UV-VIS Curable PEG Hydrogels for Biomedical Applications with Multifunctionality.

Multifunctional biomedical materials capable of integrating optical functions are highly desirable for many applications, such as advanced intra-ocular lens (IOL) implants. Therefore, poly(ethylene glycol)-diacrylate (PEG-DA) hydrogels are used with different photoinitiators (PI). In addition to standard UV PI Irgacure, Erythrosin B and Eosin Y are used as PI with high sensitivity in the optical range of the spectrum.

Influence of Network Structure on the Crystallization Behavior in Chemically Crosslinked Hydrogels.

The network structure of hydrogels is a vital factor to determine their physical properties. Two network structures within hydrogels based on eight-arm star-shaped poly(ethylene glycol)(8PEG) have been obtained; the distinction between the two depends on the way in which the macromonomers were crosslinked: either by (i) commonly-used photo-initiated chain-growth polymerization (8PEG⁻UV), or (ii) Michael addition step-growth polymerization (8PEG⁻NH₃). The crystallization of hydrogels is facilitated by a solvent drying process to obtain a thin hydrogel film.

Micro-Patterning of PEG-Based Hydrogels With Gold Nanoparticles Using a Reactive Micro-Contact-Printing Approach.

In this work a novel, relatively simple, and fast method for patterning of gold nanoparticles (Au NPs) on poly(ethylene glycol) (PEG)-based hydrogels is presented. In the hereby exploited reactive micro-contact printing (reactive-μ-CP) process, the surface of a micro-relief patterned PDMS-stamp is first functionalized with an amino-silane self-assembled monolayer (SAM), which is then inked with Au NPs. The stamp is subsequently brought into conformal contact with thiol-functionalized PEG-based hydrogel films.

Micropatterning of Au NPs on PEG Hydrogels Using Different Silanes To Control Cell Adhesion on the Nanocomposites.

Amino-silanization of silica-based substrates has proven to be effective in guiding the immobilization of citrate-stabilized Au NPs in a good, homogeneous fashion. This accomplishment has formed the basis of fabricating micropatterns of Au NPs on such substrates by patterning of oxidized silicon wafers with (3-aminopropyl)trimethoxysilane (amino-silane) using the microcontact printing (μCP) process. This micropattern of amino-silane is used to specifically adsorb Au NPs.

Self-assembly of porphyrin hexamers via bidentate metal-ligand coordination.

The supramolecular assembly of metal-porphyrin hexamers with bidentate ligands in chloroform solutions is demonstrated by UV/Vis and 1H NMR-titrations, and Small Angle Neutron Scattering (SANS) experiments. Titrations of zinc porphyrin hexamer Zn1 with 1,4-diazabicyclo[2,2,2]octane (DABCO) revealed that at a DABCO/Zn1 molar ratio of 3, intermolecular sandwich complexes are formed, which can be considered as "circular-shaped porphyrin ladders". These supramolecular complexes further aggregate into larger polymeric stacks, as a result of a combination of cooperativity effects, π-π stacking interactions, and chelate effects.

Novel Wet Micro-Contact Deprinting Method for Patterning Gold Nanoparticles on PEG-Hydrogels and Thereby Controlling Cell Adhesion.

In the present work we introduce a novel method to create linear and rectangular micro-patterns of gold nanoparticles (Au NPs) on poly(ethylene glycol) (PEG) hydrogels. The strategy consists of removing Au NPs from defined regions of the silicon wafer by virtue of the swelling effect of the hydrogel. Using this method, which we denote as "Wet Micro-Contact Deprinting", well-defined micro-patterns of Au NPs on silicon can be created.

Surface Patterning of Gold Nanoparticles on PEG-Based Hydrogels to Control Cell Adhesion.

We report on a versatile and easy approach to micro-pattern gold nanoparticles (Au NPs) on 8-arm poly(ethylene glycol)-vinyl sulfone thiol (8PEG-VS-SH) hydrogels, and the application of these patterned Au NPs stripes in controlling cell adhesion. Firstly, the Au NPs were patterned on silicon wafers, and then they were transferred onto reactive, multifunctional 8PEG-VS-SH hydrogels. The patterned, micrometer-sized Au NPs stripes with variable spacings ranging from 20 μm to 50 μm were created by our recently developed micro-contact deprinting method.

