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Tyrode, Eric
Publications (10 of 14) Show all publications
Sthoer, A. (2019). Interactions of Na+ Cations with a Highly Charged Fatty Acid Langmuir Monolayer: Molecular Description of the Phase Transition. The Journal of Physical Chemistry C
Open this publication in new window or tab >>Interactions of Na+ Cations with a Highly Charged Fatty Acid Langmuir Monolayer: Molecular Description of the Phase Transition
2019 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455Article in journal (Other (popular science, discussion, etc.)) Published
Abstract [en]

Vibrational sum frequency spectroscopy has been used to study the molecular properties upon compression of a highly charged arachidic acid Langmuir monolayer, which displays a first-order phase transition plateau in the surface pressure - molecular area (π-A) isotherm. By targeting vibrational modes from the carboxylic acid headgroup, alkyl chain, and interfacial water molecules, information regarding the surface charge, surface potential, type of ion pair formed, and conformational order of the monolayer could be extracted. The monolayer was found to be fully charged before reaching the 2D-phase transition plateau, where partial reprotonation, as well as the formation of COO⎺ Na+ contact-ion pairs, started to take place. After the transition, three headgroup species, mainly hydrated COO⎺, COOH, and COO⎺ Na+ contact-ion pairs could be identified and their proportions quantified. Comparison with theoretical models shows that predictions from the Gouy Chapman model are only adequate for the lowest surface charge densities (<-0.1 C/m2). In contrast, a modified Poisson-Boltzmann (MPB) model that accounts for finite-size of the cation, captures many of the experimental observables, including the partial reprotonation, and surface potential changes upon compression. The experimental results provide a quantitative molecular insight that could be used to test potential extensions to the theory.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
Langmuir monolayer; VSFS; Vibrational Sum Frequency Spectroscopy
National Category
Physical Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-256048 (URN)10.1021/acs.jpcc.9b06435 (DOI)000487349600035 ()2-s2.0-8507270841 (Scopus ID)
Note

QC 20190827

QC 20191015

Available from: 2019-08-16 Created: 2019-08-16 Last updated: 2019-10-15Bibliographically approved
Hore, D. K. & Tyrode, E. (2019). Probing Charged Aqueous Interfaces Near Critical Angles: Effect of Varying Coherence Length. The Journal of Physical Chemistry C, 123(27), 16911-16920
Open this publication in new window or tab >>Probing Charged Aqueous Interfaces Near Critical Angles: Effect of Varying Coherence Length
2019 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, no 27, p. 16911-16920Article in journal (Refereed) Published
Abstract [en]

Angle-resolved vibrational sum frequency generation experiments have been used to study the silica-water interface as a function of ionic strength. Well below the critical angle, the sum frequency intensity increases up to 10(-4) M NaCl and then drops. However, near the critical angle, a plateau may be observed up to 10(-4) M. We first demonstrate that this is a result of the interaction of a long Debye length at low ionic strength with a long coherence length near the critical angles. In order to account for the behavior at the lowest concentrations where surface potentials are typically large, it is necessary to consider an electrostatic potential that extends into the bulk aqueous phase beyond the Debye-Huckel approximation. Because the extent of second- and third-order contributions to the nonlinear polarization can vary with ionic strength, but not with the angle of incidence, we perform a global fit to the experimental data using our proposed model to extract the relative magnitude of the two susceptibilities. The ionic strength dependence of this ratio points to the critical nature of the silanol deprotonation and the development of surface charge and illustrates how surface water molecules respond. These results highlight the importance of varying the coherence length in order to probe the water structure at charged interfaces.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-255562 (URN)10.1021/acs.jpcc.9b05256 (DOI)000475537500045 ()
Note

QC 20190805

Available from: 2019-08-05 Created: 2019-08-05 Last updated: 2019-08-05Bibliographically approved
Tyrode, E. & Corkery, R. (2018). Charging of Carboxylic Acid Monolayers with Monovalent Ions at Low Ionic Strengths: Molecular Insight Revealed by Vibrational Sum Frequency Spectroscopy. The Journal of Physical Chemistry C, 122(50), 28775-28786
Open this publication in new window or tab >>Charging of Carboxylic Acid Monolayers with Monovalent Ions at Low Ionic Strengths: Molecular Insight Revealed by Vibrational Sum Frequency Spectroscopy
2018 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 50, p. 28775-28786Article in journal (Refereed) Published
Abstract [en]

