Surface Functionalization with Carboxylic Acids by Photochemical Microcontact Printing and Tetrazole Chemistry

Abstract

In this paper, we show that carboxylic acid-functionalized molecules can be patterned by photochemical microcontact printing on tetrazole-terminated self-assembled monolayers. Upon irradiation, tetrazoles eliminate nitrogen to form highly reactive nitrile imines, which can be ligated with several different nucleophiles, carboxylic acids being the most reactive. As a proof of concept, we immobilized trifluoroacetic acid to monitor the reaction with X-ray photoelectron spectroscopy. Moreover, we also immobilized peptides and fabricated carbohydrate-lectin as well as biotin-streptavidin microarrays using this method. Surface-patterning was demonstrated by fluorescence microscopy and time-of-flight secondary ion mass spectrometry.

Fluorogenic “Photoclick” Labeling and Imaging of DNA with Coumarin-Fused Tetrazole in Vivo

“…Recent studies have showed that tetrazoles react with different kinds of nucleophiles, upon photolysis, in a biological system. − Therefore, we performed negative control experiments to prove the importance of the tetrazole-ene photoclick reaction in living systems (Figure S15a). The cell lysates containing CTz-SO 3 exhibited very weak fluorescence under normal conditions.…”

Spatially‐Resolved Multiple Metallopolymer Surfaces by Photolithography

“…The N1ss pectra of the irradiated parts of both surfaces differ significantly fromt he respective dark parts. The signals in the non-irradiated sections at 402.7 and 400.2 eV are assigned to the surface bound tetrazole species [44,62] and are similar for both S-Pt and S-Pd,a sw ell as in the case of the free ligand surface S-LP2 ( Figure S74). In contrast,t he irradiated areas are dominated by the nitrogen atoms of ther espective metal complexesc entred at 400.2 eV,w hich are attributed to C=NÀPt and C=NÀPd, respectively.A dditionally,t he N1ss pectra shows af urther weak peak at 398.9 eV belonging to the nitrogen in the aromatic rings of LP2,w hereast he tetrazole-as-signed peak at 402.7 eV disappeared.…”

Visualized Degradation of CO 2 -Based Unsaturated Polyesters toward Structure-Controlled and High-Value-Added Fluorophores

“…μCP as a kind of soft lithography possessing many advantages, including high resolution, very short reaction times, simple large-area patterning, low cost, and so forth. [40][41][42] Certainly, it can help to solve the disadvantages encountered in microfabrication, which is the basic technology used in making all microelectronic systems, such as high cost, complex facilities and technologies for high-energy radiation needed, and limitations to extremely flat silicon substrates. μCP allows the patterned transfer of a molecular ink onto a surface using an elastomeric stamp.…”