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Green Chemistry Accepted Mnuscript This is n Accepted Mnuscript, which hs een through the Royl Society of Chemistry peer review process nd hs een ccepted for puliction.

1 Green Chemistry Accepted Mnuscript This is n Accepted Mnuscript, which hs een through the Royl Society of Chemistry peer review process nd hs een ccepted for puliction. Accepted Mnuscripts re pulished online shortly fter cceptnce, efore technicl editing, formtting nd proof reding. Using this free service, uthors cn mke their results ville to the community, in citle form, efore we pulish the edited rticle. We will replce this Accepted Mnuscript with the edited nd formtted Advnce Article s soon s it is ville. You cn find more informtion out Accepted Mnuscripts in the Informtion for Authors. Plese note tht technicl editing my introduce minor chnges to the text nd/or grphics, which my lter content. The journl s stndrd Terms & Conditions nd the Ethicl guidelines still pply. In no event shll the Royl Society of Chemistry e held responsile for ny errors or omissions in this Accepted Mnuscript or ny consequences rising from the use of ny informtion it contins.

2 Pge 1 of 6 Dynmic Article Links Cite this: DOI: 1.139/cxxx PAPER Lignin: nture-inspired sun locker for rod-spectrum sunscreens Yong Qin,, Xueqing Qiu * nd Shiping Zhu * Received (in XXX, XXX) Xth XXXXXXXXX 2XX, Accepted Xth XXXXXXXXX 2XX DOI: 1.139/x We report the evlution of lignin for development of high-performnce rod-spectrum sunscreens. Lignin is dded into severl commercil sunscreen products. Significnt enhncements in ultrviolet (UV) sornce re oserved. The results show tht the sunscreen effect of sun protection fctor (SPF) 15 could rech to tht of SPF 3 with 2wt% lignin ddition. Adding 1wt% lignin mkes SPF 15 outperform SPF 5. It is lso interesting to find tht the sunscreen performnce improves with UV-rdition time. After two hours of UV rdition, the UV sornce of the 1wt% lignin SPF 15 lotion increse drmticlly. This hs een ttriuted to some synergistic effect etween lignin nd other sunscreen ctives in the lotions, s well s the ntioxidnt property of lignin. This ntureinspired lignin system my provide green lterntive to replce some synthetic sunscreen ctives. Introduction Long-time exposure to ultrviolet (UV) rdition is hzrdous nd cuses skin prolems. In ddition to wering dequte clothing without impregntion, 1 sunscreen provides protection, 2, 3 commercil sunscreen products re divided into two ctegories ccording to their ctive ingredients, tht is, physicl nd chemicl sunscreens. In physicl sunscreens, the ctive ingredients re minly zinc oxide nd titnium dioxide, sed on reflection mechnism. 4 Physicl sunscreens re helthy, ut re not so comfortle, especilly for people with dry skins. Compred to physicl sunscreens, chemicl sunscreens re esier to use, ut hve their own drwcks. The ctive ingredients in chemicl sunscreens re often synthetic chemicls. Long-time use of such chemicls my cuse unexpected side effects on skins. 5 Nturl sunscreens re therefore receiving more nd more ttention recently. Nturl products such s green coffee oil, extrcts of cric ppy, ros kordesii, helichrysum renrium nd so on re proven to hve rdition protection functions. 6-9 Usully, mny nturl sunscreens lso hve good ntioxidnt properties. However, most of the nturl products re prtspectrum sun lockers nd cnnot lock the full spectrum of UV light. Besides, extrction of the ctive ingredients from rw mterils is costly. The nturl sun lockers re often expensive nd lrge volume commercil production is limited. Lignin is the only iomss rich in romtic rings in nture due to its sic phenylpropne unit It lso contins UV-soring functionl groups such s phenolic, ketone nd other chromophores Lignin is nturl rod-spectrum sun locker. 