{"id":{"repo_id":"aalto","oai_identifier":"oai:aaltodoc.aalto.fi:123456789/124629"},"canonical_url":"https://search.dev.ndltd.org/etd/aalto/oai:aaltodoc.aalto.fi:123456789/124629","repository":{"repo_id":"aalto","name":"Aalto University","base_url":"https://aaltodoc.aalto.fi/server/oai/request"},"display":{"title":"Computational modelling of adsorption and aggregation in bio oils at multiple length scales","abstract":"Surfactants in apolar solvents, such as common bio oils self-assemble into various colloidal assemblies, for example reverse micelles. The assemblies may also adsorb at interfaces. The shape and size of these assemblies is sensitive to factors such as surfactant chemistry, concentration, temperature, as well as the presence of co-surfactants, water, and other additives. Although the responses are qualitatively understood in chemical engineering processes, molecular scale understanding of surfactant assembly in apolar solvent environments remains sparse. In this thesis, self-assembly and adsorption of surfactants and colloidal species at solid – liquid interfaces in bio oils is critically assessed using three modelling approaches applicable to research questions at different length and time scales: atomistic detail classical molecular dynamics (MD), coarse-grained dissipative particle dynamics (DPD), and equilibrium state thermodynamics modelling. This combined approach, together with comparison to real chemical systems, allows discerning the effect of individual molecular features and e.g., hydration on adsorption strength and aggregation propensity in bio oils, but also simulation of large scale adsorption and aggregation equilibrium structures. The results presented identify the driving forces of adsorption and aggregation equilibria of bio surfactants, mostly lipids, in common bio oils. On the atomistic scale, hydrogen bonding and electrostatic interactions drive adsorption of single molecules. The interactions are affected by the presence and steric availability of functional groups, as well as, adsorbent surface chemistry and density of adsorption site functional groups. This may result in competitive intra-surface interactions. Water in the bio oil may mediate adsorption via water bridging. The findings show that surfactant aggregate in oil following a step-wise aggregation response, even at low surfactant concentrations and in the absence of water. Addition of water promotes growth and elongation of the aggregates. The surface packing is tunable by adsorbate chemistry, mainly surfactant head group charge, oil water content, and adsorbent surface hydrophilicity. On hydrophilic surfaces, water also acts as a competitive wetting agent. Overall, this thesis provides via multi scale modelling methods guidelines for understanding and manipulating surfactant adsorption/aggregation response in bio oils in terms of molecular architecture, oil water content, and adsorbent chemistry. The work also highlights the challenges and provides solutions associated with modelling self-assembly in apolar environments with sensitive self-assembly and adsorption equilibria.","abstract_html":"Surfactants in apolar solvents, such as common bio oils self-assemble into various colloidal assemblies, for example reverse micelles. The assemblies may also adsorb at interfaces. The shape and size of these assemblies is sensitive to factors such as surfactant chemistry, concentration, temperature, as well as the presence of co-surfactants, water, and other additives. Although the responses are qualitatively understood in chemical engineering processes, molecular scale understanding of surfactant assembly in apolar solvent environments remains sparse. In this thesis, self-assembly and adsorption of surfactants and colloidal species at solid – liquid interfaces in bio oils is critically assessed using three modelling approaches applicable to research questions at different length and time scales: atomistic detail classical molecular dynamics (MD), coarse-grained dissipative particle