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Engineering of Industrial Kraft Lignin: the Role of Esterification Methods in Lignin Nanoparticle Self-assembly
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Wood Chemistry and Pulp Technology.ORCID iD: 0009-0009-6424-127X
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.ORCID iD: 0000-0002-5661-0874
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.ORCID iD: 0000-0002-7880-3888
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Wood Chemistry and Pulp Technology.ORCID iD: 0000-0001-8817-2031
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(English)In: Article in journal (Other academic) Submitted
Abstract [en]

Lignin nanoparticles (LNPs) are gaining increased attention in composite materials, cosmetics and pharmaceutical applications, where the particle homogeneity, morphology and surface properties are critical for performances. In this study, industrial kraft lignin derived from softwood (spruce) and hardwood (eucalyptus) were employed as precursors for the fabrication of lignin nanoparticles with tunable physicochemical properties. Robust esterification strategies were employed to introduce linear ester groups with varying chain lengths, in order to systematically investigate the effects of hydrophilic/hydrophobic balance on lignin nanoparticle formation via solvent-shifting self-assembly. Successful esterification of lignin was confirmed by FTIR, 31P NMR, HSQC and SEC, with the improvements in morphological control and modifications in surface characteristics of the resulting lignin nanoparticles validated by TEM, DLS, 1H NMR and contact angle measurements. 

Our results demonstrate that esterification strategies significantly influence the self-assembly mechanisms of lignin nanoparticles, enabling improved control over particle size uniformity and surface hydrophobicity particularly in systems with sufficient long-chain ester coverage. Based on the findings, we propose a refined two-stage self-assembly mechanism with (i) initial nucleation driven by the stacking of lignin high molecular weight domains to form primary colloidal particles, followed by (ii) the maturation through progressive hydrophobic deposition of lignin lower molecular weight domains onto the particle surfaces. 

This work highlights esterification as an effective method to tailor LNP with regulated morphological properties and modulated surface chemistry, expanding their design flexibility for targeted applications. 

Keywords [en]
Lignin valorization, lignin esterification, lignin nanoparticles, nanoparticle morphology control, self- assembly mechanisms.
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science; Chemistry; Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-363323OAI: oai:DiVA.org:kth-363323DiVA, id: diva2:1957961
Note

QC 20250513

Available from: 2025-05-13 Created: 2025-05-13 Last updated: 2025-05-13Bibliographically approved
In thesis
1. Lignin Nanoparticles: Formation Mechanisms and UV Shielding Potential
Open this publication in new window or tab >>Lignin Nanoparticles: Formation Mechanisms and UV Shielding Potential
2025 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The research presented in this thesis focuses on the valorization of kraft lignin through nanoparticle engineering, with the aim of developing high-value applications for this abundant but underutilized biopolymer. The work integrates two key aspects: (i) the effect of lignin esterification on nanoparticle self-assembly and (ii) the functional application of unmodified lignin nanoparticles (LNPs) in sunscreen formulations.

The first study investigates the self-assembly behavior of lignin nanoparticles through controlled esterification of industrial kraft lignin. By introducing hydrophobic ester groups of varying chain lengths, the research examines the structural and interfacial properties that influence nanoparticle formation. Comprehensive characterization using FTIR, 31P NMR, HSQC, SEC, TEM, and DLS confirms that esterification modulates lignin self-assembly behaviors,allowing for precise control over LNP morphology and surface properties. A refined self-assembly mechanism is proposed to elucidate the competing molecular interactions governing nanoparticle formation, highlighting the role of lignin’s intrinsic heterogeneity in determining aggregation behavior.Building upon these findings, the second study extends the application of engineered LNPs by incorporating them into sunscreen formulations as biobased UV-protective additives. The study demonstrates that LNPs derived from both spruce and eucalyptus kraft lignin enhance UV shielding across the UVB and UVA spectra, with spruce-derived nanoparticles providing superior broad-spectrum coverage. These formulations were further assessed for stability, color, and rheological properties, confirming that LNPs contribute to functional improvements in sunscreen emulsions. The integration of LNPs into cosmetic formulations underscores their potential as sustainable alternatives to conventional UV filters, bridging fundamental nanoparticle research with real-world applications.

Through this research, lignin valorization is advanced by filling the fundamental knowledge gap between structural modification, self-assembly dynamics, and material functionality. The findings contribute to the development of lignin-based nanomaterials for eco-friendly applications, demonstrating how precise chemical modifications can enhance both fundamental understanding and industrial relevance of lignin nanoparticles.

Abstract [sv]

Denna avhandling fokuserar på förädling av kraftlignin genom nanopartikelteknik, med målet att utveckla högvärdiga tillämpningar för denna rikligt förekommande men hittills underutnyttjade biopolymer. Arbetet integrerar två centrala aspekter: (i) effekten av ligninesterifiering på självorganisering av nanopartiklar samt (ii) den funktionella användningen av omodifierade ligninnanopartiklar (LNP:er) i solskyddsformuleringar.Den första studien undersöker självorganiseringsbeteendet hos ligninnanopartiklar genom kontrollerad esterifiering av industriellt kraftlignin. Genom att introducera hydrofoba estergrupper med varierande kedjelängder studeras de strukturella och interfaciala egenskaper som påverkar nanopartikelbildning. Omfattande karakterisering med FTIR, ³¹P NMR, HSQC, SEC, TEM och DLS bekräftar att esterifiering styr ligninets självorganisering och möjliggör noggrann kontroll av LNP:ers morfologi och ytegenskaper. En avancerad mekanism för självorganisering föreslås för att klargöra betydelsen av de konkurrerande molekylära interaktioner som styr nanopartikelbildningen, med särskilt fokus på ligninets inneboende heterogenitet och dess betydelse för aggregeringsbeteende.Utifrån dessa resultat utforskar den andra studien tillämpningen av tekniskt framställda LNP:er i solskyddsformuleringar, där de fungerar som biobaserade UV-skyddande tillsatser. Studien visar att LNP:er framställda från kraftlignin med både gran- och eukalyptusursprung förbättrar UV-skyddet inom både UVB- och UVA-spektrumet, där nanopartiklar från granlignin uppvisar överlägset bredspektrumskydd. Formuleringarna utvärderades vidare avseende stabilitet, färg och reologiska egenskaper, vilket bekräftade att LNP:er bidrar till funktionella förbättringar i solskyddsemulsioner. Integrationen av LNP:er i kosmetiska formuleringar understryker deras potential som hållbara alternativ till konventionella UV-filter och förenar grundforskning kring nanopartiklar med praktiska tillämpningar.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. p. 56
Series
TRITA-CBH-FOU ; 2025:14
Keywords
Bio-based additives, lignin nanoparticles, renewable nanomaterials, sunscreen formulations, self-assembly, UV protection., Biobaserade tillsatser, förnybara nanomaterial, ligninnanopartiklar, självorganisering, solskyddsformuleringar, UV-skydd.
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-363292 (URN)978-91-8106-293-9 (ISBN)
Presentation
2025-06-10, Rånbyrummet, Teknikringen 56, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20250514

Available from: 2025-05-14 Created: 2025-05-12 Last updated: 2025-11-04Bibliographically approved

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Xu, TaoranRiazanova, AnastasiaLindén, PärHenriksson, GunnarSöderberg, DanielSevastyanova, Olena

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