Damien Jeannerat, University of Geneva, Switzerland
Repliement spectral de la dimention 13C. Un puissant outil d’étude de mélanges complexes de petites molécules utilisants des expériences basées sur l’HSQC Spectral Aliasing of the 13C dimension. A powerful tool to Study Mixtures of Small Molecules Using HSQC-Based experiments Do not hesitate to contact:
[email protected] 1
High resolution in indirect dimensions
.UMBER OF T INCREMENTS
PT (A
PT (B
(A
(B
## ##
!CQUISITION TIME MIN
!CQUISITION TIME H MIN
2
Spectral aliasing
SW0 SWa
νa = mod(ν0 + SWa/2 − CF, SWa) − SWa/2 + CF ν0 = νa ± n SWa 3
Spectral aliasing
W
4
Optimization 2D aliased heteronuclear spectrum Optimization
... ...
13 48.468 6.4
... ...
Computer-optimized spectral aliasing
2D Full-width heteronuclear spectrum
C# δ(13C) LW 1H dispersion
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
... ...
1D carbon or DEPT spectrum
13 48.468 6.4 5.8-5.7
Series of 2D aliased heteronuclear spectrum
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Optimization 2D aliased heteronuclear spectrum Optimization
... ...
13 48.468 6.4
... ...
Computer-optimized spectral aliasing
2D Full-width heteronuclear spectrum
C# δ(13C) LW 1H dispersion
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
... ...
1D carbon or DEPT spectrum
13 48.468 6.4 5.8-5.7
Series of 2D aliased heteronuclear spectrum
6:D
7' SRLQWV 6: SSP +]
7'D
6
1D carbon or DEPT spectrum
Optimization 2D aliased heteronuclear spectrum Optimization
... ...
13 48.468 6.4
... ...
2D Full-width heteronuclear spectrum
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
... ...
Computer-optimized spectral aliasing
C# δ(13C) LW 1H dispersion
13 48.468 6.4 5.8-5.7
Series of 2D aliased heteronuclear spectrum
#YCLOSPORIN ! #(./ 37A PPM 4$ PT -AX T MS &ACTOR # # # #
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SSP 7
Optimization 2D aliased heteronuclear spectrum Optimization
... ...
13 48.468 6.4
... ...
Computer-optimized spectral aliasing
2D Full-width heteronuclear spectrum
C# δ(13C) LW 1H dispersion
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
... ...
1D carbon or DEPT spectrum
13 48.468 6.4 5.8-5.7
Series of 2D aliased heteronuclear spectrum
6:D
7' SRLQWV 6: SSP +]
7'D
D. Jeannerat, J.Magn. Reson. 186, p112, 8
1D carbon or DEPT spectrum
Optimization 2D aliased heteronuclear spectrum Optimization
... ...
13 48.468 6.4
... ...
2D Full-width heteronuclear spectrum
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
... ...
Computer-optimized spectral aliasing
C# δ(13C) LW 1H dispersion
13 48.468 6.4 5.8-5.7
Series of 2D aliased heteronuclear spectrum
#
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#YCLOSPORIN ! #(./ 37A PPM 4$ PT -AX T MS &ACTOR D. Jeannerat, J.Magn. Reson. 186, p112, 9
Combining full and 10-ppm spectra
β-Cubebin
α-Cubebin
W+ SSP 10
Combining full and 10-ppm spectra
?2.04
52.0?
β-Cubebin
52.04
α-Cubebin
W+ SSP 11
Combining full and 10-ppm spectra
" " "
D E F G HI
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+ SSP
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SSP
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Bruno Vitorge 12
Applications
Combinations 2D HSQC-TOCSY 2D HSQC-NOESY Series selective-TOCSY-HSQC 2D-aliasing 3D HSQC-TOCSY 3D HSQC-COSY
D. Mury, et al. Magn. Reson. in Chem. (2009), 47, 909 13
Diffusion measurements CT-HSQC-IDOSY
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Vitorge et al. Anal. Chem. 2006, 78, 5601-5606 (/
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NMR titrations
DLU
titrant
Mixture of compounds
Rupali Shivapurkar 15
NMR titrations
O
OH
O
OH
O
O
OH OH O
H
H
O
O
OH O
+ H+ HO OH
O HO OH
OH
cinnamic acid coumaric acid caffeic cinnamic acid acid 2,3 coumaric dimethyl benz acid
Rupali Shivapurkar 16
NMR titrations
&+ $+SSP 0H DFHWLFDFLG E RUWKR&+ SDUD&+ PHWD&+ &+
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Rupali Shivapurkar 17
NMR titrations Normalization of the 13C chemical shifts
Acetic ac / coumaric ac.
Δ pKa = 0.025
COUMARIC ACID CAFEIC ACID
D" D " D !( D!
1RUPDOL]HGFKHPLFDOVKLIWV
ACETIC ACID 2EFERENCE
BENZOIC ACID CAMPHANIC ACID DIMETHOXY BENZOIC ACID
P+A
D! D ! D "( D" O
OH
O
OH
O
OH O
OH O
O O HO OH
O
4.77 4.72
OH
OH
cinnamic acid coumaric acid caffeic acid
5.26 4.24
O
4.80 4.70
2,3 dimethyl benzoic acid camphanic acid
5.79 3.71
6.60 2.9 Rupali Shivapurkar 18
Combining 10 ppm with 9.9 ppm
Any position of CF in F1
SSP
74.37 - 40 = 34.37 ppm
SSP
Mohammadali Foroozandeh 19
Combining 10 ppm with 9.9 ppm Carrier at -5 ppm scaled to +5 ppm in F1
SSP
D
D
74.37 - 40 = 34.37 ppm
Multiplicity edition
SSP
Mohammadali Foroozandeh 20
Combining 10 ppm with 9.9 ppm
W
'HF
+
W’
'HF
%
%
!%
!%
DENA-HSQC Differential Evolution for Non-ambiguous Aliasing
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t1 t1ʹ′ = 100
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FRV WW FRV WWa FRV WW WWa FRV WW WWa W a VLQ WW FRV WWa VLQ WW W W VLQ WW Wa
Mohammadali Foroozandeh 21
DENA-HSQC spectra
22
Département de Chimie Organique Quai E. Ansermet, CH-1211 Geneva 4 Switzerland
Acknowledgments
former PhD Students
Bruno Vitorge, HSQC-IDOSY, HMBC, 10 ppm experiments PhD Students
Rupali Shivapurkar, Titration experiments Mohammadali Foroozandeh, Q3 sign alternation and 10.1 ppm Technicians
André Pinto
Stéphane Grass
Patrick Romanens Collaborations
Jean-Marc Nuzillard, Univ. Champagne-Ardenne, Reim, France Philippe Christen, Phytochemistry, Univ. Geneva, Switzerland Funding SNF, Etat de Genève
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