Mechanisms of Fibrinogen Adsorption on Silica Sensors at Various pHs: Experiments and Theoretical Modeling

Langmuir. 2019 Sep 3;35(35):11275-11284. doi: 10.1021/acs.langmuir.9b01341. Epub 2019 Aug 22.

Abstract

The adsorption kinetics of human serum fibrinogen at silica substrates was studied using optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance (QCM) techniques. Measurements were performed at pH 3.5, 4, and 7.4 for various ionic strengths. The experimental data were interpreted in terms of a hybrid random sequential adsorption model. This allowed the mass transfer rate coefficient for the OWLS cell and maximum coverages to be determined at various pHs. The appearance of different, pH-dependent mechanisms of fibrinogen adsorption on silica substrates was confirmed. At pH 3.5 the molecules mostly adsorb in the side-on orientation that produces a low maximum coverage of ca. 1 mg m-2. At this pH, the kinetics derived from the OWLS measurements agree with those theoretically predicted using the convective-diffusion theory. In consequence, a comparison of the OWLS and QCM results allows the water factor and the dynamic hydration of fibrinogen molecules to be determined. At pH 7.4, the OWLS method gives inaccurate kinetic data for the low coverage range. However, the maximum coverage that was equal to ca. 4 mg m-2 agrees with the QCM results and with previous literature results. It is postulated that the limited accuracy of the OWLS method for lower coverage stems from a heterogeneous structure of fibrinogen monolayers, which consist of side-on and end-on adsorbed molecules. One can expect that the results acquired in this work allow development of a robust procedure for preparing fibrinogen monolayers of well-controlled coverage and molecule orientation, which can be exploited for efficient immunosensing purposes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Fibrinogen / chemistry*
  • Fibrinogen / metabolism
  • Humans
  • Hydrogen-Ion Concentration
  • Particle Size
  • Quartz Crystal Microbalance Techniques
  • Silicon Dioxide / chemistry*
  • Spectrum Analysis
  • Surface Properties

Substances

  • Silicon Dioxide
  • Fibrinogen