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Deakin University
1.
Sultan, Anas M. N.
Biomolecular adsorption at medical implant interfaces: Insights from molecular simulation.
Degree: 2017, Deakin University
URL: http://hdl.handle.net/10536/DRO/DU:30102710 
► Large-scale molecular simulations and first-principles calculations were used to reveal biomolecular adsorption at medical implant interfaces at the atomic scale. This work advances our knowledge…
(more)
▼ Large-scale molecular simulations and first-principles calculations were used to reveal biomolecular adsorption at medical implant
interfaces at the atomic scale. This work advances our knowledge of the critical junction between biological and synthetic matter, and paves the way for the future development of implant technologies with predictive interfacial properties.
Advisors/Committee Members: Walsh, Tiffany.
Subjects/Keywords: aqueous biomaterial interfaces; biomaterials; implant technologies
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APA (6th Edition):
Sultan, A. M. N. (2017). Biomolecular adsorption at medical implant interfaces: Insights from molecular simulation. (Thesis). Deakin University. Retrieved from http://hdl.handle.net/10536/DRO/DU:30102710
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Sultan, Anas M N. “Biomolecular adsorption at medical implant interfaces: Insights from molecular simulation.” 2017. Thesis, Deakin University. Accessed April 13, 2021.
http://hdl.handle.net/10536/DRO/DU:30102710.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Sultan, Anas M N. “Biomolecular adsorption at medical implant interfaces: Insights from molecular simulation.” 2017. Web. 13 Apr 2021.
Vancouver:
Sultan AMN. Biomolecular adsorption at medical implant interfaces: Insights from molecular simulation. [Internet] [Thesis]. Deakin University; 2017. [cited 2021 Apr 13].
Available from: http://hdl.handle.net/10536/DRO/DU:30102710.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Sultan AMN. Biomolecular adsorption at medical implant interfaces: Insights from molecular simulation. [Thesis]. Deakin University; 2017. Available from: http://hdl.handle.net/10536/DRO/DU:30102710
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Cambridge
2.
Sayer, Thomas.
Establishing faithful simulation of polar surfaces in contact with the aqueous phase.
Degree: PhD, 2020, University of Cambridge
URL: https://doi.org/10.17863/CAM.54890
;
https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.810127
► Crystal surfaces which generate polar repeat units are fundamentally unstable on electrostatic grounds. As such, they require a charge-compensation mechanism if they are to exist…
(more)
▼ Crystal surfaces which generate polar repeat units are fundamentally unstable on electrostatic grounds. As such, they require a charge-compensation mechanism if they are to exist at all. In vacuo, this usually presents as a self-ionisation (electronic reconstruction), or a non-stoichiometric reconstruction of the surface region. When a fluid is present, charge can also be provided externally by adsorbates. In this thesis, we will use molecular dynamics (MD) simulation to investigate the potential of an aqueous phase to stabilise several polar surfaces. Firstly, we address certain finite-size effects by using finite field Hamiltonians developed by Stengel, Spaldin and Vanderbilt and recently introduced to MD. We show that for the simple model of a sodium chloride (111) slab, treated with a forcefield, an electrolyte can provide charge compensation. Next, we compare our boundary conditions to those used in published work on polar silver iodide in the context of ice nucleation. We demonstrate that standard `dipole-correction' methods fail to describe not only the crystal, but also the aqueous phase. Moving forwards, we test the robustness of our method by performing ab initio MD on our NaCl (111) slab. This highlights several technical nuances whilst also allowing us to directly evaluate the role of the electronic degrees of freedom in the presence of such polarising conditions. Passing these validating steps, we investigate magnesium oxide in contact with the aqueous phase: firstly the non-polar (100) termination, which exhibits complicated water dissociation at the interface; and secondly the polar (111) termination, which forces us to evaluate our model in the face of some much more aggressive chemistry. Finally, we reflect on all the accrued queries which remain to be tackled by theory and simulation.