Design of S-Allylcysteine in Situ Production and Incorporation Based on a Novel Pyrrolysyl-tRNA Synthetase Variant.

The noncanonical amino acid S-allyl cysteine (Sac) is one of the major compounds of garlic extract and exhibits a range of biological activities. It is also a small bioorthogonal alkene tag capable of undergoing controlled chemical modifications, such as photoinduced thiol-ene coupling or Pd-mediated deprotection. Its small size guarantees minimal interference with protein structure and function.

Geometric Control of Cell Alignment and Spreading within the Confinement of Antiadhesive Poly(Ethylene Glycol) Microstructures on Laser-Patterned Surfaces.

In this study, a mask-less laser-assisted patterning method is used to fabricate well-defined cell-adhesive microdomains delimited by protein-repellent poly(ethylene glycol) (PEG) microstructures prepared from multiarm (8-PEG) macromonomers. The response of murine fibroblasts (L-929) toward these microdomains is investigated, revealing effective cell confinement within the cell-adhesive areas surrounded by nonadhesive 8-PEG microstructures. Moreover, the spatial positioning of cells in microdomains of various sizes and geometries is analyzed, indicating control of cell density, size, and elongated cell shape induced by the size of the microdomains and the geometric confinement.

Enzymatically cross-linked hyperbranched polyglycerol hydrogels as scaffolds for living cells.

Although several strategies are now available to enzymatically cross-link linear polymers to hydrogels for biomedical use, little progress has been reported on the use of dendritic polymers for the same purpose. Herein, we demonstrate that horseradish peroxidase (HRP) successfully catalyzes the oxidative cross-linking of a hyperbranched polyglycerol (hPG) functionalized with phenol groups to hydrogels. The tunable cross-linking results in adjustable hydrogel properties.

Cell phenotypic changes of mouse connective tissue fibroblasts (L-929) to poly(ethylene glycol)-based gels.

Cellular responses to various gels fabricated by photoinitiated crosslinking using acrylated linear and multi-arm poly(ethylene glycol) (PEG)-based and poly(propylene glycol)-b-poly(ethylene glycol) precursors were investigated. While no protein adsorption and cell adhesion were observed on the hydrophilic PEG-based gels, protein adsorption and cell adhesion did occur on the more hydrophobic gel generated from the block copolymer precursor. Murine fibroblast viability on the poly(ethylene glycol)-based gels was studied in the course of 72 h and the results indicated no cytotoxicity.

Microengineered PEG hydrogels: 3D scaffolds for guided cell growth.

Designing three-dimensional (3D) scaffolds for selective manipulation of cell growth is of high relevance for applications in regenerative medicine. Especially, scaffolds with oriented morphologies bear high potential to guide the restoration of specific tissues. The fabrication of hydrogel scaffolds that support long-term survival, proliferation, and unidirectional growth of embedded cells is presented here.

Topography-induced cell adhesion to Acr-sP(EO-stat-PO) hydrogels: the role of protein adsorption.

Topographic surface patterning of intrinsically non-adhesive P(EO-stat-PO)-based hydrogels can lead to the adhesion and spreading of fibroblasts. Explanations for this unexpected behavior are discussed, particularly with regard to non-specific protein adsorption from the serum-supplemented culture medium. The presence of serum proteins is shown to be essential for adhesion.

Combined influence of substrate stiffness and surface topography on the antiadhesive properties of Acr-sP(EO-stat-PO) hydrogels.

Biomaterials that prevent nonspecific protein adsorption and cell adhesion are of high relevance for diverse applications in tissue engineering and diagnostics. One of the most widely applied materials for this purpose is Poly(ethylene glycol) (PEG). We have investigated how micrometer line topography and substrate elasticity act upon the antiadhesive properties of PEG-based hydrogels.

