A versatile approach to high-throughput microarrays using thiol-ene chemistry

Materials Research Laboratory, University of California, Santa Barbara, California 93105, USA.
Nature Chemistry (Impact Factor: 23.3). 02/2010; 2(2):138-45. DOI: 10.1038/nchem.478
Source: PubMed

ABSTRACT Microarray technology has become extremely useful in expediting the investigation of large libraries of materials in a variety of biomedical applications, such as in DNA chips, protein and cellular microarrays. In the development of cellular microarrays, traditional high-throughput printing strategies on stiff, glass substrates and non-covalent attachment methods are limiting. We have developed a facile strategy to fabricate multifunctional high-throughput microarrays embedded at the surface of a hydrogel substrate using thiol-ene chemistry. This user-friendly method provides a platform for the immobilization of a combination of bioactive and diagnostic molecules, such as peptides and dyes, at the surface of poly(ethylene glycol)-based hydrogels. The robust and orthogonal nature of thiol-ene chemistry allows for a range of covalent attachment strategies in a fast and reliable manner, and two complementary strategies for the attachment of active molecules are demonstrated.

Download full-text


Available from: Sherry Hikita, Jul 02, 2015
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Thiol-ene and thiol-yne reactions are explored as efficient pathways towards rapid production of diverse monodisperse macroporous and nonporous functional beads. In a straightforward method, polymer beads containing amine, hydroxyl and carboxyl groups have been prepared by reacting a tetrafunctional thiol with a range of mono and/or multifunctional -enes/-ynes containing the desired functional groups. The thiol-ene and thiol-yne reactions have been performed in a simple home-made microfluidic device utilizing thiol and ene/yne monomers at a 1 : 1 ratio of thiol to p-bond. The porous functional beads were prepared making use of a porogen in combination with a photoinitiator. The optical and scanning electron microscopy images demonstrated monodispersity of the beads with a spherical shape ranging in size from 210 to 600 mm. The beads were characterized in terms of glass transition temperature, surface area measurement and composition. The accessible amine and hydroxyl loading in the beads ranges from 0.23 to 0.69 mmol g À1 and 0.24 to 0.64 mmol g À1 respectively, as determined by the Fmoc method. This work demonstrates the applicability of thiol-ene and thiol-yne reactions in microfluidics as a powerful tool for the rapid design of functional beads for diverse applications.
    Polymer Chemistry 01/2010; 1(1):685. DOI:10.1039/c0py00041h · 5.37 Impact Factor
  • Macromolecules 03/2010; 43(7). DOI:10.1021/ma100109t · 5.93 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Donor−acceptor chromophores were almost quantitatively introduced into the side chains of a polystyrene derivative by sequential “click chemistry”-type addition reactions as an efficient postfunctionalization method. The first click reaction is the conventional Cu(I)-catalyzed azide−alkyne cycloaddition (CuAAC), and the second one is the atom-economic addition of strong acceptor molecules, such as tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ), to the aniline-substituted electron-rich alkynes. Steric hindrance was found to be an important factor in determining the reactivity of alkyne-acceptor addition reactions. All obtained polymers showed good solubility in common organic solvents, and they were fully characterized by GPC, 1H NMR and IR spectroscopy, and elemental analysis. After the acceptor addition, the polymers showed an intense charge-transfer (CT) band centered at ca. 480 nm for the TCNE adducts and ca. 710 nm for the TCNQ adducts. Electrochemical measurements of these polymers also revealed well-defined oxidation and reduction potentials, offering consistency between the electrochemical and optical band gaps. The second harmonic generation (SHG) coefficients (d33 and d15) of the polymer thin films were evaluated by SHG measurements before and after corona poling at 150 °C, a temperature that was determined on the basis of thermal analyses. The results show that the TCNE adducted polymers possess better SHG properties than the corresponding TCNQ adducted polymers, probably reflecting the superior chromophore mobility within the polymers.
    Macromolecules 05/2010; 43(12). DOI:10.1021/ma100869m · 5.93 Impact Factor