18 In ddition to sunscreen property, the free rdicl scvenging ility of phenolic groups gives lignin n excellent ntioxidnt property Although 5 to tons of lignin is produced in nture nd over 5 million tons of industril lignin is produced nnully, lignin hs never used s sunscreen nd ntioxidnt ctives in cosmetics nd/or phrmceuticls due to some sfety concerns Except for smll mount of lignosulfontes used s low-end surfctnts, such s concrete wter reducers, wter-col-slurry dispersnts, nd dye stuff dispersnts, most lignin is urned for energy High-end pplictions of the industril lignin t lrge scle is still under explortion. Recently, Ugrtondo et l. tested the cell cytotoxicity of four types of industril lignin nd found tht the products re sfe. 3 Lignin-sed products such s microcpsules re not cytotoxic nd cn e incorported into cells. 3 These studies resolved douts out the sfety of lignin for potentil pplictions in cosmetics nd phrmceuticls. In this work, lkli lignin recovered from lck liquid is investigted for its sunscreen performnce. The lignin is dded to pure crems nd commercil sun protection fctor (SPF) 15 sun lotions, s rod-spectrum sunscreen ctive. The sunscreen results of SPF 15 sunscreen lotions contining vrious mounts of lignin re compred to those of SPF 3 nd SPF 5 sunscreen products. The irrdition stilities of the prepred lignin sunscreens re lso exmined. Experimentl section Mterils Alkli lignin ws otined from Shunti technology Corp (Huihu, Hunn, Chin). Before use, lkli lignin ws purified gin y lkli-cid treting for t lest three times nd continuous wshing with DI wter. Prticle sizes of the dry lkli lignin were rnged from nnometers to micrometers (oserved from SEM imges in supplementry informtion). Pure crems were NIVEA refreshingly soft moisturizing crem (75 ml) (Crem-N) nd LIFE glycerin hnd crem (75 ml) (Crem-L). Sun lotions were LIFE SPF 15, 3, 5 sunscreen lotions (SPF15- L, SPF3-L, nd SPF5-L) nd BIOTHERM SPF 15, 3, 5 sunscreen lotions (SPF15-B, SPF3-B, nd SPF5-B). All these pure crems nd sunscreen lotions were ought from SHOPPERS drug mrket (Hmilton, Ontrio, Cnd). Preprtion of lignin sunscreen smples All lignin-sed sunscreen crems nd lotions were prepred y simple mgnetic stirring. For exmple, 5wt% lignin sunscreen This journl is The Royl Society of Chemistry [yer], [yer], [vol], 1 Accepted Mnuscript

3 Trnsmittnce Trnsmittnce Pge 2 of 6 ws prepred y lending.1g lignin nd 1.9g pure crems t 1 rpm for 24 hours. The whole lending process ws performed under room temperture in drk room. After lending, these lignin sunscreens were trnsferred onto trnspore tpe surfce for the mesurement of UV trnsmittnce. The dry lkli lignin used in this work ws rown. The formulted lignin sunscreen lotions hd light rown to rown colors s its content incresed. Sun protection fctor (SPF) determintion 3M Trnspore tpe ws stickered on clen qurtz slides of 2 mm thickness. A tpe of 12.5 cm 2 ws used to ssure mesurements on t lest five non-overlpping spots. For ech sunscreen crem nd lotion, minimum of five smples were prepred for the UV trnsmittnce mesurement. At the sme time, reference smple of trnspore tpe ws lso prepred. In preprtion of the sunscreen smples, 1 ml fine needle syringe ws used to trnsfer the smple. For 12.5 cm 2 smple size, the slide ws plced on n nlyticl lnce nd 2 mg/cm 2 of lignin sunscreen smple ws distriuted on the tpe y dotting sunscreen on the slide. The sunscreen ws then distriuted over entire surfce y slowly ruing the slide surfce with cot coted finger. The smple ws then plced in drk room, drying 2 min prior to mesurement. The UV trnsmittnce of lignin sunscreen ws mesured y Shimdzu UV-36 with integrting sphere (Shimdzu, Jpn). Five spots were scnned for ech smple. In ech scn, trnsmittnce (T) mesurement per 1 nm ws collected in the wvelength rnge from UVB (29-32nm) to UVA (32-4nm). The SPF vlue ws clculted y the following eqution: (1) where E λ = CIE erytheml spectrl effectiveness; 31 S λ = solr spectrl irrdince; 32 T λ = spectrl trnsmittnce of the smple. Photostility test The study on photostility