Supporting Information for. 2D Mapping of NMR Signal Enhancement and Relaxation for Heterogeneously Hyperpolarized Propane Gas

Transcription

1 Supporting Information for 2D Mapping of NMR Signal Enhancement and Relaxation for Heterogeneously Hyperpolarized Propane Gas Danila A. Barskiy, a Kirill V. Kovtunov, b,c, * Evgeny Y. Gerasimov, c,d M. Anthony Phipps, a Oleg G. Salnikov, b,c Aaron M. Coffey, a Larisa M. Kovtunova, c,d Igor P. Prosvirin, c,d Valerii I. Bukhtiyarov, c,d Igor V. Koptyug, b,c Eduard Y. Chekmenev a,e,f, * a Vanderbilt University Institute of Imaging Science (VUIIS), Department of Radiology, Vanderbilt University Medical Center, Nashville, TN 37232, USA b International Tomography Center SB RAS, Novosibirsk, , Russia c Novosibirsk State University, 2 Pirogova St., Novosibirsk, Russia d Boreskov Institute of Catalysis SB RAS, Novosibirsk, , Russia e Department of Biomedical Engineering and Physics, Vanderbilt-Ingram Cancer Center (VICC), Nashville, Tennessee, 37232, USA f Russian Academy of Sciences, 14 Leninskiy Prospekt, Moscow, Russia Table of Contents 1. Additional information about Rh/TiO 2 catalysts... S-2 2. Additional information about PHIP-echo pulse sequence... S-5 3. Reaction conversion and 1 H NMR signal enhancement calculation... S-5 4. Measured 1 H NMR signal values and calculated conversion and signal enhancement factors... S-6 5. Reactants flow rates used to control propylene percentage in the reaction mixture... S-9 6. Experimental T 1 relaxation data for thermally polarized propane gas in the mixture with H 2 at various pressures.... S-12 S-1

2 1. Additional information about Rh/TiO2 catalysts %Rh/TiO2 Intensity (cps) Binding energy (ev) Figure S1. Rh3d core-level XPS spectrum, HRTEM images, and EDX spectrum of the Rh/TiO2 catalyst with 1.0 wt. % of Rh loading. S-2

3 %Rh/TiO Intensity (cps) Binding energy (ev) Figure S2. Rh3d core-level XPS spectrum, HRTEM images, and EDX spectrum of the Rh/TiO 2 catalyst with 13.7 wt. % of Rh loading. S-3

4 %Rh/TiO Intensity (cps) Binding energy (ev) Figure S3. Rh3d core-level XPS spectrum, HRTEM images, and EDX spectrum of the Rh/TiO2 catalyst with 23.2 wt. % of Rh loading. S-4

5 2. Additional information about PHIP-echo pulse sequence a PHIP-echo b CH 3 (45 ) x (180 ) x FID NMR signal (a. u.) CH Δ Δ Figure S4. a) NMR PHIP-echo pulse sequence where 45 o pulse is used (instead of 90 o pulse in conventional spin-echo experiments). PHIP-echo was used to convert antiphase nuclear spin order of PHIP-derived nuclei into in-phase spin order directly at high magnetic field. b) Simulation of the 1 H NMR signal (integral) of CH 3 -group of propane (red) and CH 2 -group of propane (blue) as a function of interpulse delay Δ = 17 ms Δ (ms) Reaction conversion and 1 H NMR signal enhancement calculation Reaction conversion values were calculated from 1 H NMR spectra of thermally polarized propane using the following equations: (S1) X "#$ = X "#+ = '( S "#$ '( S "#+ '( S "#$ 2 ', 2 + S "#+ '( 6 S "#+ ', 6 + S "#+ 3 3 where X "#$ and X "#+, are conversion values calculated from the 1 H NMR signals, S '( "#$ and S '( "#+, of CH 2 and CH 3 groups of propane, respectively. S ', "#+ is an 1 H NMR signal of CH 3 -group of unreacted propylene. The averaged conversion values, (S2) are presented in Figure S5 and in Tables S1-S3. X = X "#+ + X "#$ 2 S-5

