Title Page
Abstract
Contents
CHAPTER 1. Optimized Extraction and Purification Conditions for Bioactive Compounds from Natural Plants 16
1.1. Introduction 17
1.1.1. Extraction Methodologies 17
1.1.2. Purification using Solid-Phase Extraction 21
1.1.3. Application of New Solid-Phase Extraction Sorbent 22
1.1.4. Investigation of New Method 30
1.2. Theoretical Background 33
1.2.1. Assisted Extraction Methods 33
1.2.2. Response Surface Methodology 34
1.2.3. Solid-Phase Extraction 35
1.2.4. Molecular Imprinted Technology 35
1.3. Experimental 36
1.3.1. Optimization of Extraction Conditions 36
1.3.2. Response Surface Methodology 37
1.3.3. Solid-Phase Extraction 39
1.3.4. Molecularly Imprinted Solid-Phase Extraction 39
1.3.5. Multi-Phase Extraction 42
1.4. Results and Discussions 44
1.4.1. Optimization of Extraction Conditions 44
1.4.2. Optimized Extraction Condition by RSM 52
1.4.3. Purification of flavones by SPE 57
1.4.4. Molecularly Imprinted Solid-Phase Extraction 59
1.4.5. Multi-Phase Extraction 64
1.5. References 68
CHAPTER 2. Porous Ionic Liquid-Immobilized Polymer Sorbents 77
2.1. Introduction 78
2.1.1. Different Ionic Liquid-Modified Sorbents 78
2.1.2. Evaluation of the Adsorption Efficiency of Ionic Liquid-Immobilized Polymer 81
2.1.3. Ionic Liquid-Immbilized Polymers in SPE Method 84
2.1.4. Ionic Liquid-Immbilized Microporous Polymers with MIP 87
2.1.5. Application of Ionic Liquid-Immbilized Porous Polymers in MPE 88
2.2. Experimental 90
2.2.1. Adsorption Isotherms 90
2.2.2. Solid-Phase Extraction 91
2.2.3. Molecularly Imprinted Ionic Liquid-Modified Porous Polymers 95
2.2.4. Ionic Liquid-Modified Microporous Polymers 98
2.2.5. Application of Ionic Liquid-Immbilized Porous Polymers in MPE 99
2.3. Results and Discussion 101
2.3.1. Adsorption Isotherms 101
2.3.2. SPE with IL-polymer 113
2.3.3. Molecular Imprinted Ionic Liquid-Immobilized Polymers 123
2.3.4. Ionic Liquid-Modified Microporous Polymers 126
2.3.5. Application of Ionic Liquid-Immbilized Porous Polymers in MPE 128
2.4. References 133
Conclusions 138
Summary in Korean 139
Summary in Chinese 140
Appendix 141
Appendix 1. Removal of Toxic Essential Oils in Chamaecyparis obtusa by Headspace Single-Drop Microextraction 141
Appendix 2. Adsorption Isotherm of Caffeine and Theophylline on the Metal- Organic Frameworks 142
Appendix 3. Investigation of Ofloxacin Enantioseparation by Ligand Exchange Chromatography 143
Appendix 4. Ionic liquid-Assisted Extraction and Separation of Astaxanthin from Shrimp Waste 144
List of Publications 145
Table 1-1. Summary of MIP-SPE applications in natural plant 24
Table 1-2. Independent variables their levels used for BBD 38
Table 1-3. Different kinds of imprinted polymers and the imprint effect 42
Table 1-4. Extracted amounts of LQ with different solvents 44
Table 1-5. Extraction amount of four compounds by using liquid-solid extraction 48
Table 1-6. Extraction amount of four compounds by using ultrasonic-assistant and microwave-assistant extraction 50
Table 1-7. BBD experimental design with the independent variables 52
Table 1-8. Analysis of variance of the experimental results of the BBD 54
Table 1-9. Elution strength of several solvents 57
Table 1-10. Extracted amounts of quercitrin, myricetin and amentoflavone with different solvents in washing step (MISPE cartridge) 63
Table 1-11. Adsorbed amount of standard solvent with different sorbents 64
Table 2-1. Different characteristic between polymer and silica as the substrate of sorbent 80
Table 2-2. Effect of time on the adsorption of lactic acid 102
Table 2-3. Effect of the initial lactic acid concentration on the adsorption of lactic acid 104
Table 2-4. Effect of pH on the adsorption of lactic acid 106
Table 2-5. Adsorption of target compounds on differences sorbents 108
Table 2-6. Amounts of caffeine and theophylline in commercial tea drinks 115
Table 2-7. Extracted amounts of liquiritin and glycyrrhizin by different SPE sorbent in the steps of washing and elution 116
