Enzymatic Preparation and Characterization of Spherical Microparticles Composed of Artificial Lignin and TEMPO-Oxidized Cellulose Nanofiber

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

Cole, M.; Lindeque, P.; Halsband, C.; Galloway, T.S. Microplastics as contaminants in the marine environment: A review. Mar.

Pollut. Bull. 2011, 62, 2588–2597. [CrossRef]

Yee, M.S.L.; Hii, L.W.; Looi, C.K.; Lim, W.M.; Wong, S.F.; Kok, Y.Y.; Tan, B.K.; Wong, C.Y.; Leong, C.O. Impact of microplastics and

nanoplastics on human health. Nanomaterials 2021, 11, 496. [CrossRef] [PubMed]

Browne, M.A.; Crump, P.; Niven, S.J.; Teuten, E.; Tonkin, A.; Galloway, T.; Thompson, R. Accumulation of microplastic on

shorelines woldwide: Sources and sinks. Environ. Sci. Technol. 2011, 45, 9175–9179. [CrossRef] [PubMed]

Cheung, P.K.; Fok, L. Characterisation of plastic microbeads in facial scrubs and their estimated emissions in Mainland China.

Water Res. 2017, 122, 53–61. [CrossRef] [PubMed]

Auta, H.S.; Emenike, C.U.; Fauziah, S.H. Distribution and importance of microplastics in the marine environment: A review of

the sources, fate, effects, and potential solutions. Environ. Int. 2017, 102, 165–176. [CrossRef]

El-Habashy, S.E.; Eltaher, H.M.; Gaballah, A.; Zaki, E.I.; Mehanna, R.A.; El-Kamel, A.H. Hybrid bioactive hydroxyapatite/polycaprolactone nanoparticles for enhanced osteogenesis. Mater. Sci. Eng. C 2021, 119, 111599. [CrossRef]

Fan, X.; Zou, Y.; Geng, N.; Liu, J.; Hou, J.; Li, D.; Yang, C.; Li, Y. Investigation on the adsorption and desorption behaviors of

antibiotics by degradable MPs with or without UV ageing process. J. Hazard. Mater. 2021, 401, 123363. [CrossRef]

Im, J.; Jang, E.K.; Yim, D.B.; Kim, J.H.; Cho, K.Y. One-pot fabrication of uniform half-moon-shaped biodegradable microparticles

via microfluidic approach. J. Ind. Eng. Chem. 2020, 90, 152–158. [CrossRef]

Jiang, P.; Jacobs, K.M.; Ohr, M.P.; Swindle-Reilly, K.E. Chitosan-Polycaprolactone Core-Shell Microparticles for Sustained Delivery

of Bevacizumab. Mol. Pharm. 2020, 17, 2570–2584. [CrossRef]

Ge, Y.; Dababneh, F.; Li, L. Economic Evaluation of Lignocellulosic Biofuel Manufacturing Considering Integrated Lignin Waste

Conversion to Hydrocarbon Fuels. Procedia Manuf. 2017, 10, 112–122. [CrossRef]

Wang, Q.; Tian, D.; Hu, J.; Shen, F.; Yang, G.; Zhang, Y.; Deng, S.; Zhang, J.; Zeng, Y.; Hu, Y. Fates of hemicellulose, lignin and

cellulose in concentrated phosphoric acid with hydrogen peroxide (PHP) pretreatment. RSC Adv. 2018, 8, 12714–12723. [CrossRef]

Funahashi, R.; Okita, Y.; Hondo, H.; Zhao, M.; Saito, T.; Isogai, A. Different Conformations of Surface Cellulose Molecules in

Native Cellulose Microfibrils Revealed by Layer-by-Layer Peeling. Biomacromolecules 2017, 18, 3687–3694. [CrossRef] [PubMed]

Daicho, K.; Saito, T.; Fujisawa, S.; Isogai, A. The Crystallinity of Nanocellulose: Dispersion-Induced Disordering of the Grain

Boundary in Biologically Structured Cellulose. ACS Appl. Nano Mater. 2018, 1, 5774–5785. [CrossRef]

Moon, R.J.; Martini, A.; Nairn, J.; Simonsen, J.; Youngblood, J. Cellulose nanomaterials review: Structure, properties and

nanocomposites. Chem. Soc. Rev. 2011, 40, 3941–3994. [CrossRef] [PubMed]

