JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE) ›› 2025, Vol. 60 ›› Issue (10): 127-140.doi: 10.6040/j.issn.1671-9352.0.2025.109

Previous Articles    

pH-responsive mechanism of cuttlefish melanin nanospheres and their effect on photoprotection of hair scales

ZHU Yuanyu1, ZHAO Hongde2, ZHAO Zhiqing1, WANG Xinhao1, WANG Jiqian1, WANG Dong1*   

  1. 1. College of Chemistry and Chemical Engineering, China University of Petroleum(East China), Qingdao 266580, Shandong, China;
    2. Huangdao Customs of the Peoples Republic of China, Qingdao 266000, Shandong, China
  • Published:2025-10-17

PDF (PC)

5

Abstract: The inherent structural heterogeneity and pronounced insolubility of natural cuttlefish melanin, a biomacromolecule, pose critical bottlenecks in material characterization and functional regulation, severely limiting its advanced applications in cosmetics. To overcome these technical limitations, this study innovatively employed a pH-modulated structural remodeling strategy to systematically elucidate the structure-function relationships governing its solubility evolution and functional enhancement. Multi-scale structural analyzed(SEM/TEM)reveal that alkaline treatment induced a phase transition from native compact spherical particles(neutral pH)to fibrous-amorphous composited with elevated surface activity. This structural reconfiguration enhanced aqueous solubility and interfacial binding capacity compared to native melanin. Using human hair fibers as a photodamage protection model, FT-IR spectroscopy confirmed stable keratin-melanin complex formation through reconstructed hydrogen-bond networks following alkaline treatment. UV-Vis spectroscopy demonstrated an improvement in UVA/UVB absorption efficiency(280-400 nm wavelength range). Notably, confocal microscopy revealed that modified melanin forms continuous photoprotective films within cuticle interstices, achieved lower UV reflectivity compared to the discrete distribution pattern of native melanin. This research established a dual theoretical-technical framework for developing marine biomass-derived advanced photoprotective cosmeceuticals, offering insights into biomacromolecule functionalization through supramolecular restructuring.

Key words: cuttlefish melanin, pH sensitivity, light protection

CLC Number: 

