Molecular simulations of crystalline cellulose interfacial interactions

Zhennan Kou

Molecular simulations of crystalline cellulose interfacial interactions

Julkaisun otsikon käännös: Kiteisen nanoselluloosan rajapintavuorovaikutusten molekyylitason simulaatioita

Zhennan Kou

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Kiteinen nanoselluloosa, ja etenkin selluloosan nanokiteet (CNC), on laajasti käytössä monilla aloilla, kuten lääke- ja biolääketieteen materiaaleissa, paperinvalmistuksessa ja elintarviketeollisuudessa, polymeerikomposiittien lujitteena sekä tukimatriisina ja pakkausmateriaalina. CNC-pintojen ja muiden materiaalien väliset vuorovaikutukset voivat vaikuttaa CNC-pohjaisten materiaalien ominaisuuksiin, mikä laajentaa niiden käyttömahdollisuuksia. Tässä väitöskirjassa tutkitaan CNC:n vuorovaikutuksia veden, ionien ja ligniinihiilihydraattikompleksien (LCC) kanssa, sillä nämä vuorovaikutukset voivat merkittävästi vaikuttaa CNC-materiaaleihin, mutta myös puumaisiin ja puupohjaisiin materiaaleihin. Ensimmäiseksi tutkimme CNC-pintojen ja Na+- ja Cl--ionien välisiä vuorovaikutuksia vesiliuoksessa. Tämän jälkeen tutkimme CNC-pintojen ja LCC-yhdisteiden välisiä vuorovaikutuksia. Tutkimustulokset osoittavat, että jo hyvin pieni ionimäärä voi vaikuttaa merkittävästi CNC-pintojen välisiin vuorovaikutuksiin. Tässä tutkimuksessa havaittiin, että 0,25 mM NaCl 0,6 %wt CNCliuoksessa riitti muuttamaan viskositeettia merkittävästi. Tulokset osoittavat, että Na+- ja Cl—ionien läsnäolo voi muuttaa veden dipoliorientaatiota, mikä vaikuttaa CNC:n välisiin vuorovaikutuksiin. Hydrataatiokerroksen järjestäytyminen ionien kohdalla voi lisääntyä. Eri sitoutumiskohdat CNCpinnoilla vaikuttavat CNC-pintojen välisiin vuorovaikutuksiin ja edelleen liuoksen viskositeettiin. Tämä veden molekyylien orientaatiomuutos voi edistää pintojen hydrataatiokerrosten yhdistymistä, mikä lisää kiteisen nanoselluloosan välistä vuorovaikutusta liuoksessa ja siten kasvattaa viskositeettia. LCC-yhdisteiden ja CNC:n väliset vuorovaikutukset ovat riippuvaisia CNC-pinnan kidetasosta. Tutkimme yksinkertaisia LCC-malleja saadaksemme tarkempaa tietoa. Hydrofiiilisten CNCpintojen ja LCC-mallien välinen vuorovaikutus perustui pääasiassa vetysidoksiin, joissa ligniinin rooli korostui silloin, kun hemiselluloosaketjut olivat lyhyitä. Hydrofobisilla CNC-pinnoilla vuorovaikutus tapahtui ensisijaisesti van der Waalsin ja dipoli-dipoli -voimien välityksellä. Tässä väitöskirjassa tutkittiin CNC-pintojen välisiä vuorovaikutuksia. Näitä esiintyy sekä CNCliuoksissa että puupohjaisissa materiaaleissa. Tulokset voivat edistää selluloosapohjaisten materiaalien ominaisuuksien ymmärtämistä ja hallintaa. Löydökset voivat myös auttaa tuotteiden suunnittelussa, mikä voi lisätä tuotannon tehokkuutta ja ympäristöystävällisyyttä.

