Evaluation of Band-Selective HSQC and HMBC: Methodological Validation on the Cyclosporin Cyclic Peptide and Application for Poly(3-hydroxyalkanoate)s Stereoregularity Determination

Band-selective (bs) HSQC, improving spectral resolution by restriction of the heteronuclear dimension without inducing spectral folding, has been recently used for polymer tacticity determination. Herein is reported an evaluation of various bs-HSQC and bs-HMBC sequences, first from a methodological point of view (selectivity, dependence to INEPT interpulse delay or relaxation delay), using the cyclic peptide cyclosporin selected as a model compound, and then from an applicative approach, comparing tacticity determined from bs-HSQC and bs-HMBC experiments to the one obtained from 1D C-13{H-1} on poly(3-hydroxyalkanoate)s samples. For HSQC sequences, the C-13 selectivity scheme consisting in substituting a C-13 broadband refocalization by a selective one revealed itself problematic, with unwanted aliased signals, whereas the insertion of double pulsed field gradients spin-echo (DPFGSE) or the use of opposite sign gradients bracketing a selective refocalization gave satisfactory results. Determination of the probability of syndiotactic enchainments, P-s, by bs-HSQC is fully consistent and no precision loss was observed when decreasing acquisition time (37 min vs. 106 min for 1D C-13{H-1}). Bs-HMBC, although not straightforwardly applicable for tacticity determination, could provide (after a calibration step) an alternative for compounds of which only C-13 carbonyl signals are resolved enough for discriminating between syndiotactic and isotactic configurations.