Subjects/Keywords: Interfaces; Dielectrics; Molecular Dynamics; Chemistry; Polar Surfaces; Aqueous Electrolyte; Electrostatics
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APA (6th Edition):
Sayer, T. (2020). Establishing faithful simulation of polar surfaces in contact with the aqueous phase. (Doctoral Dissertation). University of Cambridge. Retrieved from https://doi.org/10.17863/CAM.54890 ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.810127
Chicago Manual of Style (16th Edition):
Sayer, Thomas. “Establishing faithful simulation of polar surfaces in contact with the aqueous phase.” 2020. Doctoral Dissertation, University of Cambridge. Accessed April 13, 2021.
https://doi.org/10.17863/CAM.54890 ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.810127.
MLA Handbook (7th Edition):
Sayer, Thomas. “Establishing faithful simulation of polar surfaces in contact with the aqueous phase.” 2020. Web. 13 Apr 2021.
Vancouver:
Sayer T. Establishing faithful simulation of polar surfaces in contact with the aqueous phase. [Internet] [Doctoral dissertation]. University of Cambridge; 2020. [cited 2021 Apr 13].
Available from: https://doi.org/10.17863/CAM.54890 ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.810127.
Council of Science Editors:
Sayer T. Establishing faithful simulation of polar surfaces in contact with the aqueous phase. [Doctoral Dissertation]. University of Cambridge; 2020. Available from: https://doi.org/10.17863/CAM.54890 ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.810127
University of Cambridge
3.
Sayer, Thomas.
Establishing Faithful Simulation of Polar Surfaces in Contact with the Aqueous Phase.
Degree: PhD, 2020, University of Cambridge
URL: https://www.repository.cam.ac.uk/handle/1810/307798
► Crystal surfaces which generate polar repeat units are fundamentally unstable on electrostatic grounds. As such, they require a charge-compensation mechanism if they are to exist…
(more)
▼ Crystal surfaces which generate polar repeat units are fundamentally unstable on electrostatic grounds. As such, they require a charge-compensation mechanism if they are to exist at all. In vacuo, this usually presents as a self-ionisation (electronic reconstruction), or a non-stoichiometric reconstruction of the surface region. When a fluid is present, charge can also be provided externally by adsorbates. In this thesis, we will use molecular dynamics (MD) simulation to investigate the potential of an aqueous phase to stabilise several polar surfaces. Firstly, we address certain finite-size effects by using finite field Hamiltonians developed by Stengel, Spaldin and Vanderbilt and recently introduced to MD. We show that for the simple model of a sodium chloride (111) slab, treated with a forcefield, an electrolyte can provide charge compensation. Next, we compare our boundary conditions to those used in published work on polar silver iodide in the context of ice nucleation. We demonstrate that standard `dipole-correction' methods fail to describe not only the crystal, but also the aqueous phase. Moving forwards, we test the robustness of our method by performing ab initio MD on our NaCl (111) slab. This highlights several technical nuances whilst also allowing us to directly evaluate the role of the electronic degrees of freedom in the presence of such polarising conditions. Passing these validating steps, we investigate magnesium oxide in contact with the aqueous phase: firstly the non-polar (100) termination, which exhibits complicated water dissociation at the interface; and secondly the polar (111) termination, which forces us to evaluate our model in the face of some much more aggressive chemistry. Finally, we reflect on all the accrued queries which remain to be tackled by theory and simulation.
Subjects/Keywords: Interfaces; Dielectrics; Molecular Dynamics; Chemistry; Polar Surfaces; Aqueous Electrolyte; Electrostatics
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APA ·
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APA (6th Edition):
Sayer, T. (2020). Establishing Faithful Simulation of Polar Surfaces in Contact with the Aqueous Phase. (Doctoral Dissertation). University of Cambridge. Retrieved from https://www.repository.cam.ac.uk/handle/1810/307798
Chicago Manual of Style (16th Edition):
Sayer, Thomas. “Establishing Faithful Simulation of Polar Surfaces in Contact with the Aqueous Phase.” 2020. Doctoral Dissertation, University of Cambridge. Accessed April 13, 2021.
https://www.repository.cam.ac.uk/handle/1810/307798.