Julkaisun otsikon käännös	Kiteisen nanoselluloosan rajapintavuorovaikutusten molekyylitason simulaatioita
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Ohjaaja	Sammalkorpi, Maria, Vastuuprofessori Tolmachev, Dmitry, Ohjaaja Vuorte, Maisa, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-64-2433-0
Sähköinen ISBN	978-952-64-2434-7
Tila	Julkaistu - 2025
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

selluloosa
nanokiteinen selluloosa
ligniini-hiilihydraattikompleksi
selluloosakiteiden vuorovaikutukset
molekyylidynamiikkasimulaatiot

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-64-2434-7

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Kemian tekniikan korkeakoulu
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@phdthesis{3ecc434bbb594090aeb240b2d45d7a01,

title = "Molecular simulations of crystalline cellulose interfacial interactions",

abstract = "Crystalline nanocellulose, especially cellulose nanocrystals (CNCs), is widely used in many fields, such as pharmaceutical and biomedicine materials, paper making and alimentation industries, in reinforcement of polymer composites, but also as support matrices and packaging materials. The interactions between CNC surfaces and other materials can influence the properties of CNCbased materials, which can widen the usage of CNC materials. In this thesis, CNC interactions with water, ions, and lignin-carbohydrate complexes (LCCs) are studied, since these interactions can heavily affect the properties of CNC materials but also the wood-like and wood-based materials. We first studied the interactions between CNC surfaces and Na+ and Cl- ions in water solutions. After that, the interactions between CNC surfaces and LCCs were studied. A very small amount of ions can affect CNC surface interactions strongly. In this thesis research, in a 0.6 \%wt CNC solution, 0.25 mM NaCl in the solution was sufficient to significantly change the viscosity. Our results show that the presence of NaCl as ions can change the water dipole orientation, which influences the interactions between CNCs. The hydration layer ordering at the position of the ion can increase. The change at the binding sites is enough to change the interaction between CNC surfaces, affecting solution viscosity. This kind of water molecule orientation change can help merge the hydration layers of surfaces, which increases the connections of CNCs in solution. Thus the viscosity increased. The interactions between LCCs and CNCs are dependent on the CNC surface crystal facet. We examined simple model LCCs to obtain insight. The main driving force of interaction between hydrophilic CNC surfaces and the model LCCs was hydrogen bonding, with lignin playing a bigger role when the hemicellulose chains are short. For hydrophobic CNC surfaces, the interaction was more through van der Waals and dipole-dipole forces. In summary, interactions between CNC surfaces common in CNC solutions and in wood-like and wood-based materials are studied in this thesis. This can help understanding and control the properties of these materials. The findings may help product design in these fields to be more productive and environment-friendly.",

keywords = "cellulose, nanocrystalline cellulose, lignin-carbohydrate complexes, cellulose surface, interactions, molecular dynamics simulations, selluloosa, nanokiteinen selluloosa, ligniini-hiilihydraattikompleksi, selluloosakiteiden vuorovaikutukset, molekyylidynamiikkasimulaatiot, cellulose, nanocrystalline cellulose, lignin-carbohydrate complexes, cellulose surface, interactions, molecular dynamics simulations",

author = "Zhennan Kou",

year = "2025",

language = "English",

isbn = "978-952-64-2433-0",

series = "Aalto University publication series Doctoral Theses",

publisher = "Aalto University",

number = "48",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Molecular simulations of crystalline cellulose interfacial interactions

