Title Page
Contents
LIST OF ABBREVIATIONS 11
ABSTRACT 12
Ⅰ. Introduction 14
1.1. MRI and NMR spectroscopy 14
1.2. Hyperpolarization 17
1.3. Parahydrogen-Induced Polarization (PHIP) 18
1.3.1. Signal amplification by reversible exchange (SABRE) 19
1.3.2. Heterogeneous SABRE 21
Ⅱ. Method 22
2.1. Heterogeneous catalytic hyperpolarization 24
2.1.1. The heterogeneous resin catalysts 24
2.1.2. The silica-supported heterogeneous catalysts 26
2.1.3. SABRE employing heterogeneous resin catalysts 27
2.1.4. SABRE employing heterogeneous silica-supported catalysts 27
2.2. Calculation of NMR polarization enhancement 28
Ⅲ. Results and Discussion 29
3.1. Preparation of heterogeneous catalysts 29
3.1.1. Preparation of [Ir(COD)(IMes)Cl] (2a) catalyst 29
3.1.2. Preparation of TentaGel resin catalysts 30
3.1.3. Preparation of Wang resin catalysts 30
3.1.4. Preparation of silica-supported catalysts 33
3.2. Heterogeneous catalytic hyperpolarization 34
3.2.1. SABRE employing heterogeneous resin catalysts 34
3.2.2. SABRE employing heterogeneous silica-supported catalysts 40
Ⅳ. Conclusion 42
Ⅴ. Experimental Section 43
5.1. General information 43
5.2. Reagent 44
5.3. Synthesis 46
5.4. Spectrum 50
Ⅵ. Reference 51
국문요약 56
Figure 1. Direction of the nuclear spin state in the absence/presence of an external magnetic field. 15
Figure 2. The energy difference of the spin state (α and β) as a function of the strength of the applied magnetic field. 15
Figure 3. Number of nuclear spin states for thermal polarization (a) and hyperpolarization (b). 17
Figure 4. Four spin combinations of dihydrogen divided by two isomers (left). 18
Figure 5. The graphic equilibrium equation of p-H₂ by the temperature dependence (right). 18
Figure 6. The schematic experimental process employing the p-H₂ generator at 77 K. 23
Figure 7. The structures of iridium catalysts (2a,b). 24
Figure 8. The structures of heterogeneous resin catalysts. 25
Figure 9. The structures of heterogeneous silica-supported catalysts (8,9a). 26
Figure 10. ¹H NMR spectra stacked at magnetic field (70 G) of pyridine after hyperpolarization with 3b. 35
Figure 11. (a) ¹H NMR spectra stacked at magnetic field (70 G) of pyridine after hyperpolarization with 4a. (b) ¹H NMR spectra stacked at magnetic field (70 G)... 36
Figure 12. (a) ¹H NMR spectra stacked at magnetic field (70 G) of nicotinamide after hyperpolarization with 6a. (b) NMR intensity of nicotinamide with 6a versus... 37
Figure 13. Structures and proton numbering of pyridine (Py), nicotinic acid (NAC), and nicotinamide (NAD). Stacked bar graphs of each proton signal... 38
Figure 14. Structures and proton numbering of pyridine (Py), nicotinic acid (NAC), and nicotinamide (NAD). Stacked bar graphs of each proton signal... 40
Scheme 1. Schematic representation of the catalytic SABRE cycle. p-H₂ hyperpolarizes a target substrate (sub). 20
Scheme 2. Synthesis of [Ir(COD)(IMes)Cl] (2a) catalyst. 29
Scheme 3. Synthesis of heterogeneous resin catalysts (3-6a) and (3-6b). 31
Scheme 4. Synthesis of heterogeneous resin catalysts (7a,b). 32
Scheme 5. Synthesis of heterogeneous silica-supported catalysts (8,9a). 33
Equation 1. The Boltzmann ratios of nuclear spin. N₁ and N₂ are the population of alpha and beta spin state, respectively. h is Planck's equation, and k is the... 16
Equation 2. Calculation of ¹H polarization enhancement (ε). 28