Title Page
Contents
Abbreviations 13
I. Introduction 14
1. General Aspects of Ion-Exchangers 14
2. Isotope Separations in Different Systems with Crown Ethers 15
3. Host - Guest Chemistry 17
4. Azacrown Ether 18
5. Purpose of the Present Study 18
II. Experimental 20
1. Materials and Instruments 20
2. Synthesis of Macrocyclic Ligands 20
2.1. Preparation of DTD and TTD 20
2.2. The Template Effect 23
2.3. Preparation of TD(cyclam) and TP 23
3. Synthesis of Ion-Exchanger Substituted Merrifield Peptide Resin 27
3.1. Preparation of DTDM and TTTM 27
3.2. Preparation of TDM and TPM 30
4. Measurement of the Ion-Exchange Capacity and Distribution Coefficient 33
5. Separation of Li and Mg Isotopes 35
III. Results and discussion 37
1. Characterization of DTD and TTD 37
2. Characterization of TD and TP 37
3. Characterization of DTDM and TTTM 37
4. Characterization of TDM and TPM 42
5. Measurement of the Ion-Exchange Capacity and Distribution Coefficient 48
5.1. Lithium ion 48
5.2. Magnesium ion 57
6. Separation of Lithium Isotope by Column Chromatography 65
7. Separation of Magnesium Isotope by Column Chromatography 85
IV. Conclusions 111
V. References 114
국문초록 118
Abstract 120
감사의 글 122
Table 1. Weight loss percentage of ion-exchangers in TGA thermogram 47
Table 2. Capacity of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM), 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclo-tetradecane bonded Merrifield peptide resin(TTTM), 1,4,8,11-tetraazacyclo...(이미지참조) 48
Table 3. Distribution coefficient for lithium with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) in various conc. of NH₄Cl(이미지참조) 49
Table 4. Distribution coefficient for lithium with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) in various conc. of NH₄Cl 49
Table 5. Distribution coefficient for lithium with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM) in various cone. of NH₄Cl 49
Table 6. Distribution coefficient for lithium with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM) in various cont. of NH₄Cl 50
Table 7. Distribution coefficient for magnesium with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) in various conc. of NH₄Cl(이미지참조) 57
Table 8. Distribution coefficient for magnesium with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) in various conc. of NH₄Cl 57
Table 9. Distribution coefficient for magnesium with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM) in various cone. of NH₄Cl 57
Table 10. Distribution coefficient for magnesium with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM) in various cone. of NH₄Cl 58
Table 11. The local enrichment factor for lithium isotopes in each fraction of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM)(이미지참조) 78
Table 12. The local enrichment factor for lithium isotopes in each fraction of 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) 78
Table 13. The local enrichment factor for lithium isotopes in each fraction of 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM) 79
Table 14. The local enrichment factor for lithium isotopes in each fraction of 1,4,8,12-tetraazacyclopentadecahe bonded Merrifield peptide resin(TPM) 79
Table 15. Lithium isotope separation factor for ion-exchangers 79
Table 16. Distribution coefficient(Kd) versus separation factor(α) for lithium with ion-exchangers in 2.0 M NH₄Cl 80
Table 17. Symmetry of tetraazamacrocycles substituted merrifield peptide resins and ionic diameters 80
Table 18. The local enrichment factor for magnesium isotopes in each fraction of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM)(이미지참조) 91
Table 19. The local enrichment factor for magnesium isotopes in each fraction of 1,4,8,11- tetramethyl -2,5,9,12- tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) 91
Table 20. The local enrichment factor for magnesium isotopes in each fraction of 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM) 92
Table 21. The local enrichment factor for magnesium isotopes in each fraction of 1,4,8,12-tetraazacyclopantadecane bonded Merrifield peptide resin(TPM) 93
Table 22. Magnesium isotope separation factor for ion-exchangers 94
Table 23. Distribution coefficient(Kd) versus separation factor(α) of magnesium for ion-exchangers in 2.0 M NH₄Cl 94
Fig. 1. Structure of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane(DTD) and 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane(TTD).(이미지참조) 22
Fig. 2. Structure of 1,4,8,11-tetraazacyclotetradecane([14]aneN₄)(TD) and 1,4,8,12-tetraazacyclopentadecane([15]aneN₄)(TP). 26
Fig. 3. Structure of merrifield peptide resin. 27
Fig. 4. Experimental apparatus for chromatographic Li, Mg isotopes separation and isotopes separation of Li, Mg by DTDH. 36
Fig. 5. IR spectra of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 38
Fig. 6. TGA thermogram of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]-docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 39
Fig. 7. IR spectra of 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 40
Fig. 8. TGA thermogram of 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 41
Fig. 9. IR spectra of 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 42
Fig. 10. IR spectra of 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 43
Fig. 11. IR spectra of 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin (TDM) and 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 44
Fig. 12. TGA thermogram of 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 45
Fig. 13. TGA thermogram of 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 46
Fig. 14. TGA thermogram of Merrifield peptide resin. 47
Fig. 15. Plot of log distribution coefficient for lithium with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) in various conc. of NH₄Cl.(이미지참조) 51
Fig. 16. Plot of log distribution coefficient for lithium with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) in various conc. of NH₄Cl. 52
Fig. 17. Plot of distribution coefficient for lithium with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) and 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide...(이미지참조) 53