AU - Kou, Zhennan

PY - 2025

Y1 - 2025

N2 - Crystalline nanocellulose, especially cellulose nanocrystals (CNCs), is widely used in many fields, such as pharmaceutical and biomedicine materials, paper making and alimentation industries, in reinforcement of polymer composites, but also as support matrices and packaging materials. The interactions between CNC surfaces and other materials can influence the properties of CNCbased materials, which can widen the usage of CNC materials. In this thesis, CNC interactions with water, ions, and lignin-carbohydrate complexes (LCCs) are studied, since these interactions can heavily affect the properties of CNC materials but also the wood-like and wood-based materials. We first studied the interactions between CNC surfaces and Na+ and Cl- ions in water solutions. After that, the interactions between CNC surfaces and LCCs were studied. A very small amount of ions can affect CNC surface interactions strongly. In this thesis research, in a 0.6 %wt CNC solution, 0.25 mM NaCl in the solution was sufficient to significantly change the viscosity. Our results show that the presence of NaCl as ions can change the water dipole orientation, which influences the interactions between CNCs. The hydration layer ordering at the position of the ion can increase. The change at the binding sites is enough to change the interaction between CNC surfaces, affecting solution viscosity. This kind of water molecule orientation change can help merge the hydration layers of surfaces, which increases the connections of CNCs in solution. Thus the viscosity increased. The interactions between LCCs and CNCs are dependent on the CNC surface crystal facet. We examined simple model LCCs to obtain insight. The main driving force of interaction between hydrophilic CNC surfaces and the model LCCs was hydrogen bonding, with lignin playing a bigger role when the hemicellulose chains are short. For hydrophobic CNC surfaces, the interaction was more through van der Waals and dipole-dipole forces. In summary, interactions between CNC surfaces common in CNC solutions and in wood-like and wood-based materials are studied in this thesis. This can help understanding and control the properties of these materials. The findings may help product design in these fields to be more productive and environment-friendly.

AB - Crystalline nanocellulose, especially cellulose nanocrystals (CNCs), is widely used in many fields, such as pharmaceutical and biomedicine materials, paper making and alimentation industries, in reinforcement of polymer composites, but also as support matrices and packaging materials. The interactions between CNC surfaces and other materials can influence the properties of CNCbased materials, which can widen the usage of CNC materials. In this thesis, CNC interactions with water, ions, and lignin-carbohydrate complexes (LCCs) are studied, since these interactions can heavily affect the properties of CNC materials but also the wood-like and wood-based materials. We first studied the interactions between CNC surfaces and Na+ and Cl- ions in water solutions. After that, the interactions between CNC surfaces and LCCs were studied. A very small amount of ions can affect CNC surface interactions strongly. In this thesis research, in a 0.6 %wt CNC solution, 0.25 mM NaCl in the solution was sufficient to significantly change the viscosity. Our results show that the presence of NaCl as ions can change the water dipole orientation, which influences the interactions between CNCs. The hydration layer ordering at the position of the ion can increase. The change at the binding sites is enough to change the interaction between CNC surfaces, affecting solution viscosity. This kind of water molecule orientation change can help merge the hydration layers of surfaces, which increases the connections of CNCs in solution. Thus the viscosity increased. The interactions between LCCs and CNCs are dependent on the CNC surface crystal facet. We examined simple model LCCs to obtain insight. The main driving force of interaction between hydrophilic CNC surfaces and the model LCCs was hydrogen bonding, with lignin playing a bigger role when the hemicellulose chains are short. For hydrophobic CNC surfaces, the interaction was more through van der Waals and dipole-dipole forces. In summary, interactions between CNC surfaces common in CNC solutions and in wood-like and wood-based materials are studied in this thesis. This can help understanding and control the properties of these materials. The findings may help product design in these fields to be more productive and environment-friendly.

KW - cellulose

KW - nanocrystalline cellulose

KW - lignin-carbohydrate complexes

KW - cellulose surface

KW - interactions

KW - molecular dynamics simulations

KW - selluloosa

KW - nanokiteinen selluloosa

KW - ligniini-hiilihydraattikompleksi

KW - selluloosakiteiden vuorovaikutukset

KW - molekyylidynamiikkasimulaatiot

KW - cellulose

KW - nanocrystalline cellulose

KW - lignin-carbohydrate complexes

KW - cellulose surface

KW - interactions

KW - molecular dynamics simulations

M3 - Doctoral Thesis

SN - 978-952-64-2433-0

T3 - Aalto University publication series Doctoral Theses

PB - Aalto University

ER -

Molecular simulations of crystalline cellulose interfacial interactions

Abstrakti

Tutkimusalat

Pääsy asiakirjaan

Sormenjälki

Laitteet

Biotalousinfrastruktuuri

Raaka-aineiden tutkimusinfrastruktuuri

Science-IT

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