MLA Handbook (7th Edition):
Sayer, Thomas. “Establishing Faithful Simulation of Polar Surfaces in Contact with the Aqueous Phase.” 2020. Web. 13 Apr 2021.
Vancouver:
Sayer T. Establishing Faithful Simulation of Polar Surfaces in Contact with the Aqueous Phase. [Internet] [Doctoral dissertation]. University of Cambridge; 2020. [cited 2021 Apr 13].
Available from: https://www.repository.cam.ac.uk/handle/1810/307798.
Council of Science Editors:
Sayer T. Establishing Faithful Simulation of Polar Surfaces in Contact with the Aqueous Phase. [Doctoral Dissertation]. University of Cambridge; 2020. Available from: https://www.repository.cam.ac.uk/handle/1810/307798
4.
Pezzotti, Simone.
DFT-MD simulations and theoretical SFG spectroscopy to characterize H-Bonded networks at aqueous interfaces : from hydrophobic to hydrophilic environments : Simulations DFT-MD et spectroscopie SFG théorique pour la caractérisation des interfaces aqueuses : des environnements hydrophobes à hydrophiles.
Degree: Docteur es, Chimie, 2019, Université Paris-Saclay (ComUE)
URL: http://www.theses.fr/2019SACLE008
► Améliorer notre connaissance de la structure de l'eau dans l'environnement spécial offert par une interface est essentiel pour la compréhension de nombreux phénomènes naturels et…
(more)
▼ Améliorer notre connaissance de la structure de l'eau dans l'environnement spécial offert par une interface est essentiel pour la compréhension de nombreux phénomènes naturels et applications technologiques. Pour révéler cette structure interfaciale de l'eau, des techniques capables de fournir des informations microscopiques, de manière sélective, pour cette couche interfaciale (BIL) sont nécessaires. Dans le présent travail de thèse, nous avons donc étudié les interfaces aqueuses au niveau moléculaire, en couplant la modélisation théorique à partir de simulations DFT-MD avec les spectroscopies SFG et THz-IR. En développant de nouveaux protocoles/outils d'investigation associant simulations DFT-MD et spectroscopie SFG, en particulier pour la rationalisation plus complexe des interfaces chargées, nous avons fourni une compréhension globale de l'effet des conditions interfaciales d'hydrophilicité, de pH, de force ionique sur le réseau des liaisons-H formé dans la couche interfaciale BIL, sur ses signatures spectroscopiques et sur son impact sur les propriétés physico-chimiques. Nous avons montré pour la première fois que, dans des conditions suffisamment hydrophobes, l'eau interfaciale crée des réseaux des liaisons-H bidimensionnels, révélé expérimentalement par les spectres THz-IR. Le réseau-2D dicte la dynamique de l'eau interfaciale, le potentiel de surface, l'acidité de surface, la tension superficielle et la thermodynamique d'hydratation des solutés hydrophobes. Cet "ordre horizontal" aux interfaces hydrophobes est opposé à "l'ordre verticale" obtenu aux interfaces hydrophiles. Nous avons aussi révélé comment les ions et les conditions de pH modifient ces arrangements structuraux.