The charging of arachidic acid Langmuir monolayers as a function of subphase pH and monovalent ion concentration below 100 mM was investigated using vibrational sum frequency spectroscopy. Molecular information was obtained by targeting the vibrational modes of the carboxylic acid headgroups, alkyl chains, and water molecules in the immediate surface and diffuse double layers. The surface charge in the monolayer was experimentally determined by monitoring the hydrated carboxylate stretching modes. The charging behavior was found to be in excellent agreement with that predicted by Gouy-Chapman theory using a thermodynamic pK(a) of 5.1 +/- 0.2. This resulted in an apparent pK(a) of similar to 10.8 when the only ions present in solution were those associated with adjusting the pH. Water molecules with a preferred orientation in the immediate surface region were found to primarily interact with the uncharged carboxylic acid moiety, decreasing in number as the monolayer further deprotonated. Contributions from water molecules in the diffuse double layer, partly aligned by the exponentially decaying surface electric field, closely followed the predictions of a recently proposed theoretical framework that accounts for interference and screening effects. Finally, the charging of the monolayer was experimentally found to be independent of the identity of either the monovalent cation (i.e., Li+, Na+, Rb+) or anion (i.e., F-, Cl-, I-) at low salt concentrations.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-241330 (URN)10.1021/acs.jpcc.8b09505 (DOI)000454566700033 ()2-s2.0-85058663712 (Scopus ID)
Note

QC 20190123

Available from: 2019-01-23 Created: 2019-01-23 Last updated: 2019-10-15Bibliographically approved
Sthoer, A., Hladilkova, J., Lund, M. & Tyrode, E. (2018). Molecular insight into the carboxylic acid - alkali metal cations interactions: Reversed affinity and ion pair formation. Paper presented at 256th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nanoscience, Nanotechnology and Beyond, AUG 19-23, 2018, Boston, MA. Abstract of Papers of the American Chemical Society, 256
Open this publication in new window or tab >>Molecular insight into the carboxylic acid - alkali metal cations interactions: Reversed affinity and ion pair formation
2018 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 256Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-238566 (URN)000447600003632 ()
Conference
256th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nanoscience, Nanotechnology and Beyond, AUG 19-23, 2018, Boston, MA
Note

QC 20181105

Available from: 2018-11-05 Created: 2018-11-05 Last updated: 2018-11-05Bibliographically approved
Sengupta, S., Moberg, D. R., Paesani, F. & Tyrode, E. (2018). Neat Water-Vapor Interface: Proton Continuum and the Nonresonant Background. Journal of Physical Chemistry Letters, 9(23), 6744-6749
Open this publication in new window or tab >>Neat Water-Vapor Interface: Proton Continuum and the Nonresonant Background
2018 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 9, no 23, p. 6744-6749Article in journal (Refereed) Published
Abstract [en]

Whether the surface of neat water is "acidic" or "basic" remains an active and controversial field of research. Most of the experimental evidence supporting the preferential adsorption of H3O+ ions stems from nonlinear optical spectroscopy methods typically carried out at extreme pH conditions (pH < 1). Here, we use vibrational sum frequency spectroscopy (VSFS) to target the "proton continuum", an unexplored frequency range characteristic of hydrated protons and hydroxide ions. The VSFS spectra of neat water show a broad and nonzero signal intensity between 1700 and 3000 cm-' in the three different polarization combinations examined. By comparing the SF response of water with that from dilute HCl and NaOH aqueous solutions, we conclude the intensity does not originate from either adsorbed H3O+ or OH- ions. Contributions from the nonresonant background are then critically considered by comparing the experimental results with many-body molecular dynamics (MB-MD) simulated spectra.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-240731 (URN)10.1021/acs.jpclett.8b03069 (DOI)000452929200012 ()30407831 (PubMedID)2-s2.0-85058092810 (Scopus ID)
Note

QC 20180109

Available from: 2019-01-09 Created: 2019-01-09 Last updated: 2019-01-09Bibliographically approved
Okur, H. I., Drexler, C. I., Tyrode, E., Cremer, P. S. & Roke, S. (2018). The Jones-Ray Effect Is Not Caused by Surface-Active Impurities. Journal of Physical Chemistry Letters, 9(23), 6739-6743
Open this publication in new window or tab >>The Jones-Ray Effect Is Not Caused by Surface-Active Impurities
Show others...
2018 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 9, no 23, p. 6739-6743Article in journal (Refereed) Published
Abstract [en]

