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Direct Creation of Biopatterns via Combination of Laser-Based Techniques and Click Chemistry Marianneza Chatzipetrou, Maria Massaouti, Georgios Tsekenis, Anke Kristin Trilling, Esther van Andel, Luc M.W. Scheres, Maarten Marinus Johannes Smulders, Han Zuilhof, and Ioanna Zergioti Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b02860 • Publication Date (Web): 01 Jan 2017 Downloaded from http://pubs.acs.org on January 2, 2017
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Direct Creation of Biopatterns via Combination of Laser-Based Techniques and Click Chemistry Marianneza Chatzipetrou,1 Maria Massaouti,1 George Tsekenis,2 Anke K. Trilling,3 Esther van Andel,4 Luc Scheres,3 Maarten M. J. Smulders,4 Han Zuilhof,4,5* Ioanna Zergioti1,* 1) Department of Physics, National Technical University of Athens, Iroon Polytehneiou 9, Zografou, Athens 15780, Greece. 2) Biomedical Research Foundation of the Academy of Athens, 4 Soranou Ephessiou St., 115 27 Athens, Greece 3) Surfix B.V., Dreijenplein 8, 6703 HB Wageningen, The Netherlands. 4) Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE Wageningen, The Netherlands. 5) Department of Chemical and Materials Engineering, King Abdulaziz University, Jeddah, Saudi Arabia *corresponding authors:
[email protected];
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KEYWORDS: Laser Induced Forward Transfer, Laser photo-activation, direct laser-based writing, thiol-ene reactions, thiol-yne reactions, click reactions, aptamer immobilization, biopatterning.
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ABSTRACT In this paper we present the immobilization of thiol-modified aptamers on alkyne- or alkeneterminated silicon nitride surfaces, by laser-induced click chemistry reactions. The aptamers are printed onto the surface by Laser Induced Forward Transfer (LIFT), which also induces the covalent bonding of the aptamers by thiol-ene or thiol-yne reactions that occur upon UV irradiation of the thiol-modified aptamers with ns laser pulses. This combination of LIFT and laser-induced click chemistry allows the creation of high-resolution patterns without the need of masks. While the click chemistry already takes place during the printing process (single-step process) by the laser pulse used for the printing process, further irradiation of the LIFT-printed aptamers by laser pulses (two-step process), leads to a further increase of the immobilization efficiency.
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INTRODUCTION The controlled bio-functionalization of solid surfaces and the formation of biopatterns of various sizes and dimensions is an essential step in many fields and technologies, such as biotechnology, microtechnology and fabrication of drug delivery systems. The key aspects of an efficient immobilization strategy include its robustness, stability of the attached molecules, specificity of the immobilization chemistry, spatial (and temporal) accuracy, control on pattern size, and simplicity of the process.1 In this regard, different strategies have been designed and followed, combining surface chemical methodologies, for modifying site-specifically the physical and chemical properties of the surfaces, with various techniques for depositing monolayers in specific regions. Methods include micro-contact printing (µCP),2 dip pen lithography (DPN),3 nanografting,4 nanoimprint lithography5 and photolithography,6 which all offer surface patterning with complete or partial spatial and temporal control. Among the several chemical approaches followed, click chemistry-based approaches have received growing attention in surface functionalization chemistry.7 Highly promising members of such surfacebound click chemistries are the thiol-ene and thiol-yne reactions8,9, as a result of their wide applicability and functional group tolerance,10,
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and their potential to realize patterns of
covalently attached biomolecules on solid supports through the activation via a thiyl radical mechanism by simple exposure to UV light, heat or by using radical initiators.7 Specifically the photo-induced variant of the thiol-ene(/-yne) reaction has been used for the site-specific immobilization of proteins,12,13 DNA oligonucleotides14 and enzymes,15 in conjunction with various techniques, such as irradiation through a photomask and micro-contact printing. Although the performance of these approaches is very good, the approach requires multiple
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steps: either for the fabrication of the masks or the master stamps, while intrinsically only two steps are needed (deposition of the material and covalent linking to the surface). Herein, we report an elegant approach for creating micropatterns of aptamers, nucleic acids with specific three dimensional shapes selected through the process of Systematic Evolution of Ligands through Exponential Enrichment (SELEX) so as to be able to recognize selectively a target analyte with a specificity comparable to that of antibodies.16 The aptamers used in this study were able to recognize and bind to the mycotoxin Ochratoxin A (OTA), and their micropatterns were created on silicon-based surfaces using photo-induced thiol-ene(/-yne) chemistry in combination with a direct printing technique, known as Laser-Induced Forward Transfer (LIFT).17 LIFT is a non-contact, maskless, direct laser printing technique, where by the use of a laser pulse, tiny amounts of a biological material can be ejected in the liquid state from a donor thin film, transferred and deposited in a controllable manner onto a receiving solid surface, in the form of a microdroplet. Up to now, the LIFT technique, has been applied to create patterns of functional biomaterials such as DNA,18 aptamers,19 proteins,20 enzymes and cells21 on different substrates and devices, wherein it has been shown that the biomolecules preserve their functionality after the LIFT process. The LIFT technique has significant advantages over several other deposition techniques such as the ink-jet printing22,23 and micro-spotting24 since it is a contactless, direct write technique, which does not require the use of masks or nozzles that limit the range of the printable materials according to their viscosity, and also excels in resolution (ink-jet: 50 µm25, micro-spotting: 70 µm26, LIFT:
