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Characterization of Molecular Adsorption Using Liquid Chromatography and Mass Spectrometry
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Analytical Chemistry.ORCID iD: 0000-0003-3861-9338
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Molecular adsorption is a key feature in several disciplines of chemistry, covering as diverse fields as chromatographic separation to biomaterial development. This thesis aims at developing methods and techniques for the characterization of molecular adsorption at the liquid-solid interface. Two different experimental models were used, small molecular interaction characterization using liquid chromatography and complex protein adsorption on polymeric materials possible for biological sampling. Holistic approaches, where both detailed molecular interactions and identifications of trends, could improve the fundamental understanding of adsorption systems, were invariably part of the scientific process.

The characterization of small molecular interactions on liquid chromatography stationary phases via adsorption isotherm determination used combined data from physical phase parameters i.e. carbon loading, linear-, and nonlinear-characterization methods. These experiments were conducted on high performance liquid chromatography systems, using both ordinary reversed phase stationary phases, and hybrid phases. The expansion of the improved elusion by characteristic point (ECP) for adsorption isotherm determination, led to that previous impossible isotherm types, having inflexion points, now could be determined by the method. It also reduced errors in isotherm parameters due to the elimination of inaccurate determined retention times where the mobile phase concentration was zero.

The characterization of protein adsorption where performed in an unbiased way. Adsorbed proteins on different surfaces were identified using mass spectrometry (MS) and data dependent acquisition or a targeted method. Prior MS, an improved on surface enzymatic digestion (oSED) method was used to enable identification and quantitation of adsorbed protein originating from ventricular cerebrospinal fluid (vCSF). oSED was found to be able to experimentally determine large variations in protein adsorption characteristics between native and coated polycarbonate surfaces in contact with vCSF. The method was also confirmed being mechanistic in favor of enzymatic digestion of the proteins adsorbed on a surface, rather than a prior desorption into solution before digestion.

An improvement of the overall understanding of adsorption systems was not only achieved with the oSED method as a promising tool for characterization of protein adsorption on arbitrary surfaces, but also the use of linear and nonlinear approaches in stationary phase characterization that strengthened drawn conclusions.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2015. , 50 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1248
National Category
Analytical Chemistry
Research subject
Chemistry with specialization in Analytical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-249003ISBN: 978-91-554-9235-9 (print)OAI: oai:DiVA.org:uu-249003DiVA: diva2:801638
Public defence
2015-05-22, A1:111a, Husargatan 3, BMC, Uppsala, 13:00 (English)
Opponent
Supervisors
Available from: 2015-04-27 Created: 2015-04-09 Last updated: 2015-07-07
List of papers
1. Improvement in the generation of adsorption isotherm data in the elution by characteristic points method: the ECP-slope approach.
Open this publication in new window or tab >>Improvement in the generation of adsorption isotherm data in the elution by characteristic points method: the ECP-slope approach.
2010 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1217, no 46, 7215-7221 p.Article in journal (Refereed) Published
Abstract [en]

The elution by characteristic points (ECP) method is a very rapid and precise method for determination of the phase system equilibrium of phase systems in broad solute concentration ranges. Thus, the method is especially suitable for rapid characterization of high efficient separation systems. One important source of error, the effects by the post-loop dispersion, was eliminated in a recent investigation. In this study, the systematic error caused by the selection of the integration starting point at concentration equal to 0 is eliminated. This is done by developing and validating a new procedure for isotherm data generation; the ECP-slope method. The method generates raw slope data of the adsorption isotherm instead of raw adsorption data by integrations as the classical ECP does. Both numerical and experimental data were used for the comparison of the classical ECP approach with the slope-ECP method.

Keyword
Single component adsorption, Adsorption isotherms, Elution by characteristic points method, Slope data, The ECP-slope method
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-161211 (URN)10.1016/j.chroma.2010.09.004 (DOI)000284439800005 ()
Available from: 2011-11-09 Created: 2011-11-09 Last updated: 2017-12-08Bibliographically approved
2. Expanding the elution by characteristic point method for determination of various types of adsorption isotherms
Open this publication in new window or tab >>Expanding the elution by characteristic point method for determination of various types of adsorption isotherms
2011 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1218, no 24, 3737-3742 p.Article in journal (Refereed) Published
Abstract [en]

Important improvements have recently been made on the elution by characteristic point (ECP) method to increase the accuracy of the determined adsorption isotherms. However, the method has so far been limited/used for only type I adsorption isotherms (e.g. Langmuir, Toth, bi-Langmuir). In this study, general strategies are developed to expand the ECP method for the determination of more complex adsorption isotherms including such containing inflection points. We will exemplify the methodology with type II, type III and type V isotherms. Guidelines are given for how to determine such isotherms using the ECP method and for the experimental considerations that must be taken into account or that may be eliminated in the particular case.