of the sunscreen crems with or without lignin ws performed on DU 8 UV/visile spectrophotometer (Beckmn Coulter, USA). Specificlly, the sunscreen smples were prepred ccording the sme procedure s for the SPF mesurements nd were exposed to UV rdition for two hours. UV source ws the deuterium light of the DU 8 UV/visile spectrophotometer. UV sornce in the UVB nd UVA res (29-4nm) efore nd fter rdition ws then determined for the photostility of these sunscreens. Results nd discussion Lignin dded to pure crems Two kinds of lignin sunscreens were prepred. One ws lends of lignin with Crem-N nd the other ws lignin lended with Crem-L. Becuse Crem-L ws too sticky, 1wt% wter ws dded. The pure Crem-N hd no sornce in the UVA nd UVB res s shown in Figure 1, while Crem-L with 1wt% wter hd little sornce in nm s shown in Figure 1. It ws negligile ecuse its corresponding SPF ws only 1.5. The SPF vlue of the pure Crem-N without UV sornce ws 1. When lignin ws dded into these pure crems, their UV trnsmittnce decresed nd SPF vlues incresed. When the Crem-N C+1wt% lignin C+2wt% lignin C+5wt% lignin C+1wt% lignin Crem-L C+1wt% lignin C+2wt% lignin C+5wt% lignin C+1wt% lignin SPF 15 SPF 15 Fig. 1 UV trnsmittnce of the pure crems lended with different mounts of lignin in UVB nd UVA res. The purchsed SPF 15 sunscreen provides reference. () Crem-N + lignin; () Crem-L + lignin. Tle 1. SPF vlues of the pure crems lended with different mounts of lignin. Lignin (wt%) Crem-N.99± ± ± ± ±.26 Crem-L 1.6± ± ± ± ±.47 mount of lignin incresed to 1wt%, SPF of the lignin + Crem- N incresed to 5.72, while SPF of the lignin + Crem-L incresed to Tle 1 summrizes SPF vlues of the pure crems lended with different mounts of lignin. As expected, UV trnsmittnce of the pure crem+1wt% lignin ws higher thn tht of LIFE SPF 15 sunscreen lotion. The ltter contined two kinds of ctive ingredients with the totl weight percent over 1wt% (refer to Tle S1 in the supplementry informtion). However, the trnsmittnce of the lignin sunscreens in UVA re, especilly etween 385~4nm ws lower thn tht of SPF 15. It suggested tht lignin is very good nturl cndidte for rod spectrum sunscreens. Lignin dded to sunscreen lotions It is known tht sunscreen effect of the green coffee oil itself is not ovious, ut the oil cn help to improve performnce of the synthetic sunscreen ctive. 6 This sunscreen enhncement hs een ttriuted to ntioxidnts in the green coffee oil. Similrly, lignin is not only nturl sun locker, it is lso well known for ntioxidnt ctivities due to its phenolic hydroxyl groups. Accepted Mnuscript This journl is The Royl Society of Chemistry [yer], [yer], [vol], 2

4 Trnsmittnce Trnsmittnce Pge 3 of 6 Therefore, sunscreen enhncement of the commercil SPF 15 sunscreen lotions with dded lignin ws investigted nd compred with the sunscreen performnce of SPF 3 nd 5 sunscreen products. It cn e seen in Figure 2 tht the UV trnsmittnce of SPF 15-B + 2wt% lignin ws close to tht of SPF 3, ut it ws lower thn tht of SPF 5 in the UVA re, especilly in the rnge of 38~4 nm. The SPF vlues of SPF 15-B lended with different lignin mounts, s well s SPF 3-B nd SPF 5-B, were mesured nd summrized in Tle 2. Unfortuntely, further increse in the lignin mount did not improve the sunscreen effect. When lignin ws incresed to 1wt%, the sunscreen effect disppered nd the SPF level retuned to the originl SPF 15 lotion. This ws minly cused y poor dispersion of lignin in SPF 15-B t such high loding. SPF 15-B with 1wt% lignin dried quickly when it ws distriuted on the trnspore tpe SPF15-B SPF15-B+2wt%lignin SPF15-B+5wt%lignin SPF15-B+1wt%lignin SPF3-B SPF5-B SPF15-L SPF15-L+2wt%lignin SPF15-L+1wt%lignin SPF3-L SPF5-L 3 33 Fig. 2 UV trnsmittnce of the commercil SPF 15 sunscreen lotions contining different lignin mounts in the UVB nd UVA res. The corresponding SPF 3 nd 5 sunscreen lotions re included s reference. () BIOTHERM rnd sunscreen lotions; () LIFE rnd sunscreen