Quinlan, R.J.; Sweeney, M.D.; Lo Leggio, L.; Otten, H.; Poulsen, J.C.N.; Johansen, K.S.; Krogh, K.B.R.M.; Jørgensen, C.I.; Tovborg,

M.; Anthonsen, A.; et al. Insights into the oxidative degradation of cellulose by a copper metalloenzyme that exploits biomass

components. Proc. Natl. Acad. Sci. USA 2011, 108, 15079–15084. [CrossRef]

Tamo, A.K.; Doench, I.; Helguera, A.M.; Hoenders, D.; Walther, A.; Madrazo, A.O. Biodegradation of crystalline cellulose

nanofibers by means of enzyme immobilized-alginate beads and microparticles. Polymers 2020, 12, 1522. [CrossRef]

Shen, Y.; Li, Z.; Huo, Y.Y.; Bao, L.; Gao, B.; Xiao, P.; Hu, X.; Xu, X.W.; Li, J. Structural and Functional Insights Into CmGH1, a

Novel GH39 Family β-Glucosidase From Deep-Sea Bacterium. Front. Microbiol. 2019, 10, 2922. [CrossRef]

Achyuthan, K.E.; Achyuthan, A.M.; Adams, P.D.; Dirk, S.M.; Harper, J.C.; Simmons, B.A.; Singh, A.K. Supramolecular selfassembled chaos: Polyphenolic lignin’s barrier to cost-effective lignocellulosic biofuels. Molecules 2010, 15, 8641–8688. [CrossRef]

Simon, C.; Spriet, C.; Hawkins, S.; Lion, C. Visualizing lignification dynamics in plants with click chemistry: Dual labeling is

BLISS! J. Vis. Exp. 2018, 131, e56947. [CrossRef]

Janusz, G.; Pawlik, A.; Sulej, J.; Swiderska-Burek,

U.; Jarosz-Wilkolazka, A.; Paszczynski,

A. Lignin degradation: Microorganisms,

enzymes involved, genomes analysis and evolution. FEMS Microbiol. Rev. 2017, 41, 941–962. [CrossRef] [PubMed]

Datta, R.; Kelkar, A.; Baraniya, D.; Molaei, A.; Moulick, A.; Meena, R.S.; Formanek, P. Enzymatic degradation of lignin in soil: A

review. Sustainability 2017, 9, 1163. [CrossRef]

Ohta, Y.; Hasegawa, R.; Kurosawa, K.; Maeda, A.H.; Koizumi, T.; Nishimura, H.; Okada, H.; Qu, C.; Saito, K.; Watanabe, T.;

et al. Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin.

ChemSusChem 2017, 10, 425–433. [CrossRef] [PubMed]

Thomas, B.; Raj, M.C.; Athira, B.K.; Rubiyah, H.M.; Joy, J.; Moores, A.; Drisko, G.L.; Sanchez, C. Nanocellulose, a Versatile Green

Platform: From Biosources to Materials and Their Applications. Chem. Rev. 2018, 118, 11575–11625. [CrossRef] [PubMed]

Nanomaterials 2021, 11, 917

24.

25.

26.

27.

28.

29.

30.

31.

32.

33.

34.

35.

36.

37.

38.

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

49.

11 of 12

Yang, X.; Biswas, S.K.; Han, J.; Tanpichai, S.; Li, M.C.; Chen, C.; Zhu, S.; Das, A.K.; Yano, H. Surface and interface engineering for

nanocellulosic advanced materials. Adv. Mater. 2020, 2002264. [CrossRef]

Figueiredo, P.; Lintinen, K.; Hirvonen, J.T.; Kostiainen, M.A.; Santos, H.A. Properties and chemical modifications of lignin:

Towards lignin-based nanomaterials for biomedical applications. Prog. Mater. Sci. 2018, 93, 233–269. [CrossRef]

Lu, Y.; Han, J.; Ding, Q.; Yue, Y.; Xia, C.; Ge, S.; Van Le, Q.; Dou, X.; Sonne, C.; Lam, S.S. TEMPO-oxidized cellulose

nanofibers/polyacrylamide hybrid hydrogel with intrinsic self-recovery and shape memory properties. Cellulose 2021, 8,

1469–1488. [CrossRef]

Iwatake, A.; Nogi, M.; Yano, H. Cellulose nanofiber-reinforced polylactic acid. Compos. Sci. Technol. 2008, 68, 2103–2106.

