Modular Bidentate Hybrid NHC-Thioether Ligands for the Stabilization of Palladium Nanoparticles in Various Solvents.

The synthesis of four different bidentate hybrid NHC-thioether ligands is presented. The corresponding palladium nanoparticles are stable in various solvents, depending on the ligand used, and show high chemoselectivity in the hydrogenation of olefins. The solubility of the nanoparticles can be switched multiple times depending on the pH value of the solvent. XPS analysis (which shows a subtle shift in the binding energy) was identified as a convenient tool to establish the binding mode of NHC ligands.

Photochemical Microcontact Printing by Tetrazole Chemistry.

We developed a simple method to pattern self-assembled monolayers of tetrazole triethoxylsilane with a variety of different molecules by photochemical microcontact printing. Under irradiation, tetrazoles form highly reactive nitrile imines, which react with alkenes, alkynes, and thiols. The covalent linkage to the surface could be unambiguously demonstrated by fluorescence microscopy, because the reaction product is fluorescent in contrast to tetrazole. The modified surfaces were further analyzed by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM), and contact angle goniometry. Protein-repellent micropatterns, a biotin-streptavidin array, and structured polymer brushes could be fabricated with this straightforward method for surface functionalization.

Fast and Simple Preparation of Patterned Surfaces with Hydrophilic Polymer Brushes by Micromolding in Capillaries.

Micropatterns of hydrophilic polymer brushes were prepared by micromolding in capillaries (MIMIC). The polymers are covalently bound to the surfaces by a rapid hetero Diels-Alder reaction, constituting the first example of polymers grafted to surfaces in a defined pattern by MIMIC. The polymers [poly(acrylic acid), poly(hydroxyethyl acrylate), and poly(tetraethylene glycol acrylate) ranging in molecular weight from 1500 to 6000 g mol(-1)] were prepared with narrow dispersities via the reversible addition-fragmentation chain transfer (RAFT) process using a highly electron deficient RAFT agent that can react with surface-anchored dienes such as cyclopentadiene. We demonstrate that the anchoring method is facile to perform and highly suitable for preparing patterned surfaces that are passivated against biological impact in well-defined areas.

Rewritable Polymer Brush Micropatterns Grafted by Triazolinedione Click Chemistry.

Triazolinedione (TAD) click reactions were combined with microcontact chemistry to print, erase, and reprint polymer brushes on surfaces. By patterning substrates with a TAD-tagged atom-transfer radical polymerization initiator (ATRP-TAD) and subsequent surface initiated ATRP, it was possible to graft micropatterned polymer brushes from both alkene- and indole-functionalized substrates. As a result of the dynamic nature of the Alder-ene adduct of TAD and indole at elevated temperatures, the polymer pattern could be erased while the regenerated indole substrate could be reused to print new patterns. To demonstrate the robustness of the methodology, the write-erase cycle was repeated four times.

Immobilization of enzymes via microcontact printing and thiol-ene click chemistry.

This Communication describes a bioconjugation method for the generation of enzyme microarrays on surfaces using photochemical thiol-ene chemistry in combination with microcontact printing. Glucose oxidase and lactase were readily immobilized (i.e., printing time 2 min) on alkene terminated self-assembled monolayers on glass as demonstrated by X-ray photoelectron spectroscopy and fluorescence microscopy. Furthermore, the activity of both immobilized enzymes was confirmed in single enzyme as well as cascade transformations.

One-step synthesis of patterned polymer brushes by photocatalytic microcontact printing.

A novel method to prepare microstructured polymer brushes using TiO2 nanoparticles and photocatalytic microcontact printing is described. It is shown that ethanol amine can be polymerized to linear polyethyleneimine (PEI) driven by the photocatalytic action of TiO2. Upon UV irradiation during microcontact printing of ethanol amine with a stamp coated with TiO2 nanoparticles, patterned polymer brushes with a length of around 50 nm are obtained.

Ultrafast Layer-by-Layer Assembly of Thin Organic Films Based on Triazolinedione Click Chemistry.

Layer-by-layer deposition is a widely used method for surface functionalization. It is shown here that up to 58 covalently linked molecular layers could be assembled in 20 min at room temperature on a silicon wafer by the layer-by-layer click reaction of a divalent triazolinedione and a trivalent diene. The layer growth was found to be linear. The multilayers were analyzed by ellipsometry, atomic force microscopy, and X-ray photoelectron spectroscopy.

Surface patterning with natural and synthetic polymers via an inverse electron demand Diels-Alder reaction employing microcontact chemistry.

Bioorthogonal ligation methods are the focus of current research due to their versatile applications in biotechnology and materials science for post-functionalization and immobilization of biomolecules. Recently, inverse electron demand Diels-Alder (iEDDA) reactions employing 1,2,4,5-tetrazines as electron deficient dienes emerged as powerful tools in this field. We adapted iEDDA in microcontact chemistry (µCC) in order to create enhanced surface functions. µCC is a straightforward soft-lithography technique which enables fast and large area patterning with high pattern resolutions. In this work, tetrazine functionalized surfaces were reacted with carbohydrates conjugated with norbornene or cyclooctyne acting as strained electron rich dienophiles employing µCC. It was possible to create monofunctional as well as bifunctional substrates which were specifically addressable by proteins. Furthermore we structured glass supported alkene terminated self-assembled monolayers with a tetrazine conjugated atom transfer radical polymerization (ATRP) initiator enabling surface grafted polymerizations of poly(methylacrylate) brushes. The success of the surface initiated iEDDA via µCC as well as the functionalization with natural and synthetic polymers was verified via fluorescence and optical microscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR).