Mechanisms of fibrinogen adsorption at solid substrates.

Adsorption of fibrinogen, modeled as a linear chain of touching beads of various sizes, was theoretically studied using the random sequential adsorption (RSA) model. The adsorption process was assumed to consist of two steps: (i) formation of an irreversibly bound fibrinogen monolayer under the side-on orientation, which is independent of the bulk protein concentration and (ii) formation of the reversibly bound, end-on monolayer, whose coverage was dependent on the bulk concentration. Calculation based on the RSA model showed that the maximum surface concentration of the end-on (reversible) monolayer equals N(⊥∞) = 6.13 × 10(3) μm(-2) which is much larger than the previously found value for the side-on (irreversible) monolayer, equal to N(∞) = 2.27 × 10(3) μm(-2). Hence, the maximum surface concentration of fibrinogen in both orientations is determined to be 8.40 × 10(3) μm(-2) corresponding to the protein coverage of 5.70 mg m(-2) assuming 20% hydration. Additionally, the surface blocking function (ASF) was determined for the end-on fibrinogen adsorption, approximated for the entire range of coverage by the interpolating polynomial. For the coverage approaching the jamming limit, the surface blocking function (ASF) was shown to vanish proportionally to (θ(⊥∞) - θ(⊥))(2). These calculation allowed one to theoretically predict adsorption isotherms for the end-on regime of fibrinogen and adsorption kinetics under various transport conditions (diffusion and convection). Using these theoretical results, a quantitative interpretation of experimental data obtained by TIRF and ellipsometry was successfully performed. The equilibrium adsorption constant for the end-on adsorption regime was found to be 8.04 × 10(-3) m. On the basis of this value, the depth of the adsorption energy minimum, equal to -17.4 kT, was predicted, which corresponds to ΔG = -41.8 kJ mol(-1). This is in accordance with adsorption energy derived as the sum of the van der Waals and electrostatic interactions. Besides having significance for predicting fibrinogen adsorption, theoretical results derived in this work also have implications for basic science providing information on mechanisms of anisotropic protein molecule adsorption on heterogeneous surfaces.

[1]  P. Schaaf,et al.  Irreversible adsorption of colloidal particles on solid substrates , 2000 .

[2]  S. Kalasin,et al.  Non-specific adhesion on biomaterial surfaces driven by small amounts of protein adsorption. , 2009, Colloids and surfaces. B, Biointerfaces.

[3]  H.P. Ericksen,et al.  The Trinodular Structure of Fibrinogen: Confirmation by both Shadowing and Negative Stain Electron Microscopy , 1979, Thrombosis and Haemostasis.

[4]  P. Tengvall,et al.  Molecular packing of HSA, IgG, and fibrinogen adsorbed on silicon by AFM imaging , 1998 .

[5]  Alicia Toscano,et al.  Fibrinogen adsorption on three silica-based surfaces: conformation and kinetics. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[6]  J. Blawzdziewicz,et al.  Streaming potential studies of colloid, polyelectrolyte and protein deposition. , 2010, Advances in colloid and interface science.

[7]  K. V. van Holde,et al.  Frictional coefficients of multisubunit structures. II. Application to proteins and viruses , 1967, Biopolymers.

[8]  R. Doolittle.  Fibrinogen and fibrin. , 1984, Annual review of biochemistry.

[9]  J. Feder,et al.  Geometry of random sequential adsorption , 1986 .

[10]  Pascal Viot,et al.  Random sequential adsorption of anisotropic particles. I. Jamming limit and asymptotic behavior , 1992 .

[11]  J. Kirkwood,et al.  Errata: The Intrinsic Viscosities and Diffusion Constants of Flexible Macromolecules in Solution , 1948 .

[12]  Z. Adamczyk,et al.  Fibrinogen adsorption on mica studied by AFM and in situ streaming potential measurements. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[13]  P. Viot,et al.  From car parking to protein adsorption: an overview of sequential adsorption processes , 1999, cond-mat/9906428.

[14]  D. Reinhoudt,et al.  Assembly of nanoparticles on patterned surfaces by noncovalent interactions , 2008 .

[15]  Pascal Viot,et al.  Random sequential adsorption of anisotropic particles. II. Low coverage kinetics , 1992 .