Improving our knowledge on water H-Bonded networks formed in the special environment offered by an interface is pivotal for our understanding of many natural phenomena and technological applications. To reveal the interfacial water arrangement, techniques able to provide detailed microscopic information selectively for the interfacial layer are required. In the present thesis work, we have hence investigated aqueous interfaces at the molecular level, by coupling theoretical modeling from DFT-MD simulations with SFG & THz-IR spectroscopies. By developing new investigation protocols/tools, coupling DFT-MD simulations and SFG spectroscopy, in particular for the more complex rationalization of charged interfaces, we have provided a global comprehension of the effect of various interfacial conditions (hydrophilicity, pH, ionic strength) on the HB-Network formed in the interfacial layer (BIL), on its spectroscopic signatures and on its impact on physico-chemical properties. We have shown for the first time that, in sufficiently hydrophobic conditions, BIL interfacial water creates special 2-Dimensional HB-Networks, experimentally revealed by one specific THz-IR marker band. Such 2D-network dictates HBs and orientational dynamics of interfacial water, surface potential, surface acidity, water surface tension and thermodynamics of hydration…
Advisors/Committee Members: Gaigeot, Marie-Pierre (thesis director).
Subjects/Keywords: Dft-Md; Sfg; Interfaces aqueuses; THz-IR; Hydrophobicité; Bil/dl; Dft-Md; Sfg; Aqueous interfaces; THz-IR; Hydrophobicity; Bil/dl
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APA ·
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APA (6th Edition):
Pezzotti, S. (2019). DFT-MD simulations and theoretical SFG spectroscopy to characterize H-Bonded networks at aqueous interfaces : from hydrophobic to hydrophilic environments : Simulations DFT-MD et spectroscopie SFG théorique pour la caractérisation des interfaces aqueuses : des environnements hydrophobes à hydrophiles. (Doctoral Dissertation). Université Paris-Saclay (ComUE). Retrieved from http://www.theses.fr/2019SACLE008
Chicago Manual of Style (16th Edition):
Pezzotti, Simone. “DFT-MD simulations and theoretical SFG spectroscopy to characterize H-Bonded networks at aqueous interfaces : from hydrophobic to hydrophilic environments : Simulations DFT-MD et spectroscopie SFG théorique pour la caractérisation des interfaces aqueuses : des environnements hydrophobes à hydrophiles.” 2019. Doctoral Dissertation, Université Paris-Saclay (ComUE). Accessed April 13, 2021.
http://www.theses.fr/2019SACLE008.
MLA Handbook (7th Edition):
Pezzotti, Simone. “DFT-MD simulations and theoretical SFG spectroscopy to characterize H-Bonded networks at aqueous interfaces : from hydrophobic to hydrophilic environments : Simulations DFT-MD et spectroscopie SFG théorique pour la caractérisation des interfaces aqueuses : des environnements hydrophobes à hydrophiles.” 2019. Web. 13 Apr 2021.
Vancouver:
Pezzotti S. DFT-MD simulations and theoretical SFG spectroscopy to characterize H-Bonded networks at aqueous interfaces : from hydrophobic to hydrophilic environments : Simulations DFT-MD et spectroscopie SFG théorique pour la caractérisation des interfaces aqueuses : des environnements hydrophobes à hydrophiles. [Internet] [Doctoral dissertation]. Université Paris-Saclay (ComUE); 2019. [cited 2021 Apr 13].
Available from: http://www.theses.fr/2019SACLE008.
Council of Science Editors:
Pezzotti S. DFT-MD simulations and theoretical SFG spectroscopy to characterize H-Bonded networks at aqueous interfaces : from hydrophobic to hydrophilic environments : Simulations DFT-MD et spectroscopie SFG théorique pour la caractérisation des interfaces aqueuses : des environnements hydrophobes à hydrophiles. [Doctoral Dissertation]. Université Paris-Saclay (ComUE); 2019. Available from: http://www.theses.fr/2019SACLE008
University of Colorado
5.
Perkins, Russell James.
Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.
Degree: PhD, 2017, University of Colorado
URL: https://scholar.colorado.edu/chem_gradetds/219
► Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key…
(more)
▼ Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key reactions occur in heterogeneous
aqueous systems, where interfacial effects are particularly important. Despite the importance of
aqueous environments and the tremendous amount of work done to study them, there are aspects that require further explanation and remain controversial. I have performed experimental studies to help elucidate the fundamental characteristics of
aqueous systems, while examining specific phenomena across several fields.