dynamics (DPD), and equilibrium state thermodynamics modelling. This combined approach, together with comparison to real chemical systems, allows discerning the effect of individual molecular features and e.g., hydration on adsorption strength and aggregation propensity in bio oils, but also simulation of large scale adsorption and aggregation equilibrium structures. The results presented identify the driving forces of adsorption and aggregation equilibria of bio surfactants, mostly lipids, in common bio oils. On the atomistic scale, hydrogen bonding and electrostatic interactions drive adsorption of single molecules. The interactions are affected by the presence and steric availability of functional groups, as well as, adsorbent surface chemistry and density of adsorption site functional groups. This may result in competitive intra-surface interactions. Water in the bio oil may mediate adsorption via water bridging. The findings show that surfactant aggregate in oil following a step-wise aggregation response, even at low surfactant concentrations and in the absence of water. Addition of water promotes growth and elongation of the aggregates. The surface packing is tunable by adsorbate chemistry, mainly surfactant head group charge, oil water content, and adsorbent surface hydrophilicity. On hydrophilic surfaces, water also acts as a competitive wetting agent. Overall, this thesis provides via multi scale modelling methods guidelines for understanding and manipulating surfactant adsorption/aggregation response in bio oils in terms of molecular architecture, oil water content, and adsorbent chemistry. The work also highlights the challenges and provides solutions associated with modelling self-assembly in apolar environments with sensitive self-assembly and adsorption equilibria.","abstract_has_math":false,"creators":["Vuorte, Maisa"],"institution":"Aalto University","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Kemian ja materiaalitieteen laitos","school":null,"contributors":["Aalto-yliopisto","Aalto University"],"advisors":["Sammalkorpi, Maria, D.Sc. (Tech), Aalto University, Soft Materials Modelling, Finland","Laasonen, Kari, Prof., Aalto University, Computational Chemistry, Finland"],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023","date_published":"2023","updated_at":"2026-08-21T16:42:07Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://aaltodoc.aalto.fi/handle/123456789/124629","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"source_record":{"url":"https://aaltodoc.aalto.fi/server/oai/request?verb=GetRecord&metadataPrefix=dim&identifier=oai%3Aaaltodoc.aalto.fi%3A123456789%2F124629","prefix":"dim"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Aalto-yliopisto","Aalto University"]},{"key":"dc:contributor.advisor","label":"Advisor","values":["Sammalkorpi, Maria, D.Sc. (Tech), Aalto University, Soft Materials Modelling, Finland"]},{"key":"dc:contributor.department","label":"Department","values":["Kemian ja materiaalitieteen laitos","Department of Chemistry and Materials Science"]},{"key":"dc:contributor.supervisor","label":"Supervisor","values":["Laasonen, Kari, Prof., Aalto University, Computational Chemistry, Finland"]},{"key":"dc:creator","label":"Author","values":["Vuorte, Maisa"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2023-11-28T10:00:22Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2023-11-28T10:00:22Z"]},{"key":"dc:date.issued","label":"Date","values":["2023"]},{"key":"dc:publisher","label":"Institution","values":["Aalto University","Aalto-yliopisto"]},{"key":"dc:type","label":"Dc Type","values":["G5 Artikkeliväitöskirja"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["text"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://aaltodoc.aalto.fi/handle/123456789/124629"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Surfactants in apolar solvents, such as common bio oils self-assemble into various colloidal assemblies, for example reverse micelles. The assemblies may also adsorb at interfaces. The shape