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Porous metal thin films have high potential for use in applications such as catalysis, electrical contacts, plasmonics, as well as energy storage and conversion. Structuring metal thin films on the nanoscale to generate high surface areas poses an interesting challenge as metals have high surface energy. In this communication, we demonstrate direct access to nanostructured metal nanoparticle hybrid thin films with high nanoparticle loadings through spin coating of a mixture of block copolymer and ligand stabilized platinum and palladium nanoparticles. Plasma cleaning to remove the organics results in a conductive metal thin film. We expect that the methods described here can be generalized to other metals, mixtures of metal nanoparticles, and intermetallics.

High temperature ceramics with porosity on multiple length scales offer great promise in high temperature catalytic applications for their high surface area and low flow resistance in combination with thermal and chemical stability. We have developed a bottom-up approach to functional, porous, high-temperature ceramics structured on eight distinct length scales integrating functional Pt nanoparticles from the near-atomic to the macroscopic level. Structuring is achieved through a combination of micromolding and multicomponent colloidal self-assembly. The resulting template is filled with a solution containing a solvent, a block copolymer, a ceramic precursor, and a nanoparticle catalyst precursor as well as a radical initiator. Heat treatment results in three-dimensionally interconnected, high-temperature ceramic materials functionalized with well-dispersed 1-2 nm Pt catalyst nanoparticles and very high porosity.

Block copolymer−polymer derived ceramic (PDC) precursor nanocomposites were prepared using amorphous poly(isoprene-block-(dimethylamino)ethyl methacrylate) (PI-b-PDMAEMA) and semicrystalline poly(i...

Even after a decade or so of research, the direct synthesis of highly crystalline mesoporous transition-metal oxides that are thermally stable and well ordered still constitutes a major challenge. Although various soft- and hard-templating approaches have been developed in the past, they usually suffer from multiple, tedious steps and often result in poor structure control. For many applications including power generation and energy conversion, however, high crystallinity and controlled mesoporosity are a prerequisite. To this end, here we report on an approach established for group-IV (titanium) and group-V (niobium) oxides, with potential applications to photovoltaic cells and fuel cells, respectively, which overcomes previous limitations. It gives direct access to the desired materials in a 'one-pot' synthesis using block copolymers with an sp2-hybridized carbon-containing hydrophobic block as structure-directing agents which converts to a sturdy, amorphous carbon material under appropriate heating conditions. This in situ carbon is sufficient to act as a rigid support keeping the pores of the oxides intact while crystallizing at temperatures as high as 1,000 degrees C.

Scanning transmission electron tomography was used to determine the three-dimensional structure of a poly(ethylene-alt-propylene-block-ethylene oxide-block-n-hexyl methacrylate) (PEP-b-PEO-b-PHMA) triblock copolymer/aluminosilicate material with domain volume fractions of fPEP = 0.19, fPEO+aluminosilicate = 0.32, and fPHMA = 0.49. The PEO/aluminosilicate domains formed layers of zigzag-shaped strands (concertinas). Strands were arranged in a four-layer woodpile structure (Sozuer, H. S.; Dowling, J. P. J. Mod. Opt. 1994, 41, 231−239),1 in which strands in successive layers run in alternate directions (∼75°) and the third and fourth layers are offset. Modeling suggests the PEP and PHMA domains on the outside of each PEO/aluminosilicate strand may stabilize this unusual structure. This result suggests that synthetic macromolecules with multidomain architectures, such as ABC triblock copolymers, can direct the assembly of silica and other ceramic materials into complex new morphologies.

Block copolymer (BCP) thin films are interesting material systems for nanofabrication since they can form well-defined periodic nanostructures by microphase separation. However, attaining a specific morphology with the required orientation can be challenging. In this study, we investigated the morphological behavior of polystyrene-b-poly(N-isopropylacrylamide)-b-polystyrene (PS-b-PNIPAM-b-PS) BCP thin films by using Atomic Force Microscopy (AFM) and in-situ Grazing-Incidence X-ray Scattering (GISAXS) during selective solvent annealing. Thin films of a lamellar BCP were annealed by using various solvents with different selectivity for the blocks, such as PNIPAM-selective methanol, non-selective tetrahydrofuran (THF) and PS-selective toluene. Solvent annealing using methanol: THF 1:2 (v:v) or methanol: toluene 1:1 (v:v) resulted in the formation of hexagonally ordered perpendicular cylinders, whereas no sustained long-range order was found when only one type of solvent was used. PS-b-PNIPAM-b-PS BCP thin films that have hexagonally ordered perpendicular cylinders are promising for applications where thermo-responsiveness is desired, such as nanofiltration and biomedical applications.