The genetic disorder phenylketonuria (PKU) can result in increased levels of the aromatic amino acid phenylalanine in human serum. Much of my work has focused on the driving forces behind partitioning of aromatic small molecules, including phenylalanine, into air-water or membrane-water interfacial regions, and the consequences of partitioning on interfacial properties. Drastically different behaviors for structurally similar aromatic molecules are observed, differences that cannot be explained by hydrophobic effects. These observations can be explained, however, through the development of a more detailed picture of interactions and partitioning, including the formation of interfacial aggregates. For phenylalanine, this partitioning appears to result in drastic changes in membrane morphology and permeability. This is a likely molecular-level cause for the damage associated with the disease state of PKU.
Aqueous systems are further complicated by the reactivity of water. It often serves not only the role of a solvent, but also a reactant, a product, and/or a catalyst. I explore this reactivity using an organic molecule with relevance to environmental chemistry, zymonic acid. Zymonic acid forms spontaneously from pyruvic acid, an important atmospheric species. While zymonic acid exists as a single species in solid form when dissolved in DMSO, once in
aqueous solution it quickly reacts with water and equilibrates with at least four other forms. I studied the details and kinetics of these equilibria via time-dependent NMR. Several surprising mechanistic details were uncovered, including a direct enol to geminal diol conversion and base-catalyzed lactone ring formation. The consequences of zymonic acid’s behavior are investigated in the context of environmental and prebiotic chemistry.
Advisors/Committee Members: Veronica Vaida, Joel Eaves, Amy Palmer, Loren Hough, Garret Miyake.
Subjects/Keywords: aqueous interfaces; aromatic aggregation; mechanistic organic chemistry; membrane biophysics; preboitic chemistry; surfactants; Physical Chemistry
Record Details
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Record Details
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APA ·
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APA (6th Edition):
Perkins, R. J. (2017). Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/219
Chicago Manual of Style (16th Edition):
Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2017. Doctoral Dissertation, University of Colorado. Accessed April 13, 2021.
https://scholar.colorado.edu/chem_gradetds/219.
MLA Handbook (7th Edition):
Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2017. Web. 13 Apr 2021.
Vancouver:
Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Internet] [Doctoral dissertation]. University of Colorado; 2017. [cited 2021 Apr 13].
Available from: https://scholar.colorado.edu/chem_gradetds/219.
Council of Science Editors:
Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Doctoral Dissertation]. University of Colorado; 2017. Available from: https://scholar.colorado.edu/chem_gradetds/219
University of Colorado
6.
Perkins, Russell James.
Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.
Degree: PhD, 2018, University of Colorado
URL: https://scholar.colorado.edu/chem_gradetds/273
► Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key…
(more)
▼ Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key reactions occur in heterogeneous
aqueous systems, where interfacial effects are particularly important. Despite the importance of
aqueous environments and the tremendous amount of work done to study them, there are aspects that require further explanation and remain controversial. I have performed experimental studies to help elucidate the fundamental characteristics of
aqueous systems, while examining specific phenomena across several fields. The genetic disorder phenylketonuria (PKU) can result in increased levels of the aromatic amino acid phenylalanine in human serum. Much of my work has focused on the driving forces behind partitioning of aromatic small molecules, including phenylalanine, into air-water or membrane-water interfacial regions, and the consequences of partitioning on interfacial properties. Drastically different behaviors for structurally similar aromatic molecules are observed, differences that cannot be explained by hydrophobic effects. These observations can be explained, however, through the development of a more detailed picture of interactions and partitioning, including the formation of interfacial aggregates. For phenylalanine, this partitioning appears to result in drastic changes in membrane morphology and permeability. This is a likely molecular-level cause for the damage associated with the disease state of PKU.
