Two-dimensional magic angle spinning NMR investigation of naturally occurring chitins: precise 1H and 13C resonance assignment of alpha- and beta-chitin.
13C homonuclear through-bond correlations of alpha- and beta-chitin were determined by using two-dimensional (2D) INADEQUATE spectra of these allomorphs purified from crab shell and squid pen, respectively. The 2D (13)C-(13)C correlation spectra where two directly bonded carbons share a common double-quantum frequency (DQ) enabled us to precisely assign all (13)C resonances of the chitin allomorphs for the first time. Following the complete (13)C assignment, (1)H chemical shifts of protons attached to each carbon nuclei were assigned by 2D frequency-switched Lee-Goldberg (FSLG) (1)H-(13)C heteronuclear correlation (HETCOR) spectra of the chitin allomorphs, recorded with a short mixing time (60 micros) to provide isotropic (1)H-(13)C chemical shift correlations between bonded pairs proton and carbon nuclei. From the (13)C and (1)H chemical shifts of chitin allomorphs, all 2-deoxy-2-acetamide-D-glucose (N-acetyl-D-glucosamine) monomer units in each allomorph were revealed to be an identical (13)C-(13)C backbone conformation and magnetically equivalent. In addition, it was strongly suggested that there are two different hydrogen-bonding patterns at the hydroxyl groups of alpha-chitin by comparing (1)H chemical shifts at the C6 site of alpha-chitin with those at the same site of beta-chitin.
Kono
Hiroyuki
H
Bruker BioSpin Company Ltd., Tsukuba, Ibaraki 305-0051, Japan. hiroyuki.kono@bruker-biospin.jp
D000818:Animals; D003386:Brachyura / Q000033:anatomy & histology / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002247:Carbon Isotopes; D002686:Chitin / Q000032:analysis* / Q000737:chemistry* / Q000235:genetics / Q000302:isolation & purification; D002942:Circular Dichroism; D049832:Decapodiformes / Q000033:anatomy & histology / Q000737:chemistry; D006860:Hydrogen Bonding; D017665:Hydroxyl Radical / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D011522:Protons; D011789:Quantum Theory
D002247:Carbon Isotopes; D011522:Protons; D002686:Chitin; D017665:Hydroxyl Radical; D002244:Carbon