Keyword
Elution by characteristic points, Adsorption isotherms, Inflection points, Frontal analysis by characteristic points, Moreau isotherm, BET-isotherms
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-155586 (URN)10.1016/j.chroma.2011.04.035 (DOI)000291576400002 ()
Available from: 2011-06-28 Created: 2011-06-27 Last updated: 2017-12-11Bibliographically approved
3. Evaluation of a combined linear–nonlinear approach for column characterization using modern alkaline-stable columns as model
Open this publication in new window or tab >>Evaluation of a combined linear–nonlinear approach for column characterization using modern alkaline-stable columns as model
2013 (English)In: Journal of Separation Science, ISSN 1615-9306, E-ISSN 1615-9314, Vol. 36, no 11, 1753-1761 p.Article in journal (Refereed) Published
Abstract [en]

This study investigates if deeper understanding is achieved when combining nonlinear and linear chromatographic column characterization methods. As test systems, two hybrid columns (Phenomenex Gemini-NX C18 and Kromasil Eternity C18) and one classic one (Kromasil-C18) were selected. The nonlinear methods were based on firm adsorption theory and involved determination of adsorption isotherms followed by calculations with a new numerical tool, adsorption energy distribution, on probe components at different pH values. The linear methods involved the hydrophobic subtraction model and selected probe components retention factors as a function of pH. The combined analysis indicated that both complementary and confirmative information can be achieved regarding the actual model systems.

Keyword
Adsorption isotherms, Characterization, Linear methods, Nonlinear methods, Retention
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-202052 (URN)10.1002/jssc.201201132 (DOI)000319919900009 ()
Available from: 2013-06-19 Created: 2013-06-19 Last updated: 2017-12-06Bibliographically approved
4. A mass spectrometry based method for investigating time dependent protein adsorption on surfaces in contact with complex biological samples
Open this publication in new window or tab >>A mass spectrometry based method for investigating time dependent protein adsorption on surfaces in contact with complex biological samples
(English)Article in journal (Other academic) Submitted
Keyword
time-resolved, protein adsorption, mass spectrometry, on-surface digestion, oSED, ventricular cerebrospinal fluid, polycarbonate membrane, Bottom-up, Shotgun, vCSF, Peptides
National Category
Analytical Chemistry
Research subject
Chemistry with specialization in Analytical Chemistry
Identifiers
urn:nbn:se:uu:diva-248998 (URN)
Funder
Magnus Bergvall FoundationBerzelii Centre EXSELENTÅke Wiberg Foundation
Available from: 2015-04-09 Created: 2015-04-09 Last updated: 2017-01-24
5. Mass spectrometric determination of the effect of surface deactivation on membranes used for the sampling of cerebrospinal fluid (CSF)
Open this publication in new window or tab >>Mass spectrometric determination of the effect of surface deactivation on membranes used for the sampling of cerebrospinal fluid (CSF)
(English)Manuscript (preprint) (Other academic)
Keyword
Protein Adsorption, Mass Spectrometry, oSED, Surface modification, Coating, Poloxamer 407, Pluronic F127, Trypsin, Digestion, Shotgun, Bottom-up, peptides
National Category
Analytical Chemistry
Research subject
Chemistry with specialization in Analytical Chemistry; Chemistry with specialization in Surface Biotechnology
Identifiers
urn:nbn:se:uu:diva-248631 (URN)
Funder
Magnus Bergvall FoundationÅke Wiberg FoundationSwedish Research Council for Environment, Agricultural Sciences and Spatial Planning, 621-2011-4423Berzelii Centre EXSELENT
Available from: 2015-04-05 Created: 2015-04-05 Last updated: 2017-01-24
6. Mechanistic investigation of the on surface enzymatic digestion (oSED) protein adsorption detection method using targeted mass spectrometry
Open this publication in new window or tab >>Mechanistic investigation of the on surface enzymatic digestion (oSED) protein adsorption detection method using targeted mass spectrometry
Show others...
2016 (English)In: The Analyst, ISSN 0003-2654, E-ISSN 1364-5528, Vol. 141, no 5, 1714-1720 p.Article in journal (Refereed) Published
Abstract [en]

This study describes our efforts to study some of the mechanistic aspects of the earlier established onsurface enzymatic digestion (oSED) method. In a multitude of application areas, it has become important to be able to fully characterize and understand selective protein adsorption to biomaterial surfaces for various applications, including biomedicine (implants), nanotechnology (microchip surfaces and sensors) and materials sciences. Herein, the investigation of the mechanistic aspects was based on microdialysis catheter tubes that were flushed with controlled protein solutions mimicking the extracellular fluid of the brain. The protein adsorption properties were monitored using high-resolution liquid chromatography tandem mass spectrometry (LC-MS/MS) with a targeted method. The temporally resolved results show that most proteins stay adsorbed onto the surface during the entire digestion process and are only cut away piece by piece, whereas smaller proteins and peptides seem to desorb rather easily from the surface. This information will simplify the interpretation of data generated using the oSED method and can also be used for the characterization of the physicochemical properties controlling the adsorption of individual proteins to specific surfaces.

National Category
Analytical Chemistry Engineering and Technology
Research subject
Chemistry with specialization in Analytical Chemistry
Identifiers
urn:nbn:se:uu:diva-248629 (URN)10.1039/c5an02091c (DOI)000371229600018 ()
Funder
Magnus Bergvall FoundationBerzelii Centre EXSELENTSwedish Research Council, 621-2011-4423
Available from: 2015-04-05 Created: 2015-04-05 Last updated: 2017-12-04Bibliographically approved

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