The co-assembly between a polyisoprene-block-poly(dimethylaminoethyl methacrylate) block copolymer and poly(ureamethylvinyl)silazane is investigated. The hybrid morphology can be controlled by systematically increasing the inorganic-to-organic ratio or by changing the molecular weight of the block copolymer. Temperature treatment up to 1500 °C of the hybrids resulted in mesoporous, ordered non-oxide-type ceramics. The results suggest that careful control of co-assembly processes enables access to nanostructured high-temperature ceramics that may have novel mechanical, thermal, and chemical properties.

In this work the primary mechanical property profiles of a specific class of nano-structured polymer/inorganic hybrid materials are characterized. By utilizing sol-gel aluminosilicate synthesis with amphiphilic polyisoprene-block-poly(ethylene oxide) block copolymers as structure-directing agents, block copolymer/aluminosilicate hybrid materials are prepared with nanometer scale hexagonally packed cylinders and lamellae of the inorganic hybrid components, as evidenced by small-angle X-ray scattering. Systematic thermal and dynamic mechanical analyses are performed on these hybrids as well as on the constituting components. Results reveal two transitions from the low temperature, glassy state of the hybrids into high temperature elastic plateau regions, with moduli that vary over orders of magnitude as a function of composition and morphology. The first transition can be assigned to the glass transition of the PI domains while the second is ascribed to a temperature induced softening of the organic components within the PEO/hybrid domains. The results suggest that in the present nanostructured block copolymer/aluminosilicate hybrid materials composition and morphology provide a powerful tool to tailor mechanical property profiles.

Formation of various domain shapes in submicron scale fibers of poly(styrene-block-isoprene) (PS-b-PI) has been investigated via electrospinning. Monodisperse PS-b-PI block copolymers with 29 and 53 vol % of PI were synthesized using two-step anionic polymerization and were dissolved in tetrahydrofuran (THF). Solutions of block copolymer with varying concentrations in THF were electrospun, and fibers with average diameters from 200 nm to 5 μm were obtained. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) studies revealed that cylindrical and lamellar morphology can be formed in electrospun fibers of 29% and 53% PI copolymers, respectively. We note that these domain structures in fibers are not as well developed as those in films possibly due to the short residence time and strong elongational deformation involved in the electrospinning process. For both systems we find that the d spacing in electrospun fibers is smaller than that in the cast film. This could also be attribut...

Catechols play an important role in many natural systems. They are known to readily interact with both organic (e.g., amino acids) and inorganic (e.g., metal ions, metal oxides) compounds, thereby providing a powerful system for protein curing. Catechol crosslinked protein networks, such as sclerotized cuticle and byssal threads of the mussel, have been shown to exhibit excellent mechanical properties. A lot of effort has been devoted to mimicking the natural proteins using synthetic catechol-functionalized polymers. Despite the success in developing catechol-functionalized materials, the crosslinking chemistry of catechols is still a subject of debate. To develop materials with controlled and superior properties, a clear understanding of the crosslinking mechanism of catechols is of vital importance. This review describes the crosslinking pathways of catechol and derivatives in both natural and synthetic systems. We discuss existing pathways of catechol crosslinking and parameters that affect the catechol chemistry in detail. This overview will point towards a rational direction for further investigation of the complicated catechol chemistry.

