x
Contents
3.2.3 Comparison of Surface Reactions in SAMs
and Ultrathin Polymer Films . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.3 Ultrathin PS n -b-PtBA m Polymer Films . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.1 Characterization of Polymer Thin Film Surface
Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.3.2 Characterization and Kinetics of the Hydrolysis
of PS m -b-PtBA n Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.3.3 Investigation of the Temperature Dependence
of Reaction Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3.4 Effects of Film Thickness and Thermal Pretreatment
on Reaction Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.3.5 Dependence of Hydrolysis Kinetics on Surface
Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.3.6 Comparison of Reactivity of T-Butyl Esters
in PS n -b-PtBA m Thin Films and in Solution . . . . . . . . . . . . . . 63
3.4 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4 Reactive Thin Polymer Films as Platforms
for the Immobilization of Biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.2 Investigation of the Reactivity of PNHSMA . . . . . . . . . . . . . . . . . . . . 71
4.2.1 Coupling of PEG 500 -NH 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.2.2 Coupling of Fluoresceinamine and BSA to PNHSMA
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.3 Comparison of Surface Reactions on PNHSMA Films
and NHS-C10 Monolayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.3 Swelling Behavior and Stability of PNHSMA Films . . . . . . . . . . . . . 78
4.4 Immobilization of DNA and Surface-Based Hybridization . . . . . . . . 79
4.4.1 DNA Immobilization Studied by SPR . . . . . . . . . . . . . . . . . . . 79
4.4.2 Investigation of DNA Hybridization by SPFS
and Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.5 Toward the Detection of Pathogenic Bacteria on PNHSMA
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.6 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5 Tailored Biointerfaces via Derivatization
of Polystyrene-b-Poly(Tert-Butyl Acrylate) Thin Films . . . . . . . . . . . . . 91
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2 Investigation of the Surface Chemistry of PS 690 -b-PtBA 1210
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.2.1 Surface Hydrolysis of PS 690 -b-PtBA 1210 Films . . . . . . . . . . . 93
5.2.2 Covalent Coupling of PEG to Activated
PS 690 -b-PtBA 1210 Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Contents
3.2.3 Comparison of Surface Reactions in SAMs
and Ultrathin Polymer Films . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.3 Ultrathin PS n -b-PtBA m Polymer Films . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.1 Characterization of Polymer Thin Film Surface
Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.3.2 Characterization and Kinetics of the Hydrolysis
of PS m -b-PtBA n Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.3.3 Investigation of the Temperature Dependence
of Reaction Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3.4 Effects of Film Thickness and Thermal Pretreatment
on Reaction Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.3.5 Dependence of Hydrolysis Kinetics on Surface
Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.3.6 Comparison of Reactivity of T-Butyl Esters
in PS n -b-PtBA m Thin Films and in Solution . . . . . . . . . . . . . . 63
3.4 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4 Reactive Thin Polymer Films as Platforms
for the Immobilization of Biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.2 Investigation of the Reactivity of PNHSMA . . . . . . . . . . . . . . . . . . . . 71
4.2.1 Coupling of PEG 500 -NH 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.2.2 Coupling of Fluoresceinamine and BSA to PNHSMA
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.3 Comparison of Surface Reactions on PNHSMA Films
and NHS-C10 Monolayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.3 Swelling Behavior and Stability of PNHSMA Films . . . . . . . . . . . . . 78
4.4 Immobilization of DNA and Surface-Based Hybridization . . . . . . . . 79
4.4.1 DNA Immobilization Studied by SPR . . . . . . . . . . . . . . . . . . . 79
4.4.2 Investigation of DNA Hybridization by SPFS
and Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.5 Toward the Detection of Pathogenic Bacteria on PNHSMA
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.6 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5 Tailored Biointerfaces via Derivatization
of Polystyrene-b-Poly(Tert-Butyl Acrylate) Thin Films . . . . . . . . . . . . . 91
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2 Investigation of the Surface Chemistry of PS 690 -b-PtBA 1210
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.2.1 Surface Hydrolysis of PS 690 -b-PtBA 1210 Films . . . . . . . . . . . 93
5.2.2 Covalent Coupling of PEG to Activated
PS 690 -b-PtBA 1210 Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
