Ultrafast Homonuclear Correlation Spectroscopy with Diagonal
Suppression
Supplementary Information
Abhishek Banerjee and N. Chandrakumar*
MRI-MRS Centre, Department of Chemistry, Indian Institute of Technology Madras,
Tamil Nadu, Chennai – 600036, India, Tel: +91-44-22574920
E-mail: nckumar@iitm.ac.in, chandrakumar.iitm@gmail.com
Product operator calculation for SECSY and DISSECT in UF mode
a) Two spin – ½ AX system
SECSY
 
 
 
t1 2
t1 2
I1z 
 

 


90 y , y
grad ,90 y , y , grad


rcvr x , x


 I I sin  J   sin 1 2 t1  I sin 2   J   cos 1 2 t1
2x
2
2
2
 1z 2 x
  t
1 2 t1
1 
 I 2 y sin 2   J2  sin  1 2 2  1
2   I1 z I 2 y sin   J   cos
2

2  J
  I1x cos  2   I1 y I 2 z sin  J  












DISSECT
 
 


 
t1 2
t1 2
I1z 

 

 


90 y , y
1
2
 I sin 2   J   sin
2
 2y
90 y ,  y , rcvr x , x
grad ,90 y , y , grad

1 2 t1
2
I
1x I 2 z sin  J   sin
b) Spin - ½ AX2 system
SECSY
 
 
 
t1 2
t1 2
I1z 
 

 


90 y , y
grad ,90 y , y , grad
rcvr x , x
 12 I1z  I 2 x  I 3 x  cos   J2  sin  J   sin
 14  I 2 x  I 3 x  sin   J2  sin  J   cos



2
1 2 t1
 12 I1z  I 2 y  I 3 y  cos   J2  sin  J   cos
 14  I 2 y  I 3 y  sin   J2  sin  J   sin
1 2 t1
2

1 2 t1
1 2 t1
2


2


1
2
I1x cos 4   J2  
 I1 y  I 2 z  I 3 z  sin   J2  cos3   J2   12 I1x I 2 z I 3 z sin 2  J  

1 2 t1
2

DISSECT
 
 


 
t1 2
t1 2
I1z 
 

 

90 y , y
1
4
I
2y
90 y ,  y , rcvr x , x
grad ,90 y , y , grad
 I 3 y  sin   J2  sin  J   sin
 12 I1x  I 2 z  I 3 z  cos
 
 J

1 2 t1
2

sin( J  ) sin
2

1 2 t1
2

 12 I1 y I 2 z I 3 z sin 2   J2  sin  1  2  t1 
SECSY
 
 
 
t1 2
t1 2
I 2 z  I 3 z 
 

 


90 y , y
grad ,90 y , y , grad

 cos  J   sin  
 cos  J   cos  
 12 I1x sin   J2  sin  J   cos
 I1x  I 2 z  I 3 z  sin   J2
 I1 y  I 2 z  I 3 z  sin   J2

1 2 t1
2
1
2
rcvr x , x
I1 y sin   J2   sin  J   sin




1 2 t1
2

1 2 t1
2
1 2 t1
2
 12  I 2 x  I 3 x  cos 2   J2   12 I1z  I 2 y  I 3 y  sin  J  

 sin  J   sin  



2 I1x I 2 z I 3 z sin   J2  sin  J   cos
1 2 t1
2 I1 y I 2 z I 3 z sin   J2
1 2 t1
2
2
DISSECT
 
 


 
t1 2
t1 2
I 2 z  I 3 z 
 

 


90 y , y
90 y ,  y , rcvr x , x
grad ,90 y , y , grad
I1z  I 2 x  I 3 x  sin   J2  cos  J   sin

1 2 t1
2

I sin   J2  sin  J   sin
1
2 1y

1 2 t1
2

EXPERIMENTAL
All experiments were performed at room temperature on a Bruker Avance II 500 MHz spectrometer
equipped with a 5 mm TBI inverse probe employing the z-gradient (max. 50 G/cm). All other
parameters and sample descriptions are given in the respective Figure captions. All UF-DISSECT
spectra were acquired with the pulse sequence shown in Fig. 1 and processed in TOPSPIN 1.3. Data
were zero filled to 1024 and 4096 complex points in the F1 and F2 dimensions respectively. A squared
sine bell window with shift 8 was used in the F1 dimension and a Gaussian window function (with LB
= 200, GB = 0.5) was used in the F2 dimension1. UF-SECSY spectra were acquired without any
phase cycling, employing gradient controlled echo pathway selection; UF-DISSECT spectra were
acquired with a two step phase alternation of the DISSECT pulse, co-adding the resulting FID’s.
Figure S1. NMR spectrum of a metabolite mixture in D 2O (creatine, taurine, glutamine and ɣ - amino butyric
acid, 50 mM each) obtained with UF-COSY. Spectrum was acquired with 16 scans in 39 s, other parameters:
recycle delay = 2 s; N = 128; 15 ms chirp pulses, BW = 40 kHz, G e = ±5.0 G/cm, d = 255 µs, Gd = 17.5 G/cm,
Ga = ±36.56 G/cm, Δt2 = 562 µs.
Figure S2.
NMR spectra of a four metabolite mixture in D2O/DSS (mIns, taurine, glutamine and ɣ aminobutyric acid, 55 mM each) obtained with UF-SECSY and UF-DISSECT. Spectra were acquired with 8
scans in 22 s; other parameters: recycle delay = 2 s; N = 128; 7.5 ms chirp pulses, BW = 40 kHz, Ge = ±4.55
G/cm, d = 200 µs, Gd = 17.5 G/cm, Ga = ±32.96 G/cm, Δt2 = 465 µs. Peaks around 2.8 ppm in F2 dimension
originate from DSS.
Figure S3. Left: UF-DISSECT spectrum of a five metabolite mixture in D2O/DSS (creatine, mIns, taurine,
glutamine and ɣ - aminobutyric acid, 55 mM each); Right: UF-DISSECT spectrum of a six metabolite mixture
in D2O/DSS (creatine, glutamate, mIns, taurine, glutamine and ɣ - aminobutyric acid, 55 mM each). Spectra
were acquired with 8 scans in 22 s; other parameters: recycle delay = 2 s; N = 128; 7.5 ms chirp pulses, BW =
40 kHz, Ge = ±4.55 G/cm, d = 200 µs, Gd = 17.5 G/cm, Ga = ±32.96 G/cm, Δt2 = 465 µs. Peaks around 2.8 ppm
in F2 dimension originate from DSS.
Figure S4. 2D COSY spectrum of strychnine in CDCl3. All peaks are assigned accordingly in F1 projection.
The spectrum is acquired with relaxation delay = 1s, number of increments in F1 = 384, number of points in F2
= 16k, number of dummy scan 4, number of scan 16 and spectral width 11ppm.
Figure S5. (a) 2D ultrafast COSY and (b) ultrafast SECSY, both of strychnine in CDCl 3. All parameters are the
same as in Figure 3b in the main manuscript, except Ge in ufcosy (Ge = 2.25 G/cm). The spatial encoding in
UF-COSY was performed with the help of two chirp pulses (each of duration 15 ms).
1
P. Giraudeau and S. Akoka, Magn. Reson. Chem. 49, 307 (2011).
SI description:
Includes density matrix results for SECSY and DISSECT experiments on spin-1/2 AX and
AX2 systems; experimental details; as well as COSY, UF-COSY and UF-SECSY spectra of
some of the samples reported, for reference, and UF-DISSECT spectra of other multicomponent mixtures.