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Determination of accessible amino groups on surfaces by chemical derivatization with 3,5-bis(trifluoromethyl)phenyl isothiocyanate and XPS/NEXAFS analysis

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Abstract

The determination of amino groups on surfaces capable of binding biomolecules is important for the understanding and optimization of technologically relevant coupling processes. In this study, three different types of amino-functionalized model surfaces, amino thiolate on Au, amino siloxane on Si, and polyethylene (PE) foils and films reacted with 1,2-diaminoethane (DAE) were derivatized with 3,5-bis(trifluoromethyl)phenyl isothiocyanate. Subsequently, these samples were analyzed by chemical derivatization X-ray photoelectron spectroscopy (CD-XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The determination of amino groups by this analytical approach allows gaining insight into the availability of groups on surfaces that can actually serve as attachment sites for biomolecules in technical applications. In the case of the amino thiolate on Au, almost 90% of the expected amino groups were detected by CD-XPS. Investigation of the amino siloxane films revealed lower yields for the derivatization reaction in the order of 30%. The lowered reaction yields are thought to be due to interactions between the amino siloxane’s amino and silanol groups or the underlying substrate, making them inaccessible to the derivatization agent. The aminated PE samples are characterized by a complex surface chemistry and structure, and reaction yields of the derivatization reaction cannot be unequivocally derived. However, 1–3% of the total carbon atoms in the surface layer were found to be bound to amino groups accessible to the derivatization agent. It can be concluded that, depending on the detailed character of the investigated amino-terminated surface, the amount of amino groups accessible to CD-XPS can be substantially lower than the total amount of amino groups present at the surface.

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Abbreviations

XPS:

X-ray photoelectron spectroscopy

CD:

Chemical derivatization

NEXAFS:

Near-edge X-ray fine structure

PE:

Polyethylene

DAE:

1,2-Diaminoethane

SAM:

Self-assembled monolayer

APS:

3-Aminopropylsiloxane

APhS:

p-Aminophenylsiloxane

BE:

Binding energy

FWHM:

Full width at half maximum

TEY:

Total energy electron yield

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Acknowledgements

We thank Mrs. Decker (BAM VI.5) for assistance with plasma treatment of PE foils. Special thanks are due to M. Mast, Dr. O. Schwartzkopf, Dr. W. Braun, and Dr. G. Reichardt for their support at BESSY II. A number of relevant NEXAFS references have been identified by using the Gas Phase Core Excitation Database provided by the Hitchcock Group, McMaster University, Hamilton, Canada, at http://unicorn.mcmaster.ca.

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Authors and Affiliations

  1. BAM VI.43—Surface and Thin Film Analysis, Bundesanstalt für Materialforschung und -prüfung, Unter den Eichen 44-46, 12203, Berlin, Germany

    Nora Graf, Andreas Lippitz, Thomas Gross & Wolfgang E. S. Unger

  2. Fraunhofer-Institut für Angewandte Polymerforschung, Geiselbergstr. 69, 14476, Potsdam, Germany

    Falko Pippig & Andreas Holländer

Authors
  1. Nora Graf
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  2. Andreas Lippitz
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  3. Thomas Gross
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  4. Falko Pippig
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  5. Andreas Holländer
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  6. Wolfgang E. S. Unger
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Correspondence to Wolfgang E. S. Unger.

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Graf, N., Lippitz, A., Gross, T. et al. Determination of accessible amino groups on surfaces by chemical derivatization with 3,5-bis(trifluoromethyl)phenyl isothiocyanate and XPS/NEXAFS analysis. Anal Bioanal Chem 396, 725–738 (2010). https://doi.org/10.1007/s00216-009-3233-7

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