TY - JOUR
T1 - NMR hyperfine shifts in blue copper proteins
T2 - A quantum chemical investigation
AU - Zhang, Yong
AU - Oldfield, Eric
PY - 2008/3/26
Y1 - 2008/3/26
N2 - We present the results of the first quantum chemical investigations of 1H NMR hyperfine shifts in the blue copper proteins (BCPs): amicyanin, azurin, pseudoazurin, plastocyanin, stellacyanin, and rusticyanin. We find that very large structural models that incorporate extensive hydrogen bond networks, as well as geometry optimization, are required to reproduce the experimental NMR hyperfine shift results, the best theory vs experiment predictions having R2 = 0.94, a slope = 1.01, and a SD = 40.5 ppm (or ∼4.7% of the overall ∼860 ppm shift range). We also find interesting correlations between the hyperfine shirts and the bond and ring critical point properties computed using atoms-in-molecules theory, in addition to finding that hyperfine shifts can be well-predicted by using an empirical model, based on the geometry-optimized structures, which in the future should be of use in structure refinement.
AB - We present the results of the first quantum chemical investigations of 1H NMR hyperfine shifts in the blue copper proteins (BCPs): amicyanin, azurin, pseudoazurin, plastocyanin, stellacyanin, and rusticyanin. We find that very large structural models that incorporate extensive hydrogen bond networks, as well as geometry optimization, are required to reproduce the experimental NMR hyperfine shift results, the best theory vs experiment predictions having R2 = 0.94, a slope = 1.01, and a SD = 40.5 ppm (or ∼4.7% of the overall ∼860 ppm shift range). We also find interesting correlations between the hyperfine shirts and the bond and ring critical point properties computed using atoms-in-molecules theory, in addition to finding that hyperfine shifts can be well-predicted by using an empirical model, based on the geometry-optimized structures, which in the future should be of use in structure refinement.
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U2 - 10.1021/ja075978b
DO - 10.1021/ja075978b
M3 - Article
C2 - 18314973
AN - SCOPUS:41149092925
SN - 0002-7863
VL - 130
SP - 3814
EP - 3823
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 12
ER -