Pure aqueous electrolyte solutions display a minimum in surface tension at concentrations of 2 +/- 1 mM. This effect has been a source of controversy since it was first reported by Jones and Ray in the 1930s. The Jones Ray effect has frequently been dismissed as an artifact linked to the presence of surface-active impurities. Herein we systematically consider the effect of surface-active impurities by purposely adding nanomolar concentrations of surfactants to dilute electrolyte solutions. Trace amounts of surfactant are indeed found to decrease the surface tension and influence the surface chemistry. However, surfactants can be removed by repeated aspiration and stirring cycles, which eventually deplete the surfactant from solution, creating a pristine surface. Upon following this cleaning procedure, a reduction in the surface tension by millimolar concentrations of salt is still observed. Consequently, we demonstrate that the Jones Ray effect is not caused by surface-active impurities.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-240730 (URN)10.1021/acs.jpclett.8b02957 (DOI)000452929200011 ()30398354 (PubMedID)2-s2.0-85056707754 (Scopus ID)
Funder
Swedish Research CouncilSwedish Foundation for Strategic Research EU, European Research Council, 616305
Note

QC 20190108

Available from: 2019-01-08 Created: 2019-01-08 Last updated: 2019-01-08Bibliographically approved
Cyran, J., Donovan, M., Tyrode, E., Bonn, M. & Backus, E. (2017). Hydrophobic water at a hydrophilic interface. Paper presented at 254th National Meeting and Exposition of the American-Chemical-Society (ACS) on Chemistry's Impact on the Global Economy, AUG 20-24, 2017, Washington, DC. Abstract of Papers of the American Chemical Society, 254
Open this publication in new window or tab >>Hydrophobic water at a hydrophilic interface
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2017 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 254Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2017
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-226825 (URN)000429556702833 ()
Conference
254th National Meeting and Exposition of the American-Chemical-Society (ACS) on Chemistry's Impact on the Global Economy, AUG 20-24, 2017, Washington, DC
Note

QC 20180503

Available from: 2018-05-03 Created: 2018-05-03 Last updated: 2018-05-03Bibliographically approved
Dalstein, L., Potapova, E. & Tyrode, E. (2017). The elusive silica/water interface: isolated silanols under water as revealed by vibrational sum frequency spectroscopy. Physical Chemistry, Chemical Physics - PCCP, 19(16), 10343-10349
Open this publication in new window or tab >>The elusive silica/water interface: isolated silanols under water as revealed by vibrational sum frequency spectroscopy
2017 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 16, p. 10343-10349Article in journal (Refereed) Published
Abstract [en]

It has been long recognized that the surface chemistry of silica, and in particular the type and relative amount of surface bound silanol groups, plays a critical role in many of the properties associated with the material, where a typical example is the discrepant adsorption behavior observed depending on the pretreatment history of the surface. However, in spite of its importance, the direct probing of specific surface silanol groups under water has been hampered by instrumental limitations. Here we make use of vibrational sum frequency spectroscopy (VSFS) to first, identify under water the OH stretch of isolated surface silanols, and second, explore its acid/base behavior and dependence on the surface pretreatment method. The properties of other types of silanol groups (i.e. hydrogen bonded/geminal) are also inferred from the data. The ability to directly probe these functional groups under water represents a crucial step to further improving our understanding of this widely used mineral oxide.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2017
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-207669 (URN)10.1039/c7cp01507k (DOI)000400117700016 ()28379259 (PubMedID)
Note

QC 20170602

Available from: 2017-06-02 Created: 2017-06-02 Last updated: 2017-06-02Bibliographically approved
Bain, C. D., Tyrode, E. & Woods, D. (2009). Combined Raman and SFG study of the adsorption of cationic surfactants on silica. Abstract of Papers of the American Chemical Society, 237, 188-188
Open this publication in new window or tab >>Combined Raman and SFG study of the adsorption of cationic surfactants on silica
2009 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 237, p. 188-188Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2009
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-242851 (URN)000207857800164 ()
Note

QC 20190218

Available from: 2019-02-18 Created: 2019-02-18 Last updated: 2019-02-18Bibliographically approved
Bain, C. D., Churchwell, J. H., Tyrode, E. & Walker, R. A. (2009). TIR Raman spectroscopy of planar supported lipid bilayers. Abstract of Papers of the American Chemical Society, 237
Open this publication in new window or tab >>TIR Raman spectroscopy of planar supported lipid bilayers
2009 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 237Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2009
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-242852 (URN)000207857803058 ()
Note

QC 20190218

Available from: 2019-02-18 Created: 2019-02-18 Last updated: 2019-02-18Bibliographically approved
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