  • O648
[1] AYU SHAZWANI Z, RABETA M S. Enzymatic hydrolysis as an approach toproduce alternative protein from cephalopods ink powder:a short review[J]. Food Research, 2020, 4(5):1383-1390.
[2] PYO J, JU K Y, LEE J K. Artificial pheomelanin nanoparticles and their photo-sensitization properties[J]. Journal of Photochemistry and Photobiology B:Biology, 2016, 160:330-335.
[3] XIE J W, LI H Y, CHE H X, et al. Extraction, physicochemicalcharacterisation, and bioactive properties of ink melanin from cuttlefish(Sepia esculenta)[J]. International Journal of Food Science & Technology, 2021, 56(7):3627-3640.
[4] LIN Z J, LIU L Z, WANG W, et al. The role and mechanism of polydopamine and cuttlefish ink melanin carrying copper ion nanoparticles in antibacterial properties and promoting wound healing[J]. Biomaterials Science, 2021, 9(17):5951-5964.
[5] POTA G, ZANFARDINO A, DI NAPOLI M, et al. Bioinspired antibacterial PVA/melanin-TiO2 hybrid nanoparticles: the role of poly-vinyl-alcohol on their self-assembly and biocide activity[J]. Colloids and Surfaces B: Biointerfaces, 2021, 202:111671.
[6] MENTER J M, PATTA A M, HOLLINS T D, et al. Photoprotection of mammalian acid-soluble collagen by cuttlefish sepia melaninin vitro[J]. Photochemistry and Photobiology, 1998, 68(4):532-537.
[7] BETTINGER C J, BRUGGEMAN J P, MISRA A, et al. Biocompatibility of biodegradable semiconducting melanin films for nerve tissue engineering[J]. Biomaterials, 2009, 30(17):3050-3057.
[8] PAULIN J V, BATAGIN-NETO A, NAYDENOV B, et al. High-field/high-frequency EPR spectroscopy on synthetic melanin: on the origin of carbon-centered radicals[J]. Materials Advances, 2021, 2(19):6297-6305.
[9] CUZZUBBO S, CARPENTIER A F. Applications of melanin and melanin-like nanoparticles in cancer therapy: a review of recent advances[J]. Cancers, 2021, 13(6):1463.
[10] GALVÁN I, WAKAMATSU K. Color measurement of the animal integument predicts the content of specific melanin forms[J]. RSC Advances, 2016, 6(82):79135-79142.
[11] SUGUMARAN M. Comparative biochemistry ofeumelanogenesis and the protective roles of phenoloxidase and melanin in insects[J]. Pigment Cell Research, 2002, 15(1):2-9.
[12] DMELLO S, FINLAY G, BAGULEY B, et al. Signaling pathways in melanogenesis[J]. International Journal of Molecular Sciences, 2016, 17(7):1144.
[13] KUNDU R V, MHLABA J M, RANGEL S M, et al. The convergence theory for vitiligo: a reappraisal[J]. Experimental Dermatology, 2019, 28(6):647-655.
[14] SLOMINSKI A, WORTSMAN J, PLONKA PM, et al. Hair follicle pigmentation[J]. Journal of Investigative Dermatology, 2005, 124(1):13-21.
[15] SLOMINSKI A, TOBIN D J, SHIBAHARA S, et al. Melanin pigmentation in mammalian skin and its hormonal regulation[J]. Physiological Reviews, 2004, 84(4):1155-1228.
[16] VAHIDZADEH E, KALRA A P, SHANKAR K. Melanin-based electronics: From proton conductors to photovoltaics and beyond[J]. Biosensors & Bioelectronics, 2018, 122:127-139.
[17] SOLANO F. Photoprotection and skin pigmentation: melanin-relatedmolecules and some other new agents obtained from natural sources[J]. Molecules, 2020, 25(7):1537.
[18] GHATTAVI K, HOMAEI A, KAMRANI E, et al. Melanin pigment derived from marine organisms and its industrial applications[J]. Dyes and Pigments, 2022, 201:110214.
[19] CAVALLINI C, VITIELLO G, ADINOLFI B, et al. Melanin and melanin-like hybrid materials in regenerative medicine[J]. Nanomaterials, 2020, 10(8):1518.
[20] KIM D J, JU K Y, LEE J K. The synthetic melanin nanoparticles having an excellent binding capacity of heavy metal ions[J]. Bulletin of the Korean Chemical Society, 2012, 33(11):3788-3792.
[21] PEZZELLA A, DISCHIA M, NAPOLITANO A, et al. An integrated approach to the structure of Sepia melanin. Evidence for a high proportion of degraded 5, 6-dihydroxyindole-2-carboxylic acid units in the pigment backbone[J]. Tetrahedron, 1997, 53(24):8281-8286.
[22] XUE C H, LI H G, GUO X J, et al. Superhydrophobic anti-icing coatings with self-deicing property using melanin nanoparticles from cuttlefish juice[J]. Chemical Engineering Journal, 2021, 424:130553.
[23] ESSID I, AROUSSIA H, SOUFI E, et al. Improving quality of smoked sardine fillets by soaking in cuttlefish ink[J]. Food Science and Technology, 2022, 42:e65020.
[24] SONG C H, WU X Y, WANG Y, et al. Cuttlefish-inspired photo-responsive antibacterial microparticles with natural melanin nanoparticles spray[J]. Small, 2024, 20(19):2310444.
[25] MORITA T, MATSUURA T, IZAWA H, et al. Melanin upcycling:creation of polymeric materials from melanin decomposition products[J]. ACS Sustainable Chemistry & Engineering, 2024, 12(18):7115-7125.
