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Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy

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Abstract

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), ζ-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules.

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Acknowledgement

This work is supported by the Beckman Foundation. Z. Chen wants to acknowledge the financial support from Dow Corning Corporation through the Dow Corning Assistant/Associate Professorship. Z. Paszti wants to thank to the Hungarian Scientific Research Fund (F43533) for financial support. Cornelius Kristalyn’s help during manuscript preparation is gratefully appreciated.

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Authors and Affiliations

  1. Department of Chemistry, University of Michigan, Ann Arbor, MI, 48109, USA

    Xiaoyun Chen, Jie Wang, Joel N. Schrauben & Zhan Chen

  2. Chemical Research Center of Hungarian Academy of Sciences, P.O. Box 17, 1525, Budapest, Hungary

    Zoltan Paszti

  3. Department of Civil and Environmental Engineering, Michigan State University, East Lansing, MI, 48824, USA

    Fulin Wang & Volodymyr V. Tarabara

  4. Division of Hematology/Oncology, Case Western Reserve University, 10900 Euclid Avenue, WRB2-130, Cleveland, OH, 44106, USA

    Alvin H. Schmaier

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  1. Xiaoyun Chen
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  2. Jie Wang
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  4. Fulin Wang
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  8. Zhan Chen
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Correspondence to Zhan Chen.

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Chen, X., Wang, J., Paszti, Z. et al. Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy. Anal Bioanal Chem 388, 65–72 (2007). https://doi.org/10.1007/s00216-006-0999-8

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  • DOI: https://doi.org/10.1007/s00216-006-0999-8

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