Aqueous systems are further complicated by the reactivity of water. It often serves not only the role of a solvent, but also a reactant, a product, and/or a catalyst. I explore this reactivity using an organic molecule with relevance to environmental chemistry, zymonic acid. Zymonic acid forms spontaneously from pyruvic acid, an important atmospheric species. While zymonic acid exists as a single species in solid form when dissolved in DMSO, once in
aqueous solution it quickly reacts with water and equilibrates with at least four other forms. I studied the details and kinetics of these equilibria via time-dependent NMR. Several surprising mechanistic details were uncovered, including a direct enol to geminal diol conversion and base-catalyzed lactone ring formation. The consequences of zymonic acid’s behavior are investigated in the context of environmental and prebiotic chemistry.
Advisors/Committee Members: Veronica Vaida, Joel Eaves, Amy Palmer, Loren Hough, Garret Miyake.
Subjects/Keywords: aqueous interfaces; aromatic aggregation; mechanistic organic chemistry; membrane biophysics; preboitic chemistry; surfactants; Organic Chemistry; Physical Chemistry
Record Details
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Record Details
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❌
APA ·
Chicago ·
MLA ·
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CSE |
Export
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Manager
APA (6th Edition):
Perkins, R. J. (2018). Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/273
Chicago Manual of Style (16th Edition):
Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2018. Doctoral Dissertation, University of Colorado. Accessed April 13, 2021.
https://scholar.colorado.edu/chem_gradetds/273.
MLA Handbook (7th Edition):
Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2018. Web. 13 Apr 2021.
Vancouver:
Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Internet] [Doctoral dissertation]. University of Colorado; 2018. [cited 2021 Apr 13].
Available from: https://scholar.colorado.edu/chem_gradetds/273.
Council of Science Editors:
Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Doctoral Dissertation]. University of Colorado; 2018. Available from: https://scholar.colorado.edu/chem_gradetds/273
7.
Shamay, Shachar.
Computational Studies of Environmentally Important Processes at Aqueous Interfaces.
Degree: 2012, University of Oregon
URL: http://hdl.handle.net/1794/12318
► Undoubtedly, water is the most abundant and important molecular liquid and is likely the most necessary for life on Earth. The pursuit of understanding water's…
(more)
▼ Undoubtedly, water is the most abundant and important molecular liquid and is likely the most necessary for life on Earth. The pursuit of understanding water's properties and behaviors has placed it in a unique scientific and even mythical position throughout human history. It is no surprise that much scientific research today centers around this molecule and its interactions with others. The interfacial region between liquid water solutions and other phases is still poorly understood, and only recently have experiments developed to where we can probe this unique environment. Water surfaces exist throughout the Earth's atmosphere and oceans but also make up many of the microscopic
interfaces necessary for metabolic processes within living cells. Yet, the influence of water surfaces on the chemistry that drives life and terrestrial processes is still largely unknown, and many research efforts today are attempting to gain insight to this critically important frontier. This dissertation documents several unique computational studies aimed to further our understanding of the complex interactions within a water system and between water and simple, common solutes. Reported herein are the results of molecular dynamics (MD) simulations and computational analysis of interfacial
aqueous systems of small hydrated acids, ionic
aqueous salt solutions interfaced with a liquid oil, and gas molecules adsorbing onto water surfaces. The composition of the systems chosen for the studies reported in this dissertation reflect environmentally relevant
interfaces and also complement recent experimental efforts by the Richmond laboratory. Classical and quantum ab initio MD techniques were used for simulation of the molecular systems and the subsequent analyses provided new information regarding molecular interactions, geometries, orientations, and surface behaviors of water and hydrated interfacial solute molecules.
This dissertation includes both previously published and unpublished co-authored material.
Advisors/Committee Members: Lonergan, Mark (advisor).
Subjects/Keywords: Aqueous interfaces; Computer simulations; Molecular dynamics; Surfaces; Water
…water systems in vacuum and in air,
to studying more complex interfaces such as aqueous… …35
IV. SULFUR DIOXIDE ADSORPTION TO AQUEOUS SURFACES . . .
38
4.1.
Introduction… …orientation of H2 O. . . . . . . . . . . .
