Abstract
We report a novel glycan array architecture that binds the mannose-specific glycan binding protein, concanavalin A (ConA), with sub-femtomolar avidity. A new radical photopolymerization developed specifically for this application combines the grafted-from thiol–(meth)acrylate polymerization with thiol–ene chemistry to graft glycans to the growing polymer brushes. The propagation of the brushes was studied by carrying out this grafted-to/grafted-from radical photopolymerization (GTGFRP) at >400 different conditions using hypersurface photolithography, a printing strategy that substantially accelerates reaction discovery and optimization on surfaces. The effect of brush height and the grafting density of mannosides on the binding of ConA to the brushes was studied systematically, and we found that multivalent and cooperative binding account for the unprecedented sensitivity of the GTGFRP brushes. This study further demonstrates the ease with which new chemistry can be tailored for an application as a result of the advantages of hypersurface photolithography.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 20350-20357 |
| Number of pages | 8 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 60 |
| Issue number | 37 |
| DOIs | |
| State | Published - Sep 6 2021 |
Funding
This work was supported by funding from the Air Force Office of Scientific Research (FA9550-19-1-0356), the Army Research Office (W911NF-17-1-0326), the National Science Foundation (DBI-2032176, CHE-1905270, CHE-1900509), the Army Research Office (W911NF-15-1-0568), and the Department of Defense (MURI 15RT0675). We would like to acknowledge the Surface Science Facility and the Imaging Facility of CUNY Advanced Science Research Center for instrumentation used to characterize the surfaces. The National Science Foundation (CHE 1828399) for the NEO-500 NMR spectrometer used to obtain data included in this publication; the Keck-II facility of Northwestern University's NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the International Institute for Nanotechnology at Northwestern University, and Northwestern's MRSEC program (NSF DMR-1720139). This work was supported by funding from the Air Force Office of Scientific Research (FA9550‐19‐1‐0356), the Army Research Office (W911NF‐17‐1‐0326), the National Science Foundation (DBI‐2032176, CHE‐1905270, CHE‐1900509), the Army Research Office (W911NF‐15‐1‐0568), and the Department of Defense (MURI 15RT0675). We would like to acknowledge the Surface Science Facility and the Imaging Facility of CUNY Advanced Science Research Center for instrumentation used to characterize the surfaces. The National Science Foundation (CHE 1828399) for the NEO‐500 NMR spectrometer used to obtain data included in this publication; the Keck‐II facility of Northwestern University's NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS‐2025633), the International Institute for Nanotechnology at Northwestern University, and Northwestern's MRSEC program (NSF DMR‐1720139).
Keywords
- glycopolymers
- lectins
- lithography
- microarrays
- thiol–ene
ASJC Scopus subject areas
- General Chemistry
- Catalysis