Dynamic Nuclear Polarization Mechanisms using TEMPOL and trityl OX063 radicals at 1 T and 77 K

Dynamic Nuclear Polarization Mechanisms using TEMPOL and trityl OX063 radicals at 1 T and 77 K

Data information

Ewoud Vaneeckhaute*1, Charlotte Bocquelet1, Nathan Rougier1, Shebha Anandhi Jegadeesan2, Sanjay Vinod-Kumar2, Guinevere Mathies2, Roberto Melzi3, James Kempf4, Quentin Stern1, Sami Jannin1

1.Université Claude Bernard Lyon 1, CNRS, ENS Lyon, UCBL, CRMN UMR 5082, 69100 Villeurbanne, France

2.Department of Chemistry, University of Konstanz, Universitätsstr. 10, 78464, Konstanz, Germany

3.Bruker Italia S.r.l., Viale V. Lancetti 43, 20158 Milano, Italy

4.Bruker Biospin, Billerica, Massachusetts 01821, United States

* Corresponding authors

Email: ewoud.vaneeckhaute(at)univ-lyon1.fr

1.           Data overview

All the data shown in the manuscript and the supporting information can be found in the Zenodo repository.

1.1.         Table 1 and Figure 3

The NMR data (Bruker Topspin) used for calculating the enhancement factors in Table 1 (manuscript), and plotting the 1D 1H and 13C thermal and DNP spectra in Figure 3 (manuscript), are summarized in Table D1 and can be found in the folder ‘ENHANCEMENT_DNP’.

Table D1. Experiment numbers for 1D 1H and 13C spectra in the folder ‘ENHANCEMENT_DNP’ shown in Figure 3 of the main manuscript.

Enhancement

1H TE

1H DNP

13C TE

13C DNP

TEMPOL

1

2

/

/

TEMPOL + 13C

3

4

5

6

Trityl OX063

7

8

/

/

Trityl OX063 + 13C

9

10

5

11

Due to the hardware difficulties related to obtaining the thermal equilibrium 13C signal for 3 M acetate, the same reference thermal spectrum is used for TEMPOL and trityl.

The NMR data (Bruker Topspin) used for calculating the DNP buildup times reported in Table 1 (manuscript) are summarized in Table D2 and can be found in the folder ‘BUILDUP_DNP’.

Table D2. Experiment numbers for 1H and 13C DNP buildup times in the folder ‘BUILDUP_DNP’ reported in Table 1 of the main manuscript.

DNP buildup

1H

13C

TEMPOL

1

/

TEMPOL + 13C

2

3

Trityl OX063

4

/

Trityl OX063 + 13C

5

6, 7

The NMR data (Bruker Topspin) used for constructing the DNP spectra in Figure 3 are summarized in Table D3 and can be found in the folder ‘UW_DNP’. The frequency range over which was swept is shown in Table D4. Note that for trityl OX063, the 13C DNP spectrum was measured in three stages from 27.99-28.09 GHz (exp 400), 28.09-28.1025 GHz (exp 401) and 28.1025-28.1125 GHz (exp 402) all with steps of 0.0025 GHz.

Table D3. Experiment numbers for DNP spectra in the folder ‘UW_DNP’ shown in Figure 2 of the main manuscript.

DNP spectrum

1H

13C

TEMPOL

100

200

Trityl OX063

300

400-402

Table D4. Total microwave frequency range (GHz) for DNP spectra in Figure 2 of the main manuscript.  

DNP spectrum

1H

13C

Steps

TEMPOL

27.8 - 28.44

27.83 - 28.62

0.01

Trityl OX063

27.9 - 28.2975

27.99 - 28.1125

0.0025

1.2.         Figure 4

The data for the buildup (µw on) and relaxation (µw off) decay curves for proton magnetization in presence of TEMPOL and trityl OX063 (Figure 4) can be found in the POWER_DNP folder. The experiments used for each microwave power output (watts) are summarized in Table D5. 

Table D5. Experiment numbers for DNP buildup and spin-lattice relaxation decay curves in Figure 3.

Power (W)

0.55

1.32

2.3

3.16

3.8

4.27

4.57

Trityl

11006

11005

11004

11003

11002

11001

11000

TEMPOL

30210

30209

30208

30207

30206

30205

30204

1.3.         Figure 5

The electron saturation simulations can be reproduced using the codes available in the ‘CODES’ folder. Electron_depolarization_fixed.mlx is a live script that calculates the influence of the microwave (with fixed frequency) on the depolarization of the unpaired radicals in an amorphous frozen solid.

1.4.         Figure 6

The experimental data points in Figure 6 are the same as in Figure 3 (see Table D3 and D4). Electron_depolarization_sweep.mlx is a follow-up livescript that calculates the expected lineshape of the solid effect and cross effect DNP spectrum shown in Figure 6 when the microwave frequency is varied. Guidelines are available in the codes, and the codes needs input of additional functions also present in the folder.

1.5.         Figure S1-2

The NMR data (Bruker Topspin) used for calculating the enhancement factors in Table 1 (manuscript), and plotting the 1D 1H and 13C thermal and DNP spectra in Figure S1 can be found in Table D1 under Figure 3 and can be found in the folder ‘ENHANCEMENT_DNP’. The buildup curves can be reconstructed using the experiment numbers reported in Table D2.

1.6.         Figure S3

The NMR data used for constructing the DNP spectra in Figure S3 are summarized in Table D3 and correspond to trityl OX063 without 13C.

1.7.         Figure S4

The Q-band pulsed EPR data of TEMPOL in an identical glassy solution as used in at the benchtop polarizer can be found in the folder ‘EPR_TEMPOL’ as ‘50mM_TEMPOL_Pulse’. 

1.8.         Figure S5-6

The pulse EPR data for extracting the electron spin-lattice and spin-spin relaxation time constant are available upon request. 

1.9.         Figure S7

The code for simulating the electron depolarization under microwave perturbation can be found in the ‘CODES’ folder called Electron_depolarization_fixed.mlx. It needs the input of the additional functions also present in the folder.

1.10.      Figure S8

The experiment numbers for the NMR data for the 1D hyperpolarized 13C spectra shown in Figure S8d-f are summarized in Table D6 and can be found in the folder ‘UW_DNP’.

Table D6. Experiment numbers for hyperpolarized 13C spectra shown in Figure S8.

1D NMR

Figure S8d

Figure S8e

Figure S8f

Exp

501

502

500