S³ HMBC: Spin-State-Selective HMBC for accurate measurement of homonuclear coupling constants. Application to strychnine yielding thirteen hitherto unreported J_HH

TY - JOUR

T1 - S3 HMBC

T2 - Spin-State-Selective HMBC for accurate measurement of homonuclear coupling constants. Application to strychnine yielding thirteen hitherto unreported JHH

AU - Kjaerulff, Louise

AU - Benie, Andrew J.

AU - Hoeck, Casper

AU - Gotfredsen, Charlotte H.

AU - Sørensen, Ole W.

PY - 2016/2/1

Y1 - 2016/2/1

N2 - A novel method, Spin-State-Selective (S3) HMBC, for accurate measurement of homonuclear coupling constants is introduced. As characteristic for S3 techniques, S3 HMBC yields independent subspectra corresponding to particular passive spin states and thus allows determination of coupling constants between detected spins and homonuclear coupling partners along with relative signs. In the presented S3 HMBC experiment, spin-state selection occurs via large one-bond coupling constants ensuring high editing accuracy and unequivocal sign determination of the homonuclear long-range relative to the associated one-bond coupling constant. The sensitivity of the new experiment is comparable to that of regular edited HMBC and the accuracy of the J/RDC measurement is as usual for E.COSY and S3-type experiments independent of the size of the homonuclear coupling constant of interest. The merits of the method are demonstrated by an application to strychnine where thirteen JHH coupling constants not previously reported could be measured.

AB - A novel method, Spin-State-Selective (S3) HMBC, for accurate measurement of homonuclear coupling constants is introduced. As characteristic for S3 techniques, S3 HMBC yields independent subspectra corresponding to particular passive spin states and thus allows determination of coupling constants between detected spins and homonuclear coupling partners along with relative signs. In the presented S3 HMBC experiment, spin-state selection occurs via large one-bond coupling constants ensuring high editing accuracy and unequivocal sign determination of the homonuclear long-range relative to the associated one-bond coupling constant. The sensitivity of the new experiment is comparable to that of regular edited HMBC and the accuracy of the J/RDC measurement is as usual for E.COSY and S3-type experiments independent of the size of the homonuclear coupling constant of interest. The merits of the method are demonstrated by an application to strychnine where thirteen JHH coupling constants not previously reported could be measured.

KW - HMBC

KW - J coupling constants

KW - RDC

KW - S HMBC

KW - Small molecules

U2 - 10.1016/j.jmr.2015.11.007

DO - 10.1016/j.jmr.2015.11.007

M3 - Journal article

AN - SCOPUS:84954515795

SN - 1090-7807

VL - 263

SP - 101

EP - 107

JO - Journal of Magnetic Resonance

JF - Journal of Magnetic Resonance

ER -