lotions. Tle 2. Mesured SPF vlues of the commercil sunscreen lotions nd the sunscreen lotions with different mounts of dded lignin. Lignin (wt%) (15*) (3*) (5*) BIOTHERM LIFE 2.25 ± ± ± ± ± ± ± ± ± ± ±5.9 *Commercil sunscreen lotions with SPF of 15, 3 nd 5, without lignin ddition. The sunscreen effect enhncement in SPF 15-L ws not so ovious with 2wt% lignin ddition. However, when the lignin mount ws incresed to 1wt%, the sunscreen effect ws enhnced drmticlly. The lended lotion not only ecme much etter thn SPF 15-L, ut lso significntly outperformed SPF 5- L, especilly in the UVA re, s shown in Figure 2. The SPF vlue of SPF 15-L+1wt% lignin reched (in Tle 2). SPF 15-L nd SPF 15-B contined different ctive ingredients. It ws lso esier to disperse lignin in SPF 15-L thn in SPF 15-B. Rdition-enhnced sunscreen effect We then evluted photostility of the lignin-modified sunscreen lotions. There could e concern out the service lifetime of lignin s UV locker in the lotions. To our surprise, when the lignin-modified sunscreens were exposed to UV rdition for two hours, the UV sornce in the UVA nd UVB res incresed severl times, s shown in Figure 3. In comprison, there ws little chnge in the UV sornce with the commercil sunscreen lotions without lignin, s shown in Figure 3 nd 3c. This result ws unexpected nd promising. How could the sunscreen performnce of the lignin lotions get etter with UV rdition? We mde effort to elucidte the underlying mechnisms. The first suspect ws the effect of rdition on lignin. The UV-rdited lignin somehow ecme etter UV locker. To vlidte this ssumption, the photostility of pure crem ws used s reference. Different from the lotions, the crem contined no ctive sunscreen ingredients. Figure 3d shows the rdition effect on Crem + 1wt% lignin smple. Although there ws little increse in the UVB re fter two hours of UV rdition, the sornce in the UVA re ws not ovious t ll. Therefore, the rdition effect on lignin lone could not explin the oserved results with the lignin lotions. Another possiility might e some synergistic effect of lignin nd synthetic sunscreen ctives in the lotions, such s homolete, voenzone nd so on. During the two hours of UV rdition, lignin might interct nd/or rect with some ctive ingredients, forming higher performnce UV lockers. We hope this work provoke further studies on the ctul moleculr processes involved in these interctions nd/or rections. It should lso e pointed out tht lignin is n excellent ntioxidnt. Sunscreen ctives such s voenzone nd octinoxte do not hve good photostility nd cn esily form free rdicls y photolysis. 33 Lignin is n effective rdicl scvenger nd stops further formtion of free rdicls. Conclusions Lignin is evluted s nture-inspired rod-spectrum sun locker in sunscreen lotions. As expected, lignin enhnced the sunscreen performnce when it ws dded to commercil sunscreen lotions. However, the enhncement level ws unexpectedly high. The UV sornce of lignin-contining sunscreen lotions incresed severl times. It ws prticulrly interesting to find tht the performnce improved with the UV rdition time. Although the underlying mechnism remined to e elucidted, it ws ttriuted synergistic effect etween lignin nd other sunscreen ctives, s well s ntioxidnt property of lignin. This work demonstrted potentil of lignin in such vluedded pplictions s cosmetics. Accepted Mnuscript This journl is The Royl Society of Chemistry [yer], [yer], [vol], 3