and size of these assemblies is sensitive to factors such as surfactant chemistry, concentration, temperature, as well as the presence of co-surfactants, water, and other additives. Although the responses are qualitatively understood in chemical engineering processes, molecular scale understanding of surfactant assembly in apolar solvent environments remains sparse. In this thesis, self-assembly and adsorption of surfactants and colloidal species at solid – liquid interfaces in bio oils is critically assessed using three modelling approaches applicable to research questions at different length and time scales: atomistic detail classical molecular dynamics (MD), coarse-grained dissipative particle dynamics (DPD), and equilibrium state thermodynamics modelling. This combined approach, together with comparison to real chemical systems, allows discerning the effect of individual molecular features and e.g., hydration on adsorption strength and aggregation propensity in bio oils, but also simulation of large scale adsorption and aggregation equilibrium structures. The results presented identify the driving forces of adsorption and aggregation equilibria of bio surfactants, mostly lipids, in common bio oils. On the atomistic scale, hydrogen bonding and electrostatic interactions drive adsorption of single molecules. The interactions are affected by the presence and steric availability of functional groups, as well as, adsorbent surface chemistry and density of adsorption site functional groups. This may result in competitive intra-surface interactions. Water in the bio oil may mediate adsorption via water bridging. The findings show that surfactant aggregate in oil following a step-wise aggregation response, even at low surfactant concentrations and in the absence of water. Addition of water promotes growth and elongation of the aggregates. The surface packing is tunable by adsorbate chemistry, mainly surfactant head group charge, oil water content, and adsorbent surface hydrophilicity. On hydrophilic surfaces, water also acts as a competitive wetting agent. Overall, this thesis provides via multi scale modelling methods guidelines for understanding and manipulating surfactant adsorption/aggregation response in bio oils in terms of molecular architecture, oil water content, and adsorbent chemistry. The work also highlights the challenges and provides solutions associated with modelling self-assembly in apolar environments with sensitive self-assembly and adsorption equilibria.","Surfaktantit apolaarisissa liuottimissa kuten bioöljyissä itsejärjestäytyvät erilaisiksi kolloidisiksi rakenteiksi, mukaan lukien käänteismiselleiksi. Nämä surfaktanttirakenteet adsorboituvat rajapinnoille. Muodostuneiden surfaktanttirakenteiden muoto ja koko ovat herkkiä surfaktantin molekyylirakenteelle, pitoisuudelle, lämpötilalle, sekä muiden pinta-aktiivisten aineiden, veden ja lisäaineiden läsnäololle. Tällä hetkellä ilmiön ymmärrys kemian prosessitekniikan näkökulmasta on vahvasti kvalitatiivinen, ja kuva molekyylitasolla tapahtuvasta itsejärjestäytymisestä apolaarissa liuoksessa on puutteellinen. Tässä väitöskirjassa tarkastellaan surfaktanttien itsejärjestäytymistä apolaarisessa liuoksessa (bioöljyssä), sekä adsorptiota neste – kiinteä aine rajapinnassa. Ilmiöitä lähestytään kolmella eri pituus- ja aikaskaalan mallinnusmenetelmällä: atomistisella klassisella molekyylidynamiikalla (MD), karkeistetulla dissipatiivisella partikkelidynamiikalla (DPD) ja tasapainotilan termodynamiikan mallinnuksella. Monimuotoiset mallinnusmenetelmät ja vertailu kokeellisiin tuloksiin mahdollistaa yksittäisten molekyyliominaisuuksien ja esimerkiksi hydrataation vaikutuksen eristämisen bioöljyjen adsorptiovoimakkuuteen ja aggregaatiotaipumukseen, sekä suurienkin adsorptio- ja aggregaatiotasapainorakenteiden simuloinnin. Väitöskirjan tulokset täydentävät kuvaa biosurfaktanttien, pääasiassa lipidien, adsorptio- ja aggregaatiotasapainoa ajavista voimista bioöljyissä. Atomistisella tasolla vetysidokset ja sähköstaattiset