16
3.2. Aqueous salt solution (1.2 M) and… …x29; NaNO3 , and (D) Na2 SO4 aqueous
solution densities and the (solid black… …aqueous-salt-CCl4 system. (black-dashed) The reference
CCl4 -H2 O interface spectrum…
Record Details
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Record Details
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APA ·
Chicago ·
MLA ·
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CSE |
Export
to Zotero / EndNote / Reference
Manager
APA (6th Edition):
Shamay, S. (2012). Computational Studies of Environmentally Important Processes at Aqueous Interfaces. (Thesis). University of Oregon. Retrieved from http://hdl.handle.net/1794/12318
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Shamay, Shachar. “Computational Studies of Environmentally Important Processes at Aqueous Interfaces.” 2012. Thesis, University of Oregon. Accessed April 13, 2021.
http://hdl.handle.net/1794/12318.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Shamay, Shachar. “Computational Studies of Environmentally Important Processes at Aqueous Interfaces.” 2012. Web. 13 Apr 2021.
Vancouver:
Shamay S. Computational Studies of Environmentally Important Processes at Aqueous Interfaces. [Internet] [Thesis]. University of Oregon; 2012. [cited 2021 Apr 13].
Available from: http://hdl.handle.net/1794/12318.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Shamay S. Computational Studies of Environmentally Important Processes at Aqueous Interfaces. [Thesis]. University of Oregon; 2012. Available from: http://hdl.handle.net/1794/12318
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Maryland
8.
Can, Suleyman Zuhtu.
MOLECULAR STRUCTURE AND ORGANIZATION IN ORGANIC MONOLAYERS AT AQUEOUS/VAPOR INTERFACES.
Degree: Chemistry, 2008, University of Maryland
URL: http://hdl.handle.net/1903/8030
► The goal of this thesis is to understand how the asymmetry of interfaces affects the structure of adsorbed surfactants and organization within the monolayer. These…
(more)
▼ The goal of this thesis is to understand how the asymmetry of
interfaces affects the structure of adsorbed surfactants and organization within the monolayer. These studies employ a variety of experimental techniques including surface tensiometry and vibrational sum frequency spectroscopy, a nonlinear optical method having surface specificity. The first studies in this thesis examine the ability of different neutral organic surfactants to form films at the
aqueous/vapor interface. Specifically, structure and organization within monolayers formed by insoluble and soluble alcohols at
aqueous/vapor
interfaces were investigated. Relatively simple organic molecules were used to isolate both intermolecular interactions within adsorbed films and the competition between attractive and repulsive forces experienced between monolayer monomers and the
aqueous subphase. Results of the experiments allowed us predict that linear alcohols form tightly packed monolayers at the
aqueous/vapor interface. This organization allows the alcohol OH group to make strong H-bonds with the water subphase while the hydrocarbon chains interact with each other through attractive van der Waals forces. Our studies showed that the interplay between the van der Waals attraction and the hydrophobic repulsion is the primary factor in determining the equilibrium interfacial structures of 2- and 3-position alcohols. The primary conformer structures predicted for 2-position alcohols include all-trans conformations for insoluble monolayers and a model containing two gauche defects for soluble monolayers. In an effort to model these results we initiated a series of classical molecular dynamics simulations designed to develop molecular insights into the equilibrium structures inferred from experiments. Computer simulations were also used to separate and compare the individual forces contributing to film organization.
Our studies in the last part of the thesis focus on the effect of charged soluble surfactants on the structure and organization of phospholipid monolayers adsorbed to
aqueous/air
interfaces. The self driven spreading of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) on
aqueous surfaces to form monolayers was a matter interest in these experiments. The effect of surfactants as a potentially competing surface active species was explored with a function of surfactant bulk phase concentration. The results showed significantly different effects depending on whether the surfactant was anionic or cationic.
Advisors/Committee Members: Walker, Robert A (advisor).
