DEUSS: A Perdeuterated Poly(oxyethylene)‐Based Resin for Improving HRMAS NMR Studies of Solid‐Supported Molecules

Abstract

A novel resin called DEUSS (perdeuterated poly(oxyethylene)-based solid support) has been prepared by anionic polymerization of deuterated [D4]ethylene oxide, followed by cross-linking with deuterated epichlorohydrin. DEUSS can be suspended in a wide range of solvents including organic and aqueous solutions, in which it displays a high swelling capacity. As measured by proton HRMAS of the swollen polymer, the signal intensity of the oxyethylene protons is reduced by a factor of 110 relative to the corresponding nondeuterated poly(oxyethylene)poly(oxypropylene) (POEPOP) resin, thus facilitating detailed HRMAS NMR studies of covalently linked molecules. This 1H NMR invisible matrix was used for the solid-phase synthesis of peptides, oligoureas, and a series of amides as well as their characterization by HRMAS NMR spectroscopy. On-bead NMR spectra of high quality and with resolution comparable to that of liquid samples were obtained and readily interpreted. The complete absence of the parasite resin signals will be of great advantage, for example, for the optimization of multistep solid-phase stereoselective reactions, and for the conformational study of resin-bound molecules in a large variety of solvents.

New Deuterated Oligo(ethylene glycol) Building Blocks and Their Use in the Preparation of Surface Active Lipids Possessing Labeled Hydrophilic Tethers

“…Until now, DPTL has been prepared and utilized without concern for isotope incorporation. , If DPTL were to feature a deuterated tether, one could call on neutron reflectivity measurements 27 to assess the amount of water that resides in the tethered section of the membrane . Moreover the development of isotopically labeled oligo(ethylene glycol) linkers in general would facilitate structural analysis by other techniques including IR, NMR, and mass spectrometry. , …”