vuorovaikutukset määrittävät yksittäisten molekyylien adsorption. Adsorptiovahvuuteen vaikuttavat molekyylien funktionaaliset ryhmät, ryhmien steriinen saatavuus, sekä adsorptiopinnan kemia ja pinnan funktionaalisten ryhmien tiheys. Viimeksi mainittu voi johtaa kilpaileviin pinnansisäisiin vuorovaikutuksiin. Vesi öljyssä voi myös muodostaa vesisillan adsorboituvan molekyylin ja pinnan välille. Esitetyt tulokset osoittavat, että surfaktantit aggregoituvat öljyssä vaiheittain alhaisilla surfaktanttipitoisuuksilla ja ilman vettä. Vesi öljyssä edistää aggregaattien muodostumista ja kasvua riippuen aggregaatin muodosta, sekä pääryhmän poolisuudesta ja koosta. Adsorptiossa surfaktanttien pakkautuminen pinnalla riippuu adsorbaatin molekyylirakenteesta, öljyn vesipitoisuudesta ja adsorbentin pinnan hydrofiilisuudesta. Hydrofiilisillä pinnoilla vesi toimii myös kilpailevana adsorbaattina. Väitöskirjan tulokset auttavat ymmärtämään surfaktanttien adsorptio- ja aggregaatiovasteen riippuvuutta ja säädeltävyyttä molekyyliarkkitehtuurin, öljyn vesipitoisuuden ja adsorptiokemian näkökulmasta, perustuen monen eri mittakaavan mallinnusmenetelmiin. Työ tuo esiin myös haasteet herkkien itsejärjestäytymistasapainosysteemien mallintamisessa apolaarisissa ympäristöissä."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Computational modelling of adsorption and aggregation in bio oils at multiple length scales","Adsorption ja aggregaation laskennallinen mallinnus bio öljyissa monella eri mittaskaalalla"]}]}],"canonical_facts":{"dc:contributor":["Aalto-yliopisto","Aalto University"],"dc:contributor.advisor":["Sammalkorpi, Maria, D.Sc. (Tech), Aalto University, Soft Materials Modelling, Finland"],"dc:contributor.department":["Kemian ja materiaalitieteen laitos","Department of Chemistry and Materials Science"],"dc:contributor.supervisor":["Laasonen, Kari, Prof., Aalto University, Computational Chemistry, Finland"],"dc:creator":["Vuorte, Maisa"],"dc:date.accessioned":["2023-11-28T10:00:22Z"],"dc:date.available":["2023-11-28T10:00:22Z"],"dc:date.issued":["2023"],"dc:description.abstract":["Surfactants in apolar solvents, such as common bio oils self-assemble into various colloidal assemblies, for example reverse micelles. The assemblies may also adsorb at interfaces. The shape and size of these assemblies is sensitive to factors such as surfactant chemistry, concentration, temperature, as well as the presence of co-surfactants, water, and other additives. Although the responses are qualitatively understood in chemical engineering processes, molecular scale understanding of surfactant assembly in apolar solvent environments remains sparse. In this thesis, self-assembly and adsorption of surfactants and colloidal species at solid – liquid interfaces in bio oils is critically assessed using three modelling approaches applicable to research questions at different length and time scales: atomistic detail classical molecular dynamics (MD), coarse-grained dissipative particle dynamics (DPD), and equilibrium state thermodynamics modelling. This combined approach, together with comparison to real chemical systems, allows discerning the effect of individual molecular features and e.g., hydration on adsorption strength and aggregation propensity in bio oils, but also simulation of large scale adsorption and aggregation equilibrium structures. The results presented identify the driving forces of adsorption and aggregation equilibria of bio surfactants, mostly lipids, in common bio oils. On the atomistic scale, hydrogen bonding and electrostatic interactions drive adsorption of single molecules. The interactions are affected by the presence and steric availability of functional groups, as well as, adsorbent surface chemistry and density of adsorption site functional groups. This may result in competitive intra-surface interactions. Water in the bio oil may mediate adsorption via water bridging. The findings show that surfactant aggregate in oil following a step-wise aggregation response, even at low surfactant