Fig. 18. Plot of log distribution coefficient for lithium with 1,4,8,11-tetraazacyclo-tetradecane bonded Merrifield peptide resin(TDM) in various conc. of NH₄Cl. 54
Fig. 19. Plot of log distribution coefficient for lithium with 1,4,8,12-tetraazacyclo-pentadecane bonded Merrifield peptide resin(TPM) in various conc. of NH₄Cl. 55
Fig. 20. Plot of distribution coefficient for lithium with TDM and TPM in various conc. of NH₄Cl. 56
Fig. 21. Plot of log distribution coefficient for magnesium with 3,14-dimethyl 2,6,13,17-tetraazatricyclo[14,4,01.18,07.12] docosane bonded Merrifield peptide resin(DTDM) in various cone. of NH₄Cl.(이미지참조) 59
Fig. 22. Plot of log distribution coefficient for magnesium with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) in various conc. of NH₄Cl. 60
Fig. 23. Distribution coefficient for magnesium with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) and 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide...(이미지참조) 61
Fig. 24. Plot of log distribution coefficient for magnesium with 1,4,8,11-tetraazacyclo-tetradecane bonded Merrifield peptide resin(TDM) in various conc. of NH₄Cl. 62
Fig. 25. Plot of log distribution coefficient for magnesium with 1,48,12-tetraazacyclo-pentadecane bonded Merrifield peptide resin(TPM) in various cone. of NH₄Cl. 63
Fig. 26. Distribution coefficient for magnesium with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM) and 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM) in various cont. of NH₄Cl. 64
Fig. 27. Schematic representation of the relationship between an isotope effect and the occurrence of isotope fractionation. 65
Fig. 28. Elution curve for lithium isotope separation with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) in 2.0 M NH₄Cl.(이미지참조) 68
Fig. 29. Elution curve for lithium isotope separation with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) in 2.0 M NH₄Cl. 69
Fig. 30. Elution curve for lithium isotope separation with 1,4,8,11-tetraazacyclo-tetradecane bonded Merrifield peptide resin(TDM) in 2.0 M NH₄Cl. 70
Fig. 31. Elution curve for lithium isotope separation with 1,4,8,12-tetraazacyclo-pentadecane bonded Merrifield peptide resin(TPM) in 2.0 M NH₄Cl. 71
Fig. 32. Schematic figure of the elution curve of an element with two isotopes. 73
Fig. 33. The graphic determination of & with the results of a chromatographic elution. (a) the isotope ratio of different fractions of the elution curve, (b) the isotope ratio versus the eluted part of the element amount Δm/m (c) lnR versus Δm/m on probability paper. 75
Fig. 34. The graphic determination of & with the results of a chromatographic elution for lithium ion with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 81
Fig. 35. The graphic determination of & with the results of a chromatographic elution for lithium ion with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 82
Fig. 36. The graphic determination of & with the results of a chromatographic elution for lithium ion with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 83
Fig. 37. The graphic determination of & with the results of a chromatographic elution for lithium ion with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 84
Fig. 38. Elution curve for magnesium isotope separation with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM) in 2.0 M NH₄Cl.(이미지참조) 85
Fig. 39. Elution curve for magnesium isotope separation with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM) in 2.0 M NH₄Cl. 86
Fig. 40. Elution curve for magnesium isotope separation with 1,4,8,11-tetraazacyclo-tetradecane bonded Merrifield peptide resin(TDM) in 2.0 H NH₄Cl. 87
Fig. 41. Elution curve for magnesium isotope separation with 1,4,8,12-tetraazacyclo-pentadecane bonded Merrifield peptide resin(TPM) in 2.0 M NH₄Cl. 88
Fig. 42. The graphic determination of εR₁ with the results of a chromatographic elution for magnesium ion with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 95
Fig. 43. The graphic determination of εR₂ with the results of a chromatographic elution for magnesium ion with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 96
Fig. 44. The graphic determination of εR₃ with the results of a chromatographic elution for magnesium ion with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 97
Fig. 45. The graphic determination of εR₁,₂,₃ with the results of a chromatographic elution for magnesium ion with 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane bonded Merrifield peptide resin(DTDM).(이미지참조) 98
Fig. 46. The graphic determination of εR₁ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 99
Fig. 47. The graphic determination of εR₂ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 100
Fig. 48. The graphic determination of εR₃ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 101
Fig. 49. The graphic determination of εR₁,₂,₃ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetramethyl-2,5,9,12-tetraazacyclotetradecane bonded Merrifield peptide resin(TTTM). 102
Fig. 50. The graphic determination of εR₁ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 103
Fig. 51. The graphic determination of εR₂ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 104
Fig. 52. The graphic determination of εR₃ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 105
Fig. 53. The graphic determination of εR₁,₂,₃ with the results of a chromatographic elution for magnesium ion with 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM). 106
Fig. 54. The graphic determination of εR₁ with the results of a chromatographic elution for magnesium ion with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 107
Fig. 55. The graphic determination of εR₂ with the results of a chromatographic elution for magnesium ion with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 108
Fig. 56. The graphic determination of εR₃ with the results of a chromatographic elution for magnesium ion with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 109
Fig. 57. The graphic determination of εR₁,₂,₃ with the results of a chromatographic elution for magnesium ion with 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM). 110