Photochemical Microcontact Printing by Tetrazole Chemistry

Abstract

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.

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

“…We recently showed the possibility to immobilize biotin-thiol on tetrazole-terminated SAMs by the addition of a biotin-tagged thiol to nitrile imines. 27 In this experiment, we demonstrate the immobilization of biotin without previous derivatization. To this end, we used a 25 mM solution of biotin in DMSO as ink.…”

“…Using this strategy, it was possible to grow polymers by immobilization of a maleimide-functionalized atom transfer radical polymerization initiator and to prepare a biotin−streptavidin microarray by printing a biotin-tagged thiol. 27 In 1985, Heimgartner and Meier described the nucleophilic addition of carboxylic acids to nitrile imines to yield hydrazides (Figure 1). 28 This reaction has been used to synthesize singlechain polymer nanoparticles by irradiating a polyacrylic acidbearing tetrazole moieties.…”

Diphenyltetrazole Modified Bacterial Cellulose Film: Considerations on Heterogeneous Modification and Bioconjugation

“…The diaryltetrazole group was recognized as a versatile functional group for photoclick reactions. The tetrazole ring is stable under normal conditions, but under ultraviolet irradiation it forms an intermediate that is highly reactive in the presence of some nucleophiles 22,23 . For instance, this methodology was used to promote selective coupling of thiols to a polyethyleneglycol diphenyltetrazole-modified polymer 20 .…”

Advanced Colloidal Lithography Beyond Surface Patterning

“…To promote the commercial success of structure‐based applications, it is highly demanded to development cost effective for efficient patterning of large areas. Many unconventional fabrication techniques (soft lithography) have been developed, including microcontact printing, nanoimprinting, and templating using either block copolymers or polystyrene nanospheres . However, most non‐conventional lithographic techniques require the assistance of conventional lithographic techniques such as photolithography to design and make masks or masters.…”