concentrations and in the absence of water. Addition of water promotes growth and elongation of the aggregates. The surface packing is tunable by adsorbate chemistry, mainly surfactant head group charge, oil water content, and adsorbent surface hydrophilicity. On hydrophilic surfaces, water also acts as a competitive wetting agent. Overall, this thesis provides via multi scale modelling methods guidelines for understanding and manipulating surfactant adsorption/aggregation response in bio oils in terms of molecular architecture, oil water content, and adsorbent chemistry. The work also highlights the challenges and provides solutions associated with modelling self-assembly in apolar environments with sensitive self-assembly and adsorption equilibria.","Surfaktantit apolaarisissa liuottimissa kuten bioöljyissä itsejärjestäytyvät erilaisiksi kolloidisiksi rakenteiksi, mukaan lukien käänteismiselleiksi. Nämä surfaktanttirakenteet adsorboituvat rajapinnoille. Muodostuneiden surfaktanttirakenteiden muoto ja koko ovat herkkiä surfaktantin molekyylirakenteelle, pitoisuudelle, lämpötilalle, sekä muiden pinta-aktiivisten aineiden, veden ja lisäaineiden läsnäololle. Tällä hetkellä ilmiön ymmärrys kemian prosessitekniikan näkökulmasta on vahvasti kvalitatiivinen, ja kuva molekyylitasolla tapahtuvasta itsejärjestäytymisestä apolaarissa liuoksessa on puutteellinen. Tässä väitöskirjassa tarkastellaan surfaktanttien itsejärjestäytymistä apolaarisessa liuoksessa (bioöljyssä), sekä adsorptiota neste – kiinteä aine rajapinnassa. Ilmiöitä lähestytään kolmella eri pituus- ja aikaskaalan mallinnusmenetelmällä: atomistisella klassisella molekyylidynamiikalla (MD), karkeistetulla dissipatiivisella partikkelidynamiikalla (DPD) ja tasapainotilan termodynamiikan mallinnuksella. Monimuotoiset mallinnusmenetelmät ja vertailu kokeellisiin tuloksiin mahdollistaa yksittäisten molekyyliominaisuuksien ja esimerkiksi hydrataation vaikutuksen eristämisen bioöljyjen adsorptiovoimakkuuteen ja aggregaatiotaipumukseen, sekä suurienkin adsorptio- ja aggregaatiotasapainorakenteiden simuloinnin. Väitöskirjan tulokset täydentävät kuvaa biosurfaktanttien, pääasiassa lipidien, adsorptio- ja aggregaatiotasapainoa ajavista voimista bioöljyissä. Atomistisella tasolla vetysidokset ja sähköstaattiset vuorovaikutukset määrittävät yksittäisten molekyylien adsorption. Adsorptiovahvuuteen vaikuttavat molekyylien funktionaaliset ryhmät, ryhmien steriinen saatavuus, sekä adsorptiopinnan kemia ja pinnan funktionaalisten ryhmien tiheys. Viimeksi mainittu voi johtaa kilpaileviin pinnansisäisiin vuorovaikutuksiin. Vesi öljyssä voi myös muodostaa vesisillan adsorboituvan molekyylin ja pinnan välille. Esitetyt tulokset osoittavat, että surfaktantit aggregoituvat öljyssä vaiheittain alhaisilla surfaktanttipitoisuuksilla ja ilman vettä. Vesi öljyssä edistää aggregaattien muodostumista ja kasvua riippuen aggregaatin muodosta, sekä pääryhmän poolisuudesta ja koosta. Adsorptiossa surfaktanttien pakkautuminen pinnalla riippuu adsorbaatin molekyylirakenteesta, öljyn vesipitoisuudesta ja adsorbentin pinnan hydrofiilisuudesta. Hydrofiilisillä pinnoilla vesi toimii myös kilpailevana adsorbaattina. Väitöskirjan tulokset auttavat ymmärtämään surfaktanttien adsorptio- ja aggregaatiovasteen riippuvuutta ja säädeltävyyttä molekyyliarkkitehtuurin, öljyn vesipitoisuuden ja adsorptiokemian näkökulmasta, perustuen monen eri mittakaavan mallinnusmenetelmiin. Työ tuo esiin myös haasteet herkkien itsejärjestäytymistasapainosysteemien mallintamisessa apolaarisissa ympäristöissä."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://aaltodoc.aalto.fi/handle/123456789/124629"],"dc:language.iso":["en"],"dc:publisher":["Aalto University","Aalto-yliopisto"],"dc:title":["Computational modelling of adsorption and aggregation in bio oils at multiple length scales","Adsorption ja aggregaation laskennallinen mallinnus bio öljyissa monella eri mittaskaalalla"],"dc:type":["G5 Artikkeliväitöskirja"],"dc:type.dcmitype":["text"]},"updated_at":"2026-08-21T16:42:07Z"}