Preface
The aim of the book is to investigate interfacial reactions in confinement on
stimuli-responsive homopolymer and diblock copolymer films, the immobilization of
(bio)molecules, and the fabrication of biomolecular patterns by reactive microcontact
printing on these reactive polymer films. Taking advantage of the microphase separation of diblock copolymer films, the fabrication of nanopatterns was investigated,
which could contribute to the future development of a model system that enables one
to area-selectively deposit (write) and address (read out) (bio)molecules.
Chapter 2 presented an overview of (bio)reactive surfaces and biointerfaces based
on organic and polymeric films, their characterization, as well as surface reactions
and patterning of these films. The CP technique was introduced in detail owing to its
central role in this Thesis as a flexible approach for the production of micrometer and
sub-micrometer-scale patterns. Block copolymers were also discussed as materials
used in a “bottom-up” approach to prepare nanometer-scale patterns by exploiting
the characteristic microphase separation.
In Chap. 3, the effect of spatial confinement of the reactants on the
kinetics of the hydrolysis of poly(N-hydroxysuccinimidyl methacrylate) (PNHSMA)
and polystyrene-block-poly(tert-butyl acrylate) (PS n -b-PtBA m ) ultrathin films was
systematically investigated. The activation energies determined according to the
Arrhenius equation, and in particular the activation entropies calculated according to
the transition state theory, revealed that steric crowding in the surface-near region and
tightness of the transition state is less pronounced in the polymer films compared
to related self-assembled monolayers (SAMs) that expose the same reactive ester
groups. Apparent rate constants calculated according to Fourier transform infrared
(FTIR) spectroscopy and contact angle (CA) data for both polymer films and SAMs
directly demonstrated that the polymer films are characterized by higher reactivity,
as well as a higher density of reactive functional groups near and at the polymer
surface. However, the reactivity on polymer films was reduced compared to reactivity
in solution because of restricted access of reactants and reduced mobility of the ester
functional groups in these films. Finally, it was found that polymer film thickness,
thermal pre-treatment of the films, block copolymer composition for PS n -b-PtBA m ,
and local surface composition did not affect the rate constants.
v
The aim of the book is to investigate interfacial reactions in confinement on
stimuli-responsive homopolymer and diblock copolymer films, the immobilization of
(bio)molecules, and the fabrication of biomolecular patterns by reactive microcontact
printing on these reactive polymer films. Taking advantage of the microphase separation of diblock copolymer films, the fabrication of nanopatterns was investigated,
which could contribute to the future development of a model system that enables one
to area-selectively deposit (write) and address (read out) (bio)molecules.
Chapter 2 presented an overview of (bio)reactive surfaces and biointerfaces based
on organic and polymeric films, their characterization, as well as surface reactions
and patterning of these films. The CP technique was introduced in detail owing to its
central role in this Thesis as a flexible approach for the production of micrometer and
sub-micrometer-scale patterns. Block copolymers were also discussed as materials
used in a “bottom-up” approach to prepare nanometer-scale patterns by exploiting
the characteristic microphase separation.
In Chap. 3, the effect of spatial confinement of the reactants on the
kinetics of the hydrolysis of poly(N-hydroxysuccinimidyl methacrylate) (PNHSMA)
and polystyrene-block-poly(tert-butyl acrylate) (PS n -b-PtBA m ) ultrathin films was
systematically investigated. The activation energies determined according to the
Arrhenius equation, and in particular the activation entropies calculated according to
the transition state theory, revealed that steric crowding in the surface-near region and
tightness of the transition state is less pronounced in the polymer films compared
to related self-assembled monolayers (SAMs) that expose the same reactive ester
groups. Apparent rate constants calculated according to Fourier transform infrared
(FTIR) spectroscopy and contact angle (CA) data for both polymer films and SAMs
directly demonstrated that the polymer films are characterized by higher reactivity,
as well as a higher density of reactive functional groups near and at the polymer
surface. However, the reactivity on polymer films was reduced compared to reactivity
in solution because of restricted access of reactants and reduced mobility of the ester
functional groups in these films. Finally, it was found that polymer film thickness,
thermal pre-treatment of the films, block copolymer composition for PS n -b-PtBA m ,
and local surface composition did not affect the rate constants.
v