[CrossRef]

Niu, X.; Liu, Y.; Song, Y.; Han, J.; Pan, H. Rosin modified cellulose nanofiber as a reinforcing and co-antimicrobial agents in

polylactic acid/chitosan composite film for food packaging. Carbohydr. Polym. 2018, 183, 102–109. [CrossRef]

Kanomata, K.; Fukuda, N.; Miyata, T.; Lam, P.Y.; Takano, T.; Tobimatsu, Y.; Kitaoka, T. Lignin-Inspired Surface Modification of

Nanocellulose by Enzyme-Catalyzed Radical Coupling of Coniferyl Alcohol in Pickering Emulsion. ACS Sustain. Chem. Eng.

2020, 8, 1185–1194. [CrossRef]

Gao, H.; Duan, B.; Lu, A.; Deng, H.; Du, Y.; Shi, X.; Zhang, L. Fabrication of cellulose nanofibers from waste brown algae and

their potential application as milk thickeners. Food Hydrocoll. 2018, 79, 473–481. [CrossRef]

Ullah, H.; Santos, H.A.; Khan, T. Applications of bacterial cellulose in food, cosmetics and drug delivery. Cellulose 2016, 23,

2291–2314. [CrossRef]

Yadav, H.M.; Park, J.D.; Kang, H.C.; Kim, J.; Lee, J.J. Cellulose nanofiber composite with bimetallic zeolite imidazole framework

for electrochemical supercapacitors. Nanomaterials 2021, 11, 395. [CrossRef] [PubMed]

Gopakumar, D.A.; Pai, A.R.; Pottathara, Y.B.; Pasquini, D.; Carlos De Morais, L.; Luke, M.; Kalarikkal, N.; Grohens, Y.; Thomas,

S. Cellulose nanofiber-based polyaniline flexible papers as sustainable microwave absorbers in the X-band. ACS Appl. Mater.

Interfaces 2018, 10, 20032–20043. [CrossRef] [PubMed]

Yan, C.; Wang, J.; Kang, W.; Cui, M.; Wang, X.; Foo, C.Y.; Chee, K.J.; Lee, P.S. Highly stretchable piezoresistive graphenenanocellulose nanopaper for strain sensors. Adv. Mater. 2014, 26, 2022–2027. [CrossRef] [PubMed]

Yeasmin, S.; Yeum, J.H.; Ji, B.C.; Choi, J.H. Electrically Conducting Pullulan-Based Nanobiocomposites Using Carbon Nanotubes

and TEMPO Cellulose Nanofibril. Nanomaterials 2021, 11, 602. [CrossRef]

Fujisawa, S.; Kaku, Y.; Kimura, S.; Saito, T. Magnetically Collectable Nanocellulose-Coated Polymer Microparticles by Emulsion

Templating. Langmuir 2020, 36, 9235–9240. [CrossRef]

Fujisawa, S.; Togawa, E.; Kuroda, K.; Saito, T.; Isogai, A. Fabrication of ultrathin nanocellulose shells on tough microparticles via

an emulsion-templated colloidal assembly: Towards versatile carrier materials. Nanoscale 2019, 11, 15004–15009. [CrossRef]

Zhang, B.; Zhang, Z.; Kapar, S.; Ataeian, P.; Da Silva Bernardes, J.; Berry, R.; Zhao, W.; Zhou, G.; Tam, K.C. Microencapsulation of

Phase Change Materials with Polystyrene/Cellulose Nanocrystal Hybrid Shell via Pickering Emulsion Polymerization. ACS

Sustain. Chem. Eng. 2019, 7, 17756–17767. [CrossRef]

Fujisawa, S.; Togawa, E.; Kuroda, K. Facile Route to Transparent, Strong, and Thermally Stable Nanocellulose/Polymer Nanocomposites from an Aqueous Pickering Emulsion. Biomacromolecules 2017, 18, 266–271. [CrossRef] [PubMed]

Beisl, S.; Miltner, A.; Friedl, A. Lignin from micro- to nanosize: Production methods. Int. J. Mol. Sci. 2017, 18, 2367. [CrossRef]

[PubMed]

Mishra, P.K.; Ekielski, A. The self-assembly of lignin and its application in nanoparticle synthesis: A short review. Nanomaterials

2019, 9, 243. [CrossRef]

Cathala, B.; Saake, B.; Faix, O.; Monties, B. Evaluation of the reproducibility of the synthesis of dehydrogenation polymer models

of lignin. Polym. Degrad. Stab. 1998, 59, 65–69. [CrossRef]

Touzel, J.P.; Chabbert, B.; Monties, B.; Debeire, P.; Cathala, B. Synthesis and characterization of dehydrogenation polymers in

Gluconacetobacter xylinus cellulose and cellulose/pectin composite. J. Agric. Food Chem. 2003, 51, 981–986. [CrossRef]

Mi´ci´c, M.; Jeremi´c, M.; Radoti´c, K.; Leblanc, R.M. A comparative study of enzymatically and photochemically polymerized

artificial lignin supramolecular structures using environmental scanning electron microscopy. J. Colloid Interface Sci. 2000, 231.