We describe a scalable method to fabricate nanopatterned bioinspired dry adhesives using colloidal lithography. Close-packed monolayers of polystyrene particles were formed at the air/water interface, on which polydimethylsiloxane (PDMS) was applied. The order of the colloidal monolayer and the immersion depth of the particles were tuned by altering the pH and ionic strength of the water. Initially, PDMS completely wetted the air/water interface outside the monolayer, thereby compressing the monolayer as in a Langmuir trough; further application of PDMS subsequently covered the colloidal monolayers. PDMS curing and particle extraction resulted in elastomers patterned with nanodimples. Adhesion and friction of these nanopatterned surfaces with varying dimple depth were studied using a spherical probe as a counter-surface. Compared with smooth surfaces, adhesion of nanopatterned surfaces was enhanced, which is attributed to an energy-dissipating mechanism during pull-off. All nanopatterned surfaces showed a significant decrease in friction compared with smooth surfaces.

Here we present the fabrication of polypyrrole (PPy) surfaces with a controlled overhang structure. Regularly structured PPy films were produced using interfacial polymerization around a sacrificial crystalline colloidal monolayer at the air/water interface. The morphology of the final inverse colloidal PPy film is controlled by the amount of monomer, the monomer: oxidant ratio and polymerization time. The PPy films exhibit an overhang structure due to depth of particle immersion in the water phase. As a result of the overhang structure, the PPy films are made hydrophobic, although the material itself is hydrophilic. The apparent contact angle of water on the structured surfaces is 109.5°, which is in agreement with the predicted contact angle using the Cassie–Baxter equation for air-filled cavities. This fabrication technique is scalable and can be readily extended to other systems where controlled wettability is required.

Systemic administration of bisphosphonates, e.g. sodium alendronate (Aln) is characterized by extremely low bioavailability and high toxicity. To omit aforementioned drawbacks an injectable system for the intra-bone delivery of Aln based on Aln-loaded nanoparticles (NPs-Aln) suspended in a hydrogel matrix (gellan gum, GG) was developed. Aln was encapsulated in poly(lactide-co-glycolide) (PLGA 85:15) by solid–oil–water emulsification. Drug release tests showed that within 25 days all the encapsulated drug was released from NPs-Aln and the release rate was highest at the beginning and decreased with time. In contrast, by suspending NPs-Aln in a GG matrix, the release rate was significantly lower and more constant in time. The GG–NPs-Aln system was engineered to be easily injectable and was able to reassemble its structure after extrusion as shown by rheological measurements. Invitro studies showed that the GG–NPs-Aln was cytocompatible with MG-63 osteoblast-like cells and it inhibited RANKL-mediated osteoclastic differentiation of RAW 264.7 cells. The injectability, the sustained local delivery of small doses of Aln and the biological activity render the GG–NPs-Aln system promising for the local treatment of osteoporosis and other bone tissue disorders.

Item does not contain fulltext Genetically engineered protein polymers (GEPP) are a class of multifunctional materials with precisely controlled molecular structure and property profile. Representing a promising alternative for currently used materials in biomedical applications, GEPP offer multiple benefits over natural and chemically synthesized polymers. However, producing them in sufficient quantities for preclinical research remains challenging. Here, we present results from an in vitro cellular response study of a recombinant protein polymer that is soluble at low pH but self-organizes into supramolecular fibers and physical hydrogels at neutral pH. It has a triblock structure denoted as C2S(H)48C2, which consists of hydrophilic collagen-inspired and histidine-rich silk-inspired blocks. The protein was successfully produced by the yeast Pichia pastoris in laboratory-scale bioreactors, and it was purified by selective precipitation. This efficient and inexpensive production method provided material of sufficient quantities, purity and sterility for cell culture study. Rheology and erosion studies showed that it forms hydrogels exhibiting long-term stability, self-healing behavior and tunable mechanical properties. Primary rat bone marrow cells cultured in direct contact with these hydrogels remained fully viable; however, proliferation and mineralization were relatively low compared to collagen hydrogel controls, probably because of the absence of cell-adhesive motifs. As biofunctional factors can be readily incorporated to improve material performance, our approach provides a promising route towards biomedical applications.

