Simultaneous Dual Encoding of Three‐Dimensional Structures by Light‐Induced Modular Ligation

Abstract

A highly efficient strategy for the simultaneous dual surface encoding of 2D and 3D microscaffolds is reported. The combination of an oligo(ethylene glycol)-based network with two novel and readily synthesized monomers with photoreactive side chains yields two new photoresists, which can be used for the fabrication of microstructures (by two-photon polymerization) that exhibit a dual-photoreactive surface. By combining both functional photoresists into one scaffold, a dual functionalization pattern can be obtained by a single irradiation step in the presence of adequate reaction partners based on a self-sorting mechanism. The versatility of the approach is shown by the dual patterning of halogenated and fluorescent markers as well as proteins. Furthermore, we introduce a new ToF-SIMS mode ("delayed extraction") for the characterization of the obtained microstructures that combines high mass resolution with improved lateral resolution.

Functionalized 3D Architected Materials via Thiol‐Michael Addition and Two‐Photon Lithography

“…[37] The thiol-Michael pre-functionalization approach described here also allows for the fabrication of such reactive structures, which can be used for post-functionalization reactions. To illustrate this point, we wrote plates of known dimensions using PETTA/N-BOC on glass substrates treated with 3-(trimethoxysilyl)propyl methacrylate to promote adhesion of the polymer.…”

“…To achieve spatial resolution on the surface of the structures as demonstrated in other works in the literature, [37-39] it is necessary to have photoactive functional groups, which cannot be achieved by using amines alone. However, the approach taken here does not necessarily preclude spatial resolution as photoactive groups could potentially be installed via the amines, which could be subsequently modified on the surface in a spatially controlled manner.…”

“…[35] A more modern approach has been to synthesize monomers with the functional groups of interest. By carefully designing the monomers such that the desired functional groups are not consumed during the polymerization process, structures with unique properties such as photo-reactive surfaces, [37-39] intrinsic chemical sensing, [40] chemical resistance, [41] bioactivity [42-43] and biodegradability [44-45] can be fabricated. Since the functional groups are directly installed onto the monomer, they should exhibit a higher surface density of functional groups.…”

Polymer Interfaces: Synthetic Strategies Enabling Functionality, Adaptivity, and Spatial Control

“…Figure 5 shows a recent example, a scaffold written from two different photoresists, each expressing a different secondary photochemistry. 96 The approach is realized by copolymerizing two photoreactive monomers within the respective resists: one resting on phenacyl sulfide functionalities (which release thioaldehydes after irradiation) 97 and one resting on so-called photoenols, i.e., photocaged dienes. 98 The strategy, depicted in Figure 5, allows to encode one DLW written scaffold with two functionalities in a one-pot photochemical irradiation step, paving the way for precision 3D interface design with orthogonally functionalized biomarkers for e.g.…”

Hierarchische Selbstassemblierung dreidimensional gedruckter Schlüssel/Schloss‐Kolloide durch Formerkennung

“…[10] Auch ein erster helicaler Mikrotransporter wurde schon präsentiert. Basis hierfür ist ein konfokaler Laseraufbau, der in der Lage ist, Photolacke über Zwei-Photonen-Lithographie mit hoher räumlicher Auflçsung in Voxeln zu vernetzen.…”