Table 2-8. Extracts amounts of the two compounds from three commercial medicines 117
Table 2-9. Extracted amounts of the two compounds with three recycles of PVPB 118
Table 2-10. Amounts of matrine and oxymatrine extracted with different solvents in washing and elution steps 120
Table 2-11. Determination of bound amounts of matrine and oxymatrine with milk and egg 121
Table 2-12. Extracted amounts of the two compounds from SFA within three repetitions of PSImN 122
Table 2-13. Extracted amounts of tanshinones with different solvents in washing and elution stages 123
Table 2-14. Concentrations of the three target compounds from different commercial functional drinks 125
Table 2-15. Adsorbed amount of three target compounds on different sorbents 128
Figure 1-1. The molecular structure of ET-743 21
Figure 1-2. Basic theory of MIP and SPE 23
Figure 1-3. Structures of (1) quercitrin, (2) myricetin and (3) amentoflavone 30
Figure 1-4. Process of mutil-phase extraction 31
Figure 1-5. Chemical structures of four bioactive compounds. 37
Figure 1-6. Schematic illustrations of the imprint formation and molecular recognition 40
Figure 1-7. Effect of different ultrasonic and dipping times on the extracted amount 45
Figure 1-8. Effect of volumes of methanol on the extracted amount of LQ 46
Figure 1-9. Effect of different dipping time on the extraction amount of four compounds 49
Figure 1-10. Effect of different dipping temperature on the extraction amount 49
Figure 1-11. Effect of different concentration of NaOH on the extraction amount 50
Figure 1-12. Effect of component of acetone in methanol, liquid/solid ratio and their reciprocal interaction on extraction amount 55
Figure 1-13. Effect of component of dipping time, liquid/solid ratio and their reciprocal interaction on extraction amount 55
Figure 1-14. Effect of component of dipping time, component of acetone in methanol and their reciprocal interaction on extraction amount 56
Figure 1-15. Chromatograms of (a) extract sample, (b) SPE by 15% methanol aqueous solution at first step and (c) SPE by 50% methanol aqueous solution at second step 58
Figure 1-16. Chromatograms of different SPE processes (a) SPE using C18 sorbent and (b) SPE using MIP sorbent 60
Figure 1-17. Chromatographam of C. obtusa after different extraction process 62
Figure 1-18. The amount of myricetin in collected methanol with different repetitions of MPE extraction. 65
Figure 1-19. Chromatograms of dipping extraction, washing and elution stage of MPE 66
Figure 2-1. Molecular structures of four monosaccharides 88
Figure 2-2. The preparation scheme of alkyl pyridinium polymer 93
Figure 2-3. Preparation scheme for the amino-imidazolium polymer 94
Figure 2-4. Molecular structures of target compounds (A) cryptotanshinone, (B) tanshinone I, (C) tashinone IIA and template (D) 9, 10-phenanthrenequinone 96
Figure 2-5. Chemical structures of all ionic liquid-based porous polymers 97
Figure 2-6. Chemical structures of all ionic liquid-based porous polymers 98
Figure 2-7. The preparation scheme of all functionalized microsphere polymers 99
Figure 2-8. Process of multi-phase extraction 100
Figure 2-9. Effect of the amount of adsorbents on the adsorption of lactic acid 103
Figure 2-10. Proposed scheme of the anion exchange mechanism on porous polymers 105
Figure 2-11. Adsoprtion efficiency at different temperatures on three sorbents 107
Figure 2-12. Adsorbed amounts of three flavones on different sorbents 111
Figure 2-13. Chromatograms of extracts from green tea after different extraction processes 114
Figure 2-14. Chromatogram of extract from licorice 115
Figure 2-15. Chromatograms of SPE after different extraction processes 119
Figure 2-16. Chromatograms of SPE after different extraction processes 120
Figure 2-17. Chromatograms of SPE after different extraction process 124
Figure 2-18. Chromatograms of SPE separation 127
Figure 2-19. Process of multi-phase extraction 130
Figure 2-20. Chromatograms of standards, extraction with methanol and with MPE after different extraction process 132