We tested the adhesive response of polymer surfaces structured with arrays of cylindrical fibrils having diameters of 10–20 µm and aspect ratios 1–2.4. Fibrils had two different tip shapes of end-flaps and round edges. A preload-induced mechanical buckling instability of the fibrils was used to switch between the states of adhesion and non-adhesion. Non-adhesion in fibrils with round edges was reached at preloads that caused fibril buckling, whereas fibrils with end-flaps showed adhesion loss only at very high preloads. The round edge acted as a circumferential flaw prohibiting smooth tip contact recovery leading to an adhesion loss. In situ observations showed that, after reversal of buckling, the end-flaps unfold and re-form contact under prevailing compressive stress, retaining adhesion in spite of buckling. At very high preloads, however, end-flaps are unable to re-form contact resulting in adhesion loss. Additionally, the end-flaps showed varying contact adaptability as a function of the fibril–probe alignment, which further affects the preload for adhesion loss. The combined influence of preload, tip shape and alignment on adhesion can be used to switch adhesion in bioinspired fibrillar arrays.

Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of subnanometer Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand headgroup density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar, and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal NP-based nanospheres, cylinders, and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules.

We developed a dry synthetic adhesive system inspired by gecko feet adhesion that can switch reversibly from adhesion to non-adhesion with applied pressure as external stimulus. Micropatterned polydimethylsiloxane (PDMS) surfaces with pillars of 30 μm length and 10 μm diameter were fabricated using photolithography and moulding. Adhesion properties were determined with a flat probe as a function of preload. For low and moderate applied compressive preloads, measured adhesion was 7.5 times greater than on flat controls whereas for high applied preloads adhesion dropped to very low values. In situ imaging shows that the increased preload caused the pillars to deform by bending and/or buckling and to lose their adhesive contact. The elasticity of PDMS aids the pillar recovery to the upright position upon removal of preload enabling repeatability of the switch.

Nanocomposites have great potential for the rational synthesis of tailored materials. However, the templating process that transfers the self-organized nanostructure of a block copolymer or other mesophase onto the functional material is by no means trivial, and often involves multiple steps, each of which presents its own chemical and physical challenges. As a result the nanocomposite may not be homogeneous, but can be phase-separated into various components which may feature their own specific microstructure. Here it is shown how scanning microbeam small-angle X-ray scattering (µSAXS) can be used to characterize a thermoset resol/poly(isoprene-block-ethylene oxide) nanocomposite on multiple length scales with respect to homogeneity and microphase separation.

We studied the effects of pillar dimensions and stiffness of biocompatible and biodegradable micropatterned surfaces on adhesion on different compliant substrates. The micropatterned adhesives were based on biocompatible polydimethylsiloxane (PDMS) and biodegradable poly(lactic-co-glycolic) acid (PLGA) polymer systems. Micropatterned and non-patterned compliant PDMS did not show significant differences in adhesion on compliant mice ear skin or on gelatin-glycerin model substrates. However, adhesion measurements for micropatterned stiff PLGA on compliant gelatin-glycerin model substrates showed significant enhancement in pull-off strengths compared to non-patterned controls.

Continuous core-shell nanofibers with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymer/polymer derived ceramic (PDC) precursor nanocomposites as cores enveloped in rigid polyacrylonitrile (PAN) shells were nanomanufactured using coaxial electrospinning. The cylindrical confinement imposed by the rigid shell led to ordered morphologies in the core not observed in bulk block copolymer nanocomposites.

Nature has developed reversibly adhesive surfaces whose stickiness has attracted much research attention over the last decade. The central lesson from nature is that “patterned” or “fibrillar” surfaces can produce higher adhesion forces to flat and rough substrates than smooth surfaces. This paper critically examines the principles behind fibrillar adhesion from a contact mechanics perspective, where much progress has been made in recent years. The benefits derived from “contact splitting” into fibrils are separated into extrinsic/intrinsic contributions from fibril deformation, adaptability to rough surfaces, size effects due to surface-to-volume ratio, uniformity of stress distribution, and defect-controlled adhesion. Another section covers essential considerations for reliable and reproducible adhesion testing, where better standardization is still required. It is argued that, in view of the large number of parameters, a thorough understanding of adhesion effects is required to enable the fabrication of reliable adhesive surfaces based on biological examples.

