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Photochemical Surface Functionalization: Synthesis, Nanochemistry and Glycobiological Studies
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis mainly deals with the development of photochemical approaches to immobilize carbohydrates on surfaces for glycobiological studies. These approaches have been incorporated into a number of state-of-the-art nanobio-platforms, including carbohydrate microarrays, surface plasmon resonance (SPR), quartz crystal microbalance (QCM), atomic force microscopy (AFM), and glyconanomaterials. All the surfaces have displayed good binding capabilities and selectivities after functionalization with carbohydrates, and a range of important data have been obtained concerning surface characteristics and carbohydrate-protein interactions, based on the platforms established. Besides, a variety of non-carbohydrate and carbohydrate-based molecules have been synthesized, during which process the mutarotation of 1-glycosyl thiols and the stereocontrol in 1-S-glycosylation reactions have been thoroughly studied.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology , 2011. , 86 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:47
Keyword [en]
Carbohydrates, Glycobiology, Carbohydrate-protein interactions, Perfluorophenylazide (PFPA), Photochemistry, Carbohydrate surface immobilization, Carbohydrate microarrays, Surface plasmon resonance (SPR), Quartz crystal microbalance (QCM), Atomic force microscopy (AFM), Glyconanomaterials, Concanavalin A (Con A), Cyanovirin-N (CV-N), 1-Glycosyl thiols; Mutarotation, 1-S-glycosylation, Stereocontrol
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-41973ISBN: 978-91-7501-072-4 (print)OAI: oai:DiVA.org:kth-41973DiVA: diva2:445661
Public defence
2011-10-21, F3, Lindstedtsvägen 26, KTH, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
QC 20111004Available from: 2011-10-04 Created: 2011-10-04 Last updated: 2011-10-04Bibliographically approved
List of papers
1. pH-Dependent Mutarotation of 1-Thioaldoses in Water. Unexpected Behavior of (2S)-D-Aldopyranoses
Open this publication in new window or tab >>pH-Dependent Mutarotation of 1-Thioaldoses in Water. Unexpected Behavior of (2S)-D-Aldopyranoses
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2010 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 75, no 18, 6115-6121 p.Article in journal (Refereed) Published
Abstract [en]

The pH-dependent mutarotation of 1-thioaldopyranoses in aqueous media has been investigated. Anomerization readily occurred at lower and neutral pH for all aldopyranoses studied, whereas mainly for (2S)-D-aldopyranoses at higher pH. 1-Thio-D-mannopyranose and 1-thio-D-altropyranose showed very strong pH dependence where the anomeric equilibrium ratios changed dramatically from a preference for the beta-anomer at lower pH to the alpha-anomer at higher pH.

Keyword
Anomeric equilibrium, Anomerization, Aqueous media, Mannopyranose, Mutarotation, Neutral pH, PH dependence, PH-dependent
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-26704 (URN)10.1021/jo100826e (DOI)000281585600007 ()2-s2.0-77956498793 (Scopus ID)
Note
QC 20101129 Uppdaterad från manuskript till artikel (20101129).Available from: 2010-11-29 Created: 2010-11-26 Last updated: 2017-12-12Bibliographically approved
2. Stereocontrolled 1-S-glycosylation and comparative binding studies of photoprobe-thiosaccharide conjugates with their O-linked analogs
Open this publication in new window or tab >>Stereocontrolled 1-S-glycosylation and comparative binding studies of photoprobe-thiosaccharide conjugates with their O-linked analogs
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2013 (English)In: Pure and Applied Chemistry, ISSN 0033-4545, E-ISSN 1365-3075, Vol. 85, no 9, 1789-1801 p.Article in journal (Refereed) Published
Abstract [en]

The use of thioglycosides and other glycan derivatives with anomeric sulfur linkages is gaining increasing interest, both in synthesis and in various biological contexts. Herein, we demonstrate the occurrence and circumvention of anomerization during 1-S-glycosylation reactions, and present highly efficient and stereocontrolled syntheses of a series of photoprobe-thiosaccharide conjugates. Mutarotation of glycosyl thiols proved to be the origin of the anomeric mixtures formed, and kinetic effects could be used to circumvent anomerization. The synthesized carbohydrate conjugates were then evaluated by both solution- and solid-phase-based techniques. Both binding results showed that the S-linked glycosides interact with their cognate lectins comparably to the corresponding O-analogs in the present cases, thus demonstrating the reliability of the solid-support platform built upon our photo-initiated carbohydrate immobilization method for probing protein bindings, and showing the potential of combining these two means for studying carbohydrate-protein inter-actions.