[26] GAETA M, BARCELLONA M, PURRELLO R, et al. Hybrid Porphyrin/DOPA-melanin film as self-assembled material and smart device for dye-pollutant removal in water[J]. Chemical Engineering Journal, 2022, 433:133262.
[27] SAJJAN S S. Properties and functions of melanin pigment from klebsiella sp. GSK[J]. Korean Journal of Microbiology and Biotechnology, 2013, 41(1):60-69.
[28] GUO X, CHEN S G, HU Y Q, et al. Preparation of water-soluble melanin from squid ink using ultrasound-assisted degradation and its anti-oxidant activity[J]. Journal of Food Science and Technology, 2014, 51(12):3680-3690.
[29] WATT A A R, BOTHMA J P, MEREDITH P. The supramolecular structure of melanin[J]. Soft Matter, 2009, 5(19):3754-3760.
[30] MBONYIRYIVUZE A, NURU Z Y, DIOPNGOM B, et al. Morphological and chemical composition characterization of commercial sepia melanin[J]. American Journal of Nanomaterials, 2015, 3(1):22-27.
[31] JAKUBIAK P, LACK F, THUN J, et al. Influence of melanin characteristics on drug binding properties[J]. Molecular Pharmaceutics, 2019, 16(6):2549-2556.
[32] CHEN J L, ZHANG Y Y, WU F G, et al. Cellulose nanofiber/melanin hybrid aerogel supported phase change materials with improved photothermal conversion efficiency and superior energy storage density[J]. Cellulose, 2021, 28(15):9739-9750.
[33] ADHYARU B B, AKHMEDOV N G, KATRITZKY A R, et al. Solid-state cross-polarization magic angle spinning 13C and 15N NMR characterization of Sepia melanin, Sepia melanin free acid and human hair melanin in comparison with several model compounds[J]. Magnetic Resonance in Chemistry, 2003, 41(6):466-474.
[34] BINSI P K, MUHAMED ASHRAF P, PARVATHY U, et al. Photo-protective effect of cuttlefish ink melanin on human hair[J]. Journal of Applied Polymer Science, 2022, 139(7):51631.
[35] CENTENO S A, SHAMIR J. Surface enhanced Raman scattering(SERS)and FTIR characterization of the sepia melanin pigment used in works of art[J]. Journal of Molecular Structure, 2008, 873(1/2/3):149-159.
[36] PAKDEL E, XIE W J, WANG J F, et al. Superhydrophobic natural melanin-coated cotton with excellent UV protection and personal thermal management functionality[J]. Chemical Engineering Journal, 2022, 433:133688.
[37] JALMI P, BODKE P, WAHIDULLAH S, et al. The fungus Gliocephalotrichum simplex as a source of abundant, extracellular melanin for biotechnological applications[J]. World Journal of Microbiology and Biotechnology, 2012, 28(2):505-512.
[38] WANG Y, WANG X F, LI T, et al. Effects of melanin on optical behavior of polymer:from natural pigment to materials applications[J]. ACS Applied Materials & Interfaces, 2018, 10(15):13100-13106.
[1] Juan GAO,Xiao-lin WANG,Heinz HOFFMANN,Jing-cheng HAO. Ionic liquid gels [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2019, 54(1): 1-18.
[2] ZHANG Yao-jun, WAN Gang-qiang, YAN Lei, MA Qing-chang, LI Dong-xiang, ZHAO Ji-kuan. Assembled nanostructures of ZnO nanorods prepared by seed growth method [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2016, 51(1): 14-19.
[3] ZHAO Guo-ping, CHEN Guo-hui . Stabilization of CTAB/C4H9OH/C7H16/H2O micro-emulsion system [J]. J4, 2007, 42(11): 19-22 .
[4] ZHOU Song, NING Hualong, CHEN Xiangyan, FENG Yujiao, XU Wenlong. Self-powered hydrogel sensors and their applications [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2025, 60(10): 79-104.
[5] HAN Xinxin, LI Mengqi, ZHANG Peiyu, CUI Jiwei. Synthesis and application of biosurfactants [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2025, 60(10): 13-22.
[6] MA Wenchao, DU Na, HOU Wanguo. Surface tension and adsorption behavior of liquid homogeneous mixtures [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2025, 60(10): 105-116.
[7] LIU Xinyi, LI Jieling, WANG Anhe, LI Qi, BAI Shuo. Preparation of silk fibroin enhanced peptide self-assembled hydrogel and its application in the construction of tumor organoids [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2025, 60(10): 117-126.
[8] FENG Sheng-yu, CHEN Zi-xu, WANG Deng-xu,. Polysiloxane-based fluorescent materials [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2021, 56(10): 99-112.
[9] LI Guangle, YAN Xuehai. Interfacial tension of biomolecular condensates [J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2025, 60(10): 1-12.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed   
No Suggested Reading articles found!
Copyright 2018 © Editorial office of JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE)
Supported by Beijing Magtech Co.Ltd