[CrossRef]

Micic, M.; Radotic, K.; Benitez, I.; Ruano, M.; Jeremic, M.; Moy, V.; Mabrouki, M.; Leblanc, R.M. Topographical characterization

and surface force spectroscopy of the photochemical lignin model compound. Biophys. Chem. 2001, 94, 257–263. [CrossRef]

Muraille, L.; Aguié-Béghin, V.; Chabbert, B.; Molinari, M. Bioinspired lignocellulosic films to understand the mechanical

properties of lignified plant cell walls at nanoscale. Sci. Rep. 2017, 7, 44065. [CrossRef] [PubMed]

Barone, J.R. Composites of Nanocellulose and Lignin-like Polymers. Cellul. Based Compos. New Green Nanomater. 2014, 9783527327,

185–200.

Saito, T.; Nishiyama, Y.; Putaux, J.L.; Vignon, M.; Isogai, A. Homogeneous suspensions of individualized microfibrils from

TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 2006, 7, 1687–1691. [CrossRef] [PubMed]

Jiang, J.; Chen, H.; Liu, L.; Yu, J.; Fan, Y.; Saito, T.; Isogai, A. Influence of chemical and enzymatic TEMPO-mediated oxidation on

chemical structure and nanofibrillation of lignocellulose. ACS Sustain. Chem. Eng. 2020, 8, 14198–14206. [CrossRef]

Nanomaterials 2021, 11, 917

50.

51.

52.

53.

54.

55.

56.

57.

58.

59.

60.

61.

62.

63.

64.

65.

66.

67.

68.

69.

70.

71.

72.

12 of 12

Kisszekelyi, P.; Hardian, R.; Vovusha, H.; Chen, B.; Zeng, X.; Schwingenschlögl, U.; Kupai, J.; Szekely, G. Selective electrocatalytic

oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-diformylfuran: From mechanistic investigations to catalyst recovery.

ChemSusChem 2020, 13, 3127–3136. [CrossRef] [PubMed]

Akhlaghi, Y.; Ghaffari, S.; Attar, H.; Alamir Hoor, A. A rapid hydrolysis method and DABS-Cl derivatization for complete amino

acid analysis of octreotide acetate by reversed phase HPLC. Amino Acids 2015, 47, 2255–2263. [CrossRef] [PubMed]

Sipponen, M.H.; Lange, H.; Ago, M.; Crestini, C. Understanding Lignin Aggregation Processes. A Case Study: Budesonide

Entrapment and Stimuli Controlled Release from Lignin Nanoparticles. ACS Sustain. Chem. Eng. 2018, 6, 9342–9351. [CrossRef]

[PubMed]

Moberg, T.; Sahlin, K.; Yao, K.; Geng, S.; Westman, G.; Zhou, Q.; Oksman, K.; Rigdahl, M. Rheological properties of nanocellulose

suspensions: Effects of fibril/particle dimensions and surface characteristics. Cellulose 2017, 24, 2499–2510. [CrossRef]

Bock, P.; Nousiainen, P.; Elder, T.; Blaukopf, M.; Amer, H.; Zirbs, R.; Potthast, A.; Gierlinger, N. Infrared and Raman spectra of

lignin substructures: Dibenzodioxocin. J. Raman Spectrosc. 2020, 51, 422–431. [CrossRef]

Lin, C.C.; Lin, W.J. Sun protection factor analysis of sunscreens containing titanium dioxide nanoparticles. J. Food Drug Anal.

2011, 19, 1–8. [CrossRef]

Goi, Y.; Fujisawa, S.; Saito, T.; Yamane, K.; Kuroda, K.; Isogai, A. Dual Functions of TEMPO-Oxidized Cellulose Nanofibers in

Oil-in-Water Emulsions: A Pickering Emulsifier and a Unique Dispersion Stabilizer. Langmuir 2019, 35, 10920–10926. [CrossRef]

[PubMed]

Mussatto, A.; Groarke, R.; O’Neill, A.; Obeidi, M.A.; Delaure, Y.; Brabazon, D. Influences of powder morphology and spreading

parameters on the powder bed topography uniformity in powder bed fusion metal additive manufacturing. Addit. Manuf. 2021,

38, 101807.