Keyword
carbohydrates, photochemistry, protein interactions, organic materials, organic synthesis, stereocontrol
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-41972 (URN)10.1351/PAC-CON-12-08-13 (DOI)000323700200004 ()2-s2.0-84883377211 (Scopus ID)
Funder
Swedish Research Council, 622-2003-2343
Note

QC 20130930. Updated from submitted to published.

Available from: 2011-10-04 Created: 2011-10-04 Last updated: 2017-12-08Bibliographically approved
3. Stereoselective synthesis of light-activatable perfluorophenylazide-conjugated carbohydrates for glycoarray fabrication and evaluation of structural effects on protein binding by SPR imaging
Open this publication in new window or tab >>Stereoselective synthesis of light-activatable perfluorophenylazide-conjugated carbohydrates for glycoarray fabrication and evaluation of structural effects on protein binding by SPR imaging
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2011 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 9, no 9, 3188-3198 p.Article in journal (Refereed) Published
Abstract [en]

A series of light-activatable perfluorophenylazide (PFPA)-conjugated carbohydrate structures have been synthesized and applied to glycoarray fabrication. The glycoconjugates were structurally varied with respect to anomeric attachment, S-, and O-linked carbohydrates, respectively, as well as linker structure and length. Efficient stereoselective synthetic routes were developed, leading to the formation of the PFPA-conjugated structures in good yields over few steps. The use of glycosyl thiols as donors proved especially efficient and provided the final compounds in up to 70% total yield with high anomeric purities. PFPA-based photochemistry was subsequently used to generate carbohydrate arrays on a polymeric surface, and surface plasmon resonance imaging (SPRi) was applied for evaluation of carbohydrate-protein interactions using the plant lectin Concanavalin A (Con A) as a probe. The results indicate better performance and equal efficiency of S-and O-linked structures with intermediate linker length.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-33214 (URN)10.1039/c1ob05040k (DOI)000289488000018 ()2-s2.0-79954444517 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20110523Available from: 2011-05-23 Created: 2011-05-02 Last updated: 2017-12-11Bibliographically approved
4. Perfluorophenyl Azide Immobilization Chemistry for Single Molecule Force Spectroscopy of the Concanavalin A/Mannose Interaction
Open this publication in new window or tab >>Perfluorophenyl Azide Immobilization Chemistry for Single Molecule Force Spectroscopy of the Concanavalin A/Mannose Interaction
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2010 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 26, no 22, 16677-16680 p.Article in journal (Refereed) Published
Abstract [en]

The versatility of perfluorophenyl azide (PFPA) derivatives makes them useful for attaching a wide variety of biomoleculcs and polymers to surfaces. Herein, it single molecule force spectroscopy (SMFS) study of the concanavalin A/mannose interaction was carried out using PFPA immobilization chemistry. SMFS of the concanavalin A/mannose interaction yielded in average unbinding force of 70-80 pN for loading rates between 8000 and 40 000 pN/s for mannose surfaces on aminated glass. and an unbinding force of 57 +/- 20 pN at 6960 pN/s for mannose surfaces on gold-coated glass. Dynamic force spectroscopy was used to determine the dissociation rate constant, k(off), for this interaction to be 0.16 s(-1).

Keyword
microscopy, cells, adhesion, bond
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-27946 (URN)10.1021/la1036579 (DOI)000283837800012 ()2-s2.0-78650381981 (Scopus ID)
Note
QC 20110104Available from: 2011-01-04 Created: 2011-01-03 Last updated: 2017-12-11Bibliographically approved
5. Photogenerated carbohydrate microarrays to study carbohydrate-protein interactions using surface plasmon resonance imaging
Open this publication in new window or tab >>Photogenerated carbohydrate microarrays to study carbohydrate-protein interactions using surface plasmon resonance imaging
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2010 (English)In: Biosensors & bioelectronics, ISSN 0956-5663, E-ISSN 1873-4235, Vol. 26, no 2, 344-350 p.Article in journal (Refereed) Published
Abstract [en]

A photochemical strategy to generate carbohydrate microarrays on flat sensor surfaces, and to study the protein-binding effects of these arrays by surface plasmon resonance imaging is described. The approach was validated using a panel of carbohydrate-binding proteins. The coupling agents, thiol-functionalized perfluorophenyl azides, allow the covalent attachment of underivatized carbohydrates to gold surfaces by a fast photochemical reaction. Carbohydrate microarrays composed of 3,6-di-O-(alpha-D-mannopyranosyl)-D-mannopyranose (Man3), 2-O-alpha-D-mannopyranosyl-D-mannopyranose (Man2), D-mannose (Man), D-glucose (Glc), and D-galactose (Gal) were constructed, and the binding studies were carried out in real-time using surface plasmon resonance imaging. Results showed that the immobilized carbohydrate ligands retained their binding affinities with lectins, the rank order of which was consistent with that of the free ligands in solution. The detection limit of Man3, Man2, Man, and Glc with the lectin Concanavalin A was measured to be 0.29 nM, 0.18 nM, 0.61 nM, and 3.1 nM, respectively. In addition, soybean agglutinin and Griffonia simplicifolia lectin II were tested on the array, and the results were consistent with the binding selectivity of these lectins with the carbohydrate ligands.