We report the first successful application of an ordered bicontinuous gyroid semiconducting network in a hybrid bulk heterojunction solar cell. The freestanding gyroid network is fabricated by electrochemical deposition into the 10 nm wide voided channels of a self-assembled, selectively degradable block copolymer film. The highly ordered pore structure is ideal for uniform infiltration of an organic hole transporting material, and solid-state dye-sensitized solar cells only 400 nm thick exhibit up to 1.7% power conversion efficiency. This patterning technique can be readily extended to other promising heterojunction systems and is a major step toward realizing the full potential of self-assembly in the next generation of device technologies. © 2009 American Chemical Society.

We explore the morphology space of nanocomposites prepared from poly(isoprene-block-ethylene oxide) (PI-b-PEO) diblock copolymers as structure directing agents for aluminosilicate nanoparticles prepared from (3-glycidyloxypropyl)trimethoxysilane (GLYMO) and aluminum(III) sec-butoxide. The results of structural investigations of over 60 polymer-inorganic nanocomposites are reported. They are obtained from 12 different block copolymers of varying molecular weight (10-100 kg/mol) and PEO weight fraction (fw 0.1-0.8) through addition of different amounts of inorganic components. Eight different morphologies as well as composites with biphasic character are observed. Individual block copolymers show up to five different well-defined morphologies upon addition of the inorganic sols. Differential scanning calorimetry (DSC) studies on the composites show that the addition of the inorganic components suppresses PEO crystallization when the inorganic to PEO weight fraction ratio of the composites is greater than 1.3-1.5. The eight phases are mapped out using two- and three-component morphology diagrams.

The synthesis of ordered mesoporous metal composites and ordered mesoporous metals is a challenge because metals have high surface energies that favor low surface areas. We present results from the self-assembly of block copolymers with ligand-stabilized platinum nanoparticles, leading to lamellar CCM-Pt-4 and inverse hexagonal (CCM-Pt-6) hybrid mesostructures with high nanoparticle loadings. Pyrolysis of the CCM-Pt-6 hybrid produces an ordered mesoporous platinum-carbon nanocomposite with open and large pores (≥10 nanometers). Removal of the carbon leads to ordered porous platinum mesostructures. The platinum-carbon nanocomposite has very high electrical conductivity (400 siemens per centimeter) for an ordered mesoporous material fabricated from block copolymer self-assembly.

In the present study, a poly(isoprene-block-dimethylamino ethyl methacrylate) diblock copolymer (PI-b-PDMAEMA) is used to structure-direct a polysilazane pre-ceramic polymer, commercially known as Ceraset. To the polymer was added a 2-fold excess in weight of the silazane oligomer (Ceraset). The resulting composite was cast into films, and after cooperative self-assembly of block copolymer and Ceraset, the structure was permanently set in the hexagonal columnar morphology, as evidenced by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Cross-linking of the silazane oligomer was achieved with a radical initiator at 120 degrees C. Upon heating of the composite to 1500 degrees C under nitrogen, the structure is preserved and a mesoporous ceramic material is obtained, as demonstrated by SAXS and TEM. The pores are open and accessible, as evidenced by nitrogen sorption/desorption measurements indicating a surface area of about 51 m2 g-1 and a pore diameter of 13 nm, consistent with TEM analysis. These results suggest that the use of block copolymer mesophases may provide a simple, easily controlled pathway for the preparation of various high-temperature ceramic mesostructures.

Here, we present systematic studies on the removal of the polymer template from inverse hexagonally ordered poly(butadiene-block-2-dimethylaminoethyl methacrylate)–phosphomolybdic acid (H3PMo12O40) nanocomposites. Highly ordered mesophases are obtained via an evaporation-induced self-assembly process. Different techniques are used to remove the organic template: direct calcination in air, a two-step heat treatment ((1) argon atmosphere and (2) oxidative atmosphere), and a combination of heat and plasma treatment. Our studies show that direct calcination in air and two-step heat treatment lead to a collapse of mesostructure before complete carbon removal is accomplished. In contrast, plasma etching of heat treated ultra-microtomed samples results in hexagonally ordered porous nanofilms.

