We present a microcontact printing (μCP) routine suitable to introduce defined (sub-) microscale patterns on surface substrates exhibiting a high capillary activity and receptive to a silane-based chemistry. This is achieved by transferring functional trivalent alkoxysilanes, such as (3-aminopropyl)-triethoxysilane (APTES) as a low-molecular weight ink via reversible covalent attachment to polymer brushes grafted from elastomeric polydimethylsiloxane (PDMS) stamps. The brushes consist of poly{N-[tris(hydroxymethyl)-methyl]acrylamide} (PTrisAAm) synthesized by reversible addition–fragmentation chain-transfer (RAFT)-polymerization and used for immobilization of the alkoxysilane-based ink by substituting the alkoxy moieties with polymer-bound hydroxyl groups. Upon physical contact of the silane-carrying polymers with surfaces, the conjugated silane transfers to the substrate, thus completely suppressing ink-flow and, in turn, maximizing printing accuracy even for otherwise not addressable substrate topographies. We provide a concisely conducted investigation on polymer brush formation using atomic force microscopy (AFM) and ellipsometry as well as ink immobilization utilizing two-dimensional proton nuclear Overhauser enhancement spectroscopy (¹H–¹H-NOESY-NMR). We analyze the μCP process by printing onto Si-wafers and show how even distinctively rough surfaces can be addressed, which otherwise represent particularly challenging substrates.

Debondable pressure‐sensitive adhesives (PSAs) promise access to recyclability in microelectronics in the transition toward a circular economy. Two PSAs were synthesized from a tetravalent thiol star‐polyester forming thiol‐catechol‐connectivities (TCC) with either the biorelated DiDopa‐bisquinone (BY*Q) or the fossil‐based bisquinone A (BQA). The PSAs enable debonding by oxidation of TCC‐catechols to quinones. The extent of debonding efficiency depends on the interaction modes, which are determined by the chemical structure differences of both TCC‐motifs. BY*Q‐TCC‐PSA debonds with exceptional loss of 99 % of its approx. 2 MPa shear strength in glass‐on‐glass junctions. For BQA‐TCC‐PSA, a debonding efficiency of only approx. 60 % was found, irrespective of its initial shear strength, which could be tuned up to approx. 7 MPa. The efficiency of debonding for BY*Q‐TCC‐PSA after TCC‐oxidation is linked to the loss of synergistic interactions without strongly affecting the bulk glue properties, outperforming the purely catechol‐based BQA‐analogue.

We present a PDMS-based stamp featuring xanthates within its framework, to graft polymer brushes from its surface. The stamp demonstrates a high efficacy of polymer-supported μCP, but does not show leakage of oligomeric PDMS, which represents a common source of contamination in soft lithography.

We present a novel protocol for the synthesis of enzymatically active microgels. The protocol is based on the precipitation polymerization of N-isopropylacrylamide (NIPAm) in the presence of an enzyme and a protein binding comonomer. A basic investigation on the influence of different reaction parameters such as monomer concentration and reaction temperature on the microgel size and size distribution is performed and immobilization yields are determined. Microgels exhibiting hydrodynamic diameters between 100 nm and 1 μm and narrow size distribution could be synthesized while about 31–44% of the enzyme present in the initial reaction mixture can be immobilized. Successful immobilization including a verification of enzymatic activity of the microgels is achieved for glucose oxidase (GOx) and 2-deoxy-D-ribose-5-phosphate aldolase (DERA). The thermoresponsive properties of the microgels are assessed and discussed in the light of activity evolution with temperature. The positive correlation of enzymatic activity with temperature for the GOx containing microgel originates from a direct interaction of the enzyme with the PNIPAm based polymer matrix whose magnitude is highly influenced by temperature.