[16]  M. Cieśla,et al.  Kinetics of fibrinogen adsorption on hydrophilic substrates. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[17]  Julian Talbot,et al.  Surface exclusion effects in adsorption processes , 1989 .

[18]  J. Weisel,et al.  A model for fibrinogen: domains and sequence. , 1985, Science.

[19]  J. Weisel,et al.  Carboxyl-terminal portions of the alpha chains of fibrinogen and fibrin. Localization by electron microscopy and the effects of isolated alpha C fragments on polymerization. , 1993, The Journal of biological chemistry.

[20]  Gibum Kim,et al.  The Vroman effect: a molecular level description of fibrinogen displacement. , 2003, Journal of the American Chemical Society.

[21]  S. Harding,et al.  On the hydrodynamic analysis of macromolecular conformation. , 1995, Biophysical chemistry.

[22]  P. Schaaf,et al.  Irreversible adsorption/deposition kinetics: A generalized approach , 1999 .

[23]  J. Dahn,et al.  Fibrinogen adsorption onto 316L stainless steel, Nitinol and titanium , 2009 .

[24]  Sit Ps,et al.  Surface-dependent conformations of human fibrinogen observed by atomic force microscopy under aqueous conditions. , 1999 .

[25]  C. L. Berrie,et al.  Conformational Changes in the Plasma Protein Fibrinogen upon Adsorption to Graphite and Mica Investigated by Atomic Force Microscopy , 2003 .

[26]  C. Werner,et al.  Electrokinetic surface characterization of biomedical polymers — a survey , 1999 .

[27]  Reiner Salzer,et al.  In situ conformational analysis of fibrinogen adsorbed on Si surfaces. , 2005, Colloids and surfaces. B, Biointerfaces.

[28]  E. Wajnryb,et al.  Friction of rodlike particles adsorbed to a planar surface in shear flow. , 2008, The Journal of chemical physics.

[29]  James W. Evans,et al.  Random and cooperative sequential adsorption , 1993 .

[30]  M. Santore,et al.  Effect of Surface Hydrophobicity on Adsorption and Relaxation Kinetics of Albumin and Fibrinogen: Single-Species and Competitive Behavior , 2001 .

[31]  Henry S. Slayter,et al.  The Fibrinogen Molecule: Its Size, Shape, and Mode of Polymerization , 1959, The Journal of biophysical and biochemical cytology.

[32]  Radan Slavik,et al.  Molecular arrangement of adsorbed fibrinogen molecules characterized by specific monoclonal antibodies and a surface plasmon resonance sensor , 1998 .

[33]  Paweł,et al.  Random sequential adsorption of spheroidal particles: Kinetics and jamming limit , 1996 .

[34]  R. D. Vigil,et al.  Random sequential adsorption of unoriented rectangles onto a plane , 1989 .

[35]  J. Barbasz,et al.  Deposition of colloid particles at heterogeneous and patterned surfaces. , 2009, Advances in colloid and interface science.

[36]  J. G. de la Torre,et al.  Transport properties and hydrodynamic centers of rigid macromolecules with arbitrary shapes , 1980 .

[37]  Y. Missirlis,et al.  pH and ionic strength effect on single fibrinogen molecule adsorption on mica studied with AFM. , 2007, Colloids and surfaces. B, Biointerfaces.

[38]  Peter J. Scales,et al.  Electrokinetics of the silica-solution interface: a flat plate streaming potential study , 1992 .

[39]  Adamczyk.  Kinetics of Diffusion-Controlled Adsorption of Colloid Particles and Proteins. , 2000, Journal of colloid and interface science.

[40]  Martin Malmsten,et al.  Ellipsometry Studies of Protein Layers Adsorbed at Hydrophobic Surfaces , 1994 .

[41]  P. Tengvall,et al.  Aggregation of HSA, IgG, and Fibrinogen on Methylated Silicon Surfaces. , 1998, Journal of colloid and interface science.

[42]  P. Viot,et al.  A structural comparison of random sequential adsorption and equilibrium configurations of spherocylinders , 1994 .

[43]  J. Barbasz,et al.  Particle assembly on patterned surfaces bearing circular (dots) and rectangular (stripes) surface features. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[44]  J. G. Torre,et al.  Effects from bead size and hydrodynamic interactions on the translational and rotational coefficients of macromolecular bead models , 1983 .

[45]  Saturation coverage in random sequential adsorption of very elongated particles , 1992 .