Subjects/Keywords: Chemistry, Physical; Chemistry, Physical; aqueous interfaces; sum frequency spectroscopy; phospholipid monolayers; alcohol monolayers
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APA (6th Edition):
Can, S. Z. (2008). MOLECULAR STRUCTURE AND ORGANIZATION IN ORGANIC MONOLAYERS AT AQUEOUS/VAPOR INTERFACES. (Thesis). University of Maryland. Retrieved from http://hdl.handle.net/1903/8030
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Can, Suleyman Zuhtu. “MOLECULAR STRUCTURE AND ORGANIZATION IN ORGANIC MONOLAYERS AT AQUEOUS/VAPOR INTERFACES.” 2008. Thesis, University of Maryland. Accessed April 13, 2021.
http://hdl.handle.net/1903/8030.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Can, Suleyman Zuhtu. “MOLECULAR STRUCTURE AND ORGANIZATION IN ORGANIC MONOLAYERS AT AQUEOUS/VAPOR INTERFACES.” 2008. Web. 13 Apr 2021.
Vancouver:
Can SZ. MOLECULAR STRUCTURE AND ORGANIZATION IN ORGANIC MONOLAYERS AT AQUEOUS/VAPOR INTERFACES. [Internet] [Thesis]. University of Maryland; 2008. [cited 2021 Apr 13].
Available from: http://hdl.handle.net/1903/8030.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Can SZ. MOLECULAR STRUCTURE AND ORGANIZATION IN ORGANIC MONOLAYERS AT AQUEOUS/VAPOR INTERFACES. [Thesis]. University of Maryland; 2008. Available from: http://hdl.handle.net/1903/8030
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
9.
Reeser, Dorea Irma.
Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species.
Degree: 2013, University of Toronto
URL: http://hdl.handle.net/1807/43714
► Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the…
(more)
▼ Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.
PhD
Advisors/Committee Members: Donaldson, D. James, Chemistry.
Subjects/Keywords: aqueous organic coatings; gas transport; sea surface microlayer (SML); nitrogen dioxide (NO2); molecular iodine (I2); carbon dioxide (CO2); water surfaces; air – water interfaces; gas to solution partitioning; Incoherent Broadband Cavity-Enhanced Absorption Spectroscopy (IBBC-EAS); 0725; 0768; 0485; 0494; 0608
…surfaces represent a
substantial portion of air—aqueous interfaces in the environment. The ocean… …air—aqueous interfaces may be different than those that occur in the corresponding
bulk… …aqueous or gas-phases. Organic coatings, or films, at air-aqueous interfaces can lower
the… …properties at air—aqueous interfaces can influence the fate of
important chemicals in the… …x29; Elsevier.73
1.2 Gas Transport Across Air—Aqueous Interfaces
1.2.1
Summary
Heat…
Record Details
Similar Records
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Share »
Record Details
Similar Records
Cite
« Share
❌
APA ·
Chicago ·
MLA ·
Vancouver ·
CSE |
Export
to Zotero / EndNote / Reference
Manager
APA (6th Edition):
Reeser, D. I. (2013). Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species. (Doctoral Dissertation). University of Toronto. Retrieved from http://hdl.handle.net/1807/43714
Chicago Manual of Style (16th Edition):
Reeser, Dorea Irma. “Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species.” 2013. Doctoral Dissertation, University of Toronto. Accessed April 13, 2021.
http://hdl.handle.net/1807/43714.
MLA Handbook (7th Edition):
Reeser, Dorea Irma. “Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species.” 2013. Web. 13 Apr 2021.
Vancouver:
Reeser DI. Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species. [Internet] [Doctoral dissertation]. University of Toronto; 2013. [cited 2021 Apr 13].
Available from: http://hdl.handle.net/1807/43714.
Council of Science Editors:
Reeser DI. Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species. [Doctoral Dissertation]. University of Toronto; 2013. Available from: http://hdl.handle.net/1807/43714
. 
Open Access Theses and Dissertations