Keyword
Carbohydrate microarray, Photocoupling chemistry, Immobilization, Lectins, Surface plasmon resonance imaging
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-26220 (URN)10.1016/j.bios.2010.08.009 (DOI)000283804400008 ()2-s2.0-77956904068 (Scopus ID)
Funder
EU, European Research Council, MRTN-CT-19561
Note

QC 20150728

Available from: 2011-02-24 Created: 2010-11-21 Last updated: 2017-12-11Bibliographically approved
6. Multivalent glyconanoparticles with enhanced affinity to the anti-viral lectin Cyanovirin-N
Open this publication in new window or tab >>Multivalent glyconanoparticles with enhanced affinity to the anti-viral lectin Cyanovirin-N
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2011 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 47, no 30, 8620-8622 p.Article in journal (Refereed) Published
Abstract [en]

Low-mannose (LM) structures were coupled to gold nanoparticles (Au NPs) to amplify the affinity of LMs with Cyanovirin-N (CV-N) lectins and to study the structures of CV-N variants CVN(Q50C) and CVN(MutDB).

Keyword
HIV-INACTIVATING PROTEIN, GOLD NANOPARTICLES, LIGAND PRESENTATION, BINDING, GP120, GLYCOPROTEINS, RECOGNITION, MAN(8)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-37281 (URN)10.1039/c1cc12981c (DOI)000292986800042 ()2-s2.0-79960493666 (Scopus ID)
Note

QC 20110808

Available from: 2011-08-08 Created: 2011-08-08 Last updated: 2017-12-08Bibliographically approved
7. Photo-Click Immobilization of Carbohydrates on Polymeric Surfaces - A Quick Method to Functionalize Surfaces for Biomolecular Recognition Studies
Open this publication in new window or tab >>Photo-Click Immobilization of Carbohydrates on Polymeric Surfaces - A Quick Method to Functionalize Surfaces for Biomolecular Recognition Studies
2009 (English)In: Bioconjugate chemistry, ISSN 1043-1802, E-ISSN 1520-4812, Vol. 20, no 12, 2364-2370 p.Article in journal (Refereed) Published
Abstract [en]

Methods to rapidly functionalize specific polymeric surfaces with alkynes, which can subsequently be linked to azide-containing carbohydrates, are presented. The methods comprise two main concepts: azide photoligation and Cu-catalyzed azide-alkyne cycloaddition. 2-Azidoethyl-functionalized CL-D-mannopyranoside was synthesized and covalently attached to alkyne-functionalized polymeric surfaces using the techniques. The protein recognition properties of the carbollydrate-presenting surfaces were evaluated using quartz crystal microbalance biosensor instrumentation.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-19043 (URN)10.1021/bc9003519 (DOI)000272690100021 ()19888719 (PubMedID)2-s2.0-72449192287 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
8. Photo-Click Immobilization on Quartz Crystal Microbalance Sensors for Selective Carbohydrate-Protein Interaction Analyses
Open this publication in new window or tab >>Photo-Click Immobilization on Quartz Crystal Microbalance Sensors for Selective Carbohydrate-Protein Interaction Analyses
Show others...
2011 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 83, no 3, 1000-1007 p.Article in journal (Refereed) Published
Abstract [en]

A photoclick method based on azide photoligation and Cu-catalyzed azide-alkyne cycloaddition has been evaluated for the immobilization of carbohydrates to polymeric materials. The biomolecular recognition properties of the materials have been investigated with regard to applicable polymeric substrates and selectivity of protein binding. The method was used to functionalize a range of polymeric surfaces (polystyrene, polyacrylamide, poly(ethylene glycol), poly(2-ethyl-2-oxazoline), and polypropene) with various carbohydrate structures (based on alpha-D-mannose, beta-D-galactose, and N-acetyl-beta-D-glucosamine). The functionalized surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow through system with a series of different carbohydrate-binding proteins (lectins). The method proved to be robust and versatile, resulting in a range of efficient sensors showing high and predictable protein selectivities.

National Category
Analytical Chemistry
Identifiers
urn:nbn:se:kth:diva-30971 (URN)10.1021/ac102781u (DOI)000286689600053 ()2-s2.0-79952126793 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20110318Available from: 2011-03-18 Created: 2011-03-07 Last updated: 2017-12-11Bibliographically approved

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