6 Values of 1 H NMR signal enhancement, ε, were calculated using the following equation: ε = 8 2 I '( '( "#$ + I "#+ S '( '( "#$ + S "#+ (S3) where I '( "#$ and I '( "#+ are measured PHIP-echo values for -CH 2 - and -CH 3 groups of propane, respectively. Numerical factors 2 and 8 take into account the fact that only 2 protons give rise to the PHIP-echo signal while all 8 protons are responsible for the formation of 1 H NMR signal for thermally polarized propane. We note that the computed in the fashion signal enhancement ε reports on the signal enhancement of the two (out of eight) protons of propane spin system: H A and H B as shown in Figure 3. Percentage polarization (%P H ) for these two protons can be computed using the following equation: (S4) %P 4 = ε P 64789:; where P THERMAL is equilibrium thermal polarization of proton spins at 9.4 T and 298 K corresponding to %. The maximum observed ε in the experiments presented in Figure 4 was ~55 corresponding to %P H ~ 0.18%. We note that while the enhancement factor is field dependent, the %P H is field independent, because it takes into account the equilibrium nuclear spin polarization at the field of reference. 4. Measured 1 H NMR signal values and calculated conversion and signal enhancement factors (1%)Rh/TiO 2 (14%)Rh/TiO 2 (23%)Rh/TiO Pressure (atm) Conversion (%) Pressure (atm) Conversion (%) Pressure (atm) Conversion (%) Propylene fraction (%) Propylene fraction (%) Propylene fraction (%) Figure S5. Reaction conversion values measured for three different Rh/TiO 2 catalysts with 1.0 wt.%, 13.7 wt.% and 23.2 wt.% of rhodium (Rh) metal loading. Conversion values are calculated form 1 H NMR spectra of thermally polarized mixture after the reaction. The numerical values are presented in Tables S1-S3 (see below). S-6

7 Conversion values Table S1. Measured conversion values for the propylene hydrogenation reaction over 1.0 wt.% Rh/TiO Table S2. Measured conversion values for the propylene hydrogenation reaction over 13.7 wt.% Rh/TiO Table S3. Measured conversion values for the propylene hydrogenation reaction over 23.2 wt.% Rh/TiO 2. Propylene percentage (%) in the mixture with H S-7

8 PHIP-echo values Table S4. Measured PHIP-echo integral values (sum of signals for CH 2 and CH 3 groups of propane) for propane produced in the propylene hydrogenation reaction over 1.0 wt% Rh/TiO Table S5. Measured PHIP-echo integral values (sum of signals for CH 2 and CH 3 groups of propane) for propane produced in the propylene hydrogenation reaction over 13.7 wt% Rh/TiO Table S6. Measured PHIP-echo integral values (sum of signals for CH 2 and CH 3 group of propane) for propane produced in the propylene hydrogenation reaction over 23.2 wt% Rh/TiO S-8

9 Thermal 1 H NMR signal values Table S7. Measured 1 H NMR thermal integral values (sum of signals for CH 2 and CH 3 groups of propane) for propane produced in the propylene hydrogenation reaction over 1.0 wt% Rh/TiO Table S8. Measured 1 H NMR thermal integral values (sum of signals for CH 2 and CH 3 group of propane) for propane produced in the propylene hydrogenation reaction over 13.7 wt% Rh/TiO Table S9. Measured 1 H NMR thermal integral values (sum of signals for CH 2 and CH 3 group of propane) for propane produced in the propylene hydrogenation reaction over 23.2 wt% Rh/TiO S-9

10 1 H NMR signal enhancement factor values Table S10. Calculated 1 H NMR signal enhancement values for hyperpolarized propane produced in the propylene hydrogenation reaction with p-h 2 over 1.0 wt% Rh/TiO Table S11. Calculated 1 H NMR signal enhancement values for hyperpolarized propane produced in the propylene hydrogenation reaction with p-h 2 over 13.7 wt% Rh/TiO Table S12. Calculated 1 H NMR signal enhancement values for hyperpolarized propane produced in the propylene hydrogenation reaction with p-h 2 over 23.2 wt% Rh/TiO S-10

11 5. Reactants flow rates used to control propylene percentage in the reaction mixture Table S13. Reactants flow rates used to control propylene percentage in the reaction mixture. Pressure (psig) Flow Rate (sccm) Percentage (%) in the mixture Propylene Hydrogen Total Propylene Hydrogen S-11

12 6. Experimental T 1 and T 2 relaxation data for thermally polarized propane gas in the mixture with H 2 at various pressures. Table S14. Experimentally obtained 1 H T 1 relaxation data for thermally polarized propane gas in the mixture with H 2 and at various pressures. Pressure (psig) Propane fraction Propane flow (sccm) H 2 flow (sccm) Propane/H 2 ratio CH 2 peak T 1 (ms) CH 3 peak T 1 (ms) S-12

13 S-13

14 a T 1 (s) CH CH 2 - -CH 3 T 2 (s) Pressure (atm) b CH Pressure (atm) Figure S6. (a) Longitudinal (T 1 ) and (b) transverse (T 2 ) relaxation time for protons in CH 2 - and -CH 3 groups of propane as a function of thermally polarized propane gas pressure at 9.4 T. Each data point is a separate T 1 /T 2 measurement. T 1 relaxation was measured using inversion-recovery NMR pulse sequence, while T 2 relaxation was measured using Carr-Purcell-Meiboom-Gill (CPMG) experiment with spin-echo block (delay-180 o -delay) of 10 ms. S-14