Z.P., Li, Y.W., 2022. Polyphenolic sunscreens for photoprotection. Green Chem. 24, 3605–3622. doi: 10.1039/d1gc04828g
    Wang, W.T., Wang, F., Zhang, C., Tang, J.N., Zeng, X.R., Wan, X.J., 2021. Versatile value-added application of hyperbranched lignin derivatives: water-resistance adhesive, UV protection coating, self-healing and skin-adhesive sensing. Chem. Eng. J. 404, 126358. doi: 10.1016/j.cej.2020.126358
    Wen, J.L., Xue, B.L., Xu, F., Sun, R.C., Pinkert, A., 2013. Unmasking the structural features and property of lignin from bamboo. Ind. Crops Prod. 42, 332–343. doi: 10.1016/j.indcrop.2012.05.041
    Wu, X.W., Zhou, M.S., Ouyang, X.P., Qiu, X.Q., Qian, Y., 2024. Whiten lignin-based sunscreen via fractionation and ultrasonic cavitation. ACS Sustain. Chem. Eng. 12, 6539–6546. doi: 10.1021/acssuschemeng.3c08101
    Wu, Y., Qian, Y., Lou, H.M., Yang, D.J., Qiu, X.Q., 2019. Enhancing the broad-spectrum adsorption of lignin through methoxyl activation, grafting modification, and reverse self-assembly. ACS Sustain. Chem. Eng. 7, 15966–15973. doi: 10.1021/acssuschemeng.9b02317
    Wu, Y., Qian, Y., Zhang, A.C., Lou, H.M., Yang, D.J., Qiu, X.Q., 2020. Light color dihydroxybenzophenone grafted lignin with high UVA/UVB absorbance ratio for efficient and safe natural sunscreen. Ind. Eng. Chem. Res. 59, 17057–17068. doi: 10.1021/acs.iecr.9b06970
    Yu, J., Wang, J.F., Wang, C.P., Liu, Y.P., Xu, Y.Z., Tang, C.B., Chu, F.X., 2015. UV-absorbent lignin-based multi-arm star thermoplastic elastomers. Macromol. Rapid Commun. 36, 398–404. doi: 10.1002/marc.201400663
    Zhang, H., Chen, F.G., Liu, X.X., Fu, S.Y., 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. doi: 10.1021/acssuschemeng.8b03464
    Zhang, H., Liu, X.X., Fu, S.Y., Chen, Y.C., 2019. High-value utilization of kraft lignin: color reduction and evaluation as sunscreen ingredient. Int. J. Biol. Macromol. 133, 86–92. doi: 10.2355/isijinternational.isijint-2018-502
    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. doi: 10.1021/acssuschemeng.0c06998
    Zhao, Y., Truhlar, D.G., 2008. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 120, 215–241. doi: 10.1007/s00214-007-0310-x
    Zhou, Y.J., Qian, Y., Wang, J.Y., Qiu, X.Q., Zeng, H.B., 2020. Bioinspired lignin-polydopamine nanocapsules with strong bioadhesion for long-acting and high-performance natural sunscreens. Biomacromolecules 21, 3231–3241. doi: 10.1021/acs.biomac.0c00696
    Zhu, J.D., Yan, C.Y., Zhang, X., Yang, C., Jiang, M.J., Zhang, X.W., 2020. A sustainable platform of lignin: from bioresources to materials and their applications in rechargeable batteries and supercapacitors. Prog. Energy Combust. Sci. 76, 100788. doi: 10.1016/j.pecs.2019.100788
    Zollinger, H., 2003. Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments. Hoboken: John Wiley & Sons.
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