Dai, L.; Liu, R.; Hu, L.Q.; Zou, Z.F.; Si, C.L. Lignin Nanoparticle as a Novel Green Carrier for the Efficient Delivery of Resveratrol.

ACS Sustain. Chem. Eng. 2017, 5, 8241–8249. [CrossRef]

Bhattacharjee, S. DLS and zeta potential-What they are and what they are not? J. Control. Release 2016, 235, 337–351. [CrossRef]

Park, J.Y.; Park, C.W.; Han, S.Y.; Kwon, G.J.; Kim, N.H.; Lee, S.H. Effects of pH on nanofibrillation of TEMPO-oxidized paper

mulberry bast fibers. Polymers 2019, 11, 414. [CrossRef]

Wu, Y.; Qian, Y.; Zhang, A.; Lou, H.; Yang, D.; Qiu, X. Light Color Dihydroxybenzophenone Grafted Lignin with High UVA/UVB

Absorbance Ratio for Efficient and Safe Natural Sunscreen. Ind. Eng. Chem. Res. 2020, 59, 17057–17068. [CrossRef]

Micic, M.; Radotic, K.; Jeremic, M.; Djikanovic, D.; Kämmer, S.B. Study of the lignin model compound supramolecular structure

by combination of near-field scanning optical microscopy and atomic force microscopy. Colloids Surf. B Biointerfaces 2004, 34,

33–40. [CrossRef] [PubMed]

Da Silva Ferez, D.; Ruggiero, R.; Morais, L.C.; Machado, A.E.H.; Mazea, K. Theoretical and experimental studies on the adsorption

of aromatic compounds onto cellulose. Langmuir 2004, 20, 3151–3158. [CrossRef] [PubMed]

Tarasov, D.; Leitch, M.; Fatehi, P. Lignin-carbohydrate complexes: Properties, applications, analyses, and methods of extraction:

A review. Biotechnol. Biofuels 2018, 11, 269. [CrossRef] [PubMed]

Anchisi, C.; Meloni, M.C.; Maccioni, A.M. Chitosan beads loaded with essential oils in cosmetic formulations. J. Cosmet. Sci. 2006,

57, 205–214. [CrossRef]

Manca, M.L.; Castangia, I.; Zaru, M.; Nácher, A.; Valenti, D.; Fernàndez-Busquets, X.; Fadda, A.M.; Manconi, M. Development of

curcumin loaded sodium hyaluronate immobilized vesicles (hyalurosomes) and their potential on skin inflammation and wound

restoring. Biomaterials 2015, 71, 100–109. [CrossRef]

Zhou, Y.; Qian, Y.; Wang, J.; Qiu, X.; Zeng, H. Bioinspired lignin-polydopamine nanocapsules with strong bioadhesion for

long-acting and high-performance natural sunscreens. Biomacromolecules 2020, 21, 3231–3241. [CrossRef] [PubMed]

Fertah, M.; Belfkira, A.; Taourirte, M.; Brouillette, F. Controlled release of diclofenac by a new system based on a cellulosic

substrate and calcium alginate. BioResources 2015, 10, 5932–5948. [CrossRef]

Chin, S.F.; Jimmy, F.B.; Pang, S.C. Size controlled fabrication of cellulose nanoparticles for drug delivery applications. J. Drug

Deliv. Sci. Technol. 2018, 43, 262–266. [CrossRef]

Maeno, K. Direct Quantification of Natural Moisturizing Factors in Stratum Corneum using Direct Analysis in Real Time Mass

Spectrometry with Inkjet-Printing Technique. Sci. Rep. 2019, 9, 17789. [CrossRef]

Izawa, H.; Miyazaki, Y.; Ifuku, S.; Morimoto, M.; Saimoto, H. Fully biobased oligophenolic nanoparticle prepared by horseradish

peroxidase-catalyzed polymerization. Chem. Lett. 2016, 45, 631–633. [CrossRef]

Li, Z.; Renneckar, S.; Barone, J.R. Nanocomposites prepared by in situ enzymatic polymerization of phenol with TEMPO-oxidized

nanocellulose. Cellulose 2010, 17, 57–68. [CrossRef]

...