Many insects are considered to be pests and can be serious threats to buildings. Insecticides represent an effective way to control pest insects but are harmful to the environment. As an eco-friendlier alternative, we have formulated waterborne, organic paints which provided a slippery physical barrier for leafcutter ants ( Atta cephalotes ) on vertical surfaces. Different paints were produced by varying the Pigment Volume Concentration (PVC) and amount of TiO 2 and CaCO 3 particles, and characterised in terms of contact angles, surface roughness and scrub resistance. The paints’ slipperiness for A. cephalotes ants was evaluated in climbing tests on vertical paint panels (by recording the percentage of fallen ants). Two main factors reduced the insects’ attachment to vertical paint surfaces: (1) the PVC: in paints above a critical PVC, more loose particles detach from the coating and thereby reduce insect attachment; and (2) the type, dimensions and shape of solid particles: CaCO 3 particles detach more easily from the paint than TiO 2, probably due to their larger size and platelet shape. Paints formulated at PVC 70 and containing 20 wt% CaCO 3 showed the best performance in terms of slipperiness, as well as providing good scrub resistance.

Insect pests cause considerable damage worldwide to plants, buildings and human health. This review explores how controlling insect adhesion to coatings might mitigate these problems. We summarise the current knowledge of the mechanisms of insect adhesion on natural and synthetic surfaces and natural examples of non-adhesive and slippery surfaces. Biomimetic, multi-scaled rough and particle-transferring surfaces provide an efficient method to reduce adhesion of crawling insects.

We can learn from nature that, next to chemistry, surface structures can be used for tuning different functions of surfaces. In this thesis we present a novel fabrication method using colloidal templating on the air/water interface. Two distinct ways to obtain nanopatterned surfaces are described, namely (i) addition of PDMS on top of the colloidal monolayer and (ii) synthesis of polypyrrole around the particles of the monolayer. An increase in adhesion is found for the nanopatterned PDMS surfaces, and the contact angle of water on the nanopatterned polypyrrole surface is increased.

Tissue engineering is a relatively new, but actively developing field of biomedical science. It aims at organ or tissue regeneration by use of scaffolds, which are usually seeded with cells prior to implantation, and stimulated by bioactive cues or growth factors. It is a promising and valuable alternative to the use of transplants, for which the demand is greater than the supply, and for which application is connected with high risk of rejection and infection due to immunosuppressant medication. One of the main challenges of tissue engineering, that we tried to address in this thesis, is the design of biocompatible and functional biomaterials that could serve as cell scaffold. We investigated, if protein-based polymers, more specifically, if the de novo designed, C2SH48C2 copolymer, which self-assembles into fibers upon a pH-trigger, is a suitable material for cell scaffolds. In Chapter 2 we described the design and production, by means of recombinant DNA technology, of C2SH48C2. The protein was efficiently secreted by Pichia pastoris at high yields of g/l levels and we proposed an effective purification method. We showed that fibers and gels form by self-assembly upon pH adjustment, and that rheological properties of the obtained hydrogels depend on the total protein concentration. In view of potential biomedical applications, erosion studies were performed, which indicated that the gels exhibited long term stability in conditions mimicking those in body fluid. The biocompatibility of the gel scaffolds was demonstrated in a 2D cell culture study. However, despite the cell viability, a low proliferation rate was observed. To improve cell performance in contact with C2SH48C2 hydrogels (Chapter 3) we incorporated active domains in the C2SH48C2 protein by recombinant functionalization. We described the synthesis of two protein variants: (1) BRGDC2SH48C2, N-terminally enriched in integrin-binding domains (RGD) and (2) BKRSRC2SH48C2, N-terminally enriched in heparin binding domains (KRSR). We showed precise control over the amount of active domains in the final gels, by simply mixing the variants of the proteins in the desired molar ratio before inducing gelation. A 23-day cell culture study, performed using MG-63 cells, revealed that the presence of RGD and KRSR domains positively influenced cell attachment, spreading and activity. A synergistic effect was observed, i.e. scaffolds containing both bioactive domains yielded fully confluent layers of cells at an earlier stage during cell culture than the other gels. We concluded that cell behavior can be controlled by tuning the content of functional domains. In Chapter 4, we tested the suitability of the C2SH48C2 protein, enriched in RGD domains, for cell encapsulation, as the conditions of 3D cell culturing are more similar to the environment of cells in the body. We independently varied gel stiffness (by means of protein concentration) and functional motif (RGD) density, and analyzed the influence of these parameters on the cellular response. The viability and proliferation of MG-63 cells, encapsulated in the gels at different protein concentrations and RGD densities, was investigated with a cell activity assay, and by quantitative analysis of confocal pictures of nuclei (DAPI stain) and F-actin (phalloidin). We showed that optimal cell behavior is obtained in the presence of RGD domains and at low protein concentrations. The results indicated that RGD functionality is not the sole requirement; the gel matrix needs to exhibit the right mechanical properties and architecture to allow for cell growth, cytoplasmic extension and migration. Finally, in Chapter 5, we showed that active domains (here KRSR) can serve multiple functions in the material. We demonstrated the cross-linking ability of KRSR domains in the presence of heparin, leading to structural and mechanical changes in the scaffolds. In dilute systems (0.1 % (w/v)), heparin increases the rate of fiber growth, and induces fiber bundling. At higher protein concentrations, leading to the hydrogel formation (2 % (w/v)), the gelation rate and final storage modulus can be tuned by the amount of heparin and KRSR domain density. We concluded that with this approach, the material properties of C2SH48C2 protein gels can be effectively and simply controlled in a straightforward and biocompatible way. In Chapter 6 we described the main requirements for biomaterials and discussed to what extent they are fulfilled by protein-based polymers, and in particular, by the presented C2SH48C2 protein. The main advantages over alternative materials, and the challenges that need to be addressed before application in tissue engineering becomes a reality, were discussed. We ended with suggestions to improve the properties of C2SH48C2 protein for use as a biomaterial, especially its biodegradability, and its structural and mechanical properties.