5 Asornce Asornce Asornce Asornce Pge 4 of fter UV fter UV 3 2 efore UV 1.5 efore UV c efore UV fter UV d efore UV fter UV Fig. 3 UV sornce of the sunscreens efore nd fter two-hour UV rdition: () SPF 15-L+1wt% lignin; () SPF 15-L; (c) SPF 3-L; (d) Crem-L+1wt% lignin. Acknowledgements Yong Qin would like to cknowledge the Chin Scholrship Council (CSC) for supporting his visit t McMster. We lso thnk the Nturl Sciences nd Engineering Reserch Council (NSERC) of Cnd for supporting this reserch. Notes nd references Deprtment of Chemicl Engineering, McMster University, Hmilton, Ontrio L8S 4L7, Cnd. E mil: shipingzhu@mcmster.c. School of Chemistry nd Chemicl Engineering, South Chin University of Technology, Gungzhou, 5164, People's Repulic of Chin. E mil: xueqingqiu66@163.com. Electronic Supplementry Informtion (ESI) ville: Active nd inctive ingredients of purchsed sunscreen lotions nd pure crems. See DOI: 1.139/x/ 1 EPA, The urning fcts, United Sttes Air nd Rdition EPA 43-F-6-13 Environmentl Protection (625J) Septemer 26; 2 N. J. Lowe, MD nd FRCP, Dermtol. Clin., 26, 24, Sun protection clothing guide: Shield your skin without sunscreen; clothing. 4 Z. A. Lewick, A. F. Benedetto, D. N. Benoit, W. W. Yu, J. D. Fortner nd V. L. Colvin, J. Neurosci. Res., 211, 13, S.T. Butt nd T. Christensen, Rdit. Prot. Dosimetry, 2, 91, B. G. Chiri, E. Trovtti, É. Pecorro, M. A. Corrê, R. M. B. Cicrelli, S. J. L. Rieiro nd V. L. B Isc, Ind. Crops Prod., 214, 52, P. N. Shenekr, P. S. Ukirde, S. D. Slunkhe, S. T. Sutr, C. S. Mgdum, S. K. Mohite, S. G. Lokpure nd S. M. Metri. Eur. J. Exp. Biol., 214, 4, P. P. Mske, S. G. Lokpure, D. Nimlkr, S. Mlvi nd J. I. D souz, J. Phrm. Res., 213, 7, A. Jrzyck, A. Lewinsk, R. Gncrz nd K. A. Wilk, J. Photochem. Photoiol., B: Biology, 213, 128, S. S. Y. Tn, D. R. McFrlne, J. Upfl, L. A. Edye, W. O. S. Doherty, A. F. Ptti, J. M. Pringle nd J. L. Scott, Green Chem.,29, 11, S. Nnykkr, A. F. Ptti nd K. Sito, Green Chem., 214, 16, Z. J. Wei, Y. Yng, R. Yng nd C. Y. Wng, Green Chem., 212, 14, E. Windeisen nd G. Wegener, in Polymer Science: A Comprehensive Reference, ed. K. Mtyjszewski nd M. Möller, Elsevier, Amsterdm, Oxford, Wlthm, 212, vol. 1, pp E. Windeisen nd G. Wegener, In Sustinle solutions for modern economies, ed. R. Höfer, RSC Pul., Cmridge, 29, Accepted Mnuscript This journl is The Royl Society of Chemistry [yer], [yer], [vol], 4

6 Pge 5 of 6 ch. 9.4, pp O. Lnzlung nd M., Bietti, J. Photochem. Photoiol., B : Biology, 2, 56, S. Brserg, T. Elder nd C. Fely, Chem. Mter., 23, 15, S. I. Flkehg, J. Mrton nd E. Adler, in Lignin structure nd rections, ed. J. Mrton, E-Pulishing Inc., ACS, 1966, vol. 59, ch. 7, pp M. Zimniewsk, J. Btog, E. Bogcz nd B. Romnowsk, Journl of Fier Bioengineering & Informtics, 212, 5, T. Dizhite, G. Telyshev, V. Jurkjne nd U. Viesturs, Bioresour. Technol., 24, 95, X. J. Pn, J. F. Kdl, K. Ehr, N. Gilkes nd J. N. Sddler, J. Agric. Food Chem., 26, 54, M. P. Vinrdell, V. Ugrtondo nd M. Mitjns, Ind. Crops Prod., 28, 27, A. Grcí, M. G. Alriols, G. Spigno nd J. Lid, Biochem. Eng. J., 212, 67, G. Gellerstedt nd G. Henriksson, in Monomers, polymers nd composites from renewle resources, ed. M. N. Belcgem nd A. Gndini. Elsevier, Amsterdm, 28, ch. 9, pp R. J. A. Gosselink, E. de Jong, B. Gurn nd A. Acherli, Ind. Crops Prod., 24, 2, T. Sito, R. H. Brown, M. A. Hunt, D. L. Pickel, J. M. Pickel, J. M. Messmn, F. S. Bker, M. Keller nd A. K. Nskr, Green Chem., 212, 14, M. S. Zhou, X. Q. Qiu, D. J. Yng, H. M. Lou nd X. P. Ouyng, Fuel Process. Technol., 27, 88, X. P. Ouyng, L. X. Ke, X. Q. Qiu, Y. X. Guo nd Y. X. Png, J. Dispersion Sci. Technol., 29, 3, H. R. Wu, F. G. Chen, Q. G. Feng, X. P. Yue. Bioresources, 212, 7, V. Ugrtondo, M. Mitjns, nd M. P. Vinrdell, Bioresour. Technol., 28, 99, M. Tortor, F. Cvlieri, P. Mosesso, F. Ciffrdini, F. Melone nd C. Crestini. Biomcromolecules, 214, 15, A. F. McKinley, B. L. Diffey, CIE J., 1987, 6, Erythem reference ction spectrum nd stndrd erythem dose. Commission Interntionle de l Eclirge Interntionl (CIE) Centrl Bureu. Pul. CIE S7/E, Vienn, Austri, R. M. Syre, J. C. Dowdy, A. J. Gerwig, W. J. Shields nd R. V. Lloyd, Photochem. Photoiol., 25, 81, Accepted Mnuscript This journl is The Royl Society of Chemistry [yer], [yer], [vol], 5

7 Pge 6 of 6 Tle of contents entry Lignin is evluted s nture-inspired rod-spectrum sun locker in sunscreen lotions. Accepted Mnuscript

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