A hydrophobic perfluoropolyether elastomer as a patternable biomaterial for cell culture and tissue engineering.

We present a systematic study of a perfluoropolyether (PFPE)-based elastomer as a new biomaterial. Besides its excellent long-term stability and inertness, PFPE can be decorated with topographical surface structures by replica molding. Micrometer-sized pillar structures led to considerably different cell morphology of fibroblasts.

Deformation of nanostructures on polymer molds during soft UV nanoimprint lithography.

Soft nanoimprint lithography (soft NIL) relies on a mechanical deformation of a resist by a patterned polymer used as a mold. Here, we report on the investigation of the nanopattern fidelity of the high pressure imprint process based on a perfluorinated polyether (PFPE) soft mold material. The perfluorinated polyether material was found to be well suited to transfer the mold pattern into the resist by a direct imprinting process at low cost.

Induction of specific macrophage subtypes by defined micro-patterned structures.

In this study, we investigated the influence of different perfluoropolyether (PFPE) microstructures on the inflammatory response of human macrophages. We generated four different microstructured PFPE surfaces by replica molding from silicon masters. The function-associated surface markers 27E10 and CD163 were monitored using flow cytometry to measure the pro- and anti-inflammatory reactions.

Nanomolding of PEG-based hydrogels with sub-10-nm resolution.

A simple, soft nanolithographic method is used to fabricate sub-10-nm structures on star polyethylene glycol-based hydrogels and perfluoropolyether-based materials. Very small features, for example, gold nanoparticles of size approximately 8 nm with an interparticle distance of approximately 100 nm, are successfully reproduced from a hard silicon master into both elastomers. Scanning force microscopy is used to investigate the replicas, and the original hexagonal pattern of the nanoparticles is clearly recognized.

Surface topography induces fibroblast adhesion on intrinsically nonadhesive poly(ethylene glycol) substrates.

Important in developing new biomaterials is the prevention of unspecific protein adsorption and cell interactions that in vivo can lead to a foreign body reaction. On the other hand, the material should support the growth of a specific cell type in a defined way. We investigate the possibility of manipulating cellular behavior on an intrinsically nonadhesive material by topographic patterning without additional surface chemistry modifications.

Microcontact deprinting: a technique to pattern gold nanoparticles.

A simple and general patterning technique for inorganic nanoparticles (NPs, e.g., gold NPs) is demonstrated, consisting of the selective lift-off of metal precursor loaded block copolymer micelles.

Giant porphyrin disks: control of their self-assembly at liquid-solid interfaces through metal-ligand interactions.

The synthesis and self-assembly behaviour of porphyrin dodecamers 1H(2) and Zn-1, which consist of twelve porphyrins that are covalently attached to a central aromatic core, is described. According to STM, 1D and 2D NMR studies, and molecular modelling calculations, the porphyrin dodecamers have a yo-yo-shaped structure. Their large pi surface, in combination with their disk-like shape, allows them to form self-assembled structures, which in the case of Zn-1 can be tuned by adding bidentate ligands.

Micro- and nanopatterned star poly(ethylene glycol) (PEG) materials prepared by UV-based imprint lithography.

A UV-based imprint lithography method is used for the direct surface structuring of hydrogel-based biomaterials, which are prepared from a family of tailor-made star poly(ethylene glycol) formulations. Bulk star poly(ethylene glycol) (PEG) hydrogels are fabricated by cross-linking acrylate-functionalized star PEG macromolecules. Cross-linking is achieved by radical reactions initiated by UV irradiation.

Aided self-assembly of porphyrin nanoaggregates into ring-shaped architectures.

The formation of micrometer-sized, highly ordered porphyrin rings on surfaces has been investigated. The porphyrin-based nanoarchitectures are formed by deposition from evaporating solutions through a surface dewetting process which can be tuned by variations in the substitution pattern of the molecules used, the coating of the surface and the conditions under which the evaporation takes place. Control over the combined self-assembly and surface dewetting results in nanorings possessing a defined internal architecture.