Mussels can affix themselves to a variety of wet surfaces under harsh marine conditions by secreting liquid mussel foot proteins (mfps) as superglues. Inside the mussel, the superglues are fluid-like and are kept at low pH, i.e. pH 3. Upon secretion into seawater at pH 8, the superglues are cured efficiently through crosslinking of the catecholic amino acid 3, 4-dihydroxyphenylalanine (DOPA). Currently, a lot of efforts have been devoted to developing functional materials using biomimetic polymers, although the crosslinking chemistry of the catechols in DOPA is still under debate. The goal of this thesis is twofold : 1) better understanding of crosslinking chemistry of catechols; 2) the design and synthesis of catechol-containing functional materials. To gain better understanding of the crosslinking mechanism, we summarized the possible crosslinking mechanisms of catechols that have been proposed in the last few decades. We rationalize the parameters that may affect the crosslinking pathways and kinetics such as pH, temperature, types of oxidant and so on. Motivated by the open questions as discussed in the literatures, we investigate the crosslinking mechanism of catechols with amines using model compounds 4-methyl catechol (4MC) and propylamine (PA) in aqueous media. From the spectroscopic and chromatographic studies, we find that the reaction between 4MC and PA is very fast and complicated. In the first five minutes, more than 60 products have already been formed. These products are mainly formed via three pathways, i.e., Michael-type addition, Schiff-base reaction, and phenol-phenol coupling. Among these products, the majority are amine-catechol adducts formed by Michael-type addition. In addition, we also designed catechol-containing functional copolymers. We designed a copolymer containing both functionalities-amines and catechols: poly(dopamine acrylamide-co-2-aminoethyl methacrylamide hydrochloride). We synthesized the copolymer in aqueous medium using free radical polymerization. The polymer is pH-responsive and meets two important requirements for a binder that can be used in water-borne coatings: (1) it is water-soluble at acidic pH during storage; (2) during drying and curing at basic pH, it becomes water-insoluble. The aqueous solubility switch is ascribed to the crosslinking reactions between catechols and amines at basic pH. Besides fulfilling the requirement of solubility switch, the coatings should also have proper adhesion properties. Therefore, we synthesize five copolymers with different amount of catechols from free radical polymerization of N-(3,4-dihydroxyphenethyl)methacrylamide (DMA) and 2-methoxyethyl methacrylate (MEA) with different compositions. We find that, under dry and wet conditions, an optimal composition for the best adhesion is achieved at 5 mol% of DMA. Polymers with a higher concentration of DMA show little adhesion, which is attributed to the high stiffness of the material, resulting in poor contact with the probe.