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목차
제1장 연구과제의 개요 17
제1절 연구의 필요성 17
제2절 연구의 목적과 범위 20
제2장 국내외 기술개발 현황 22
제3장 연구수행 내용 및 결과 23
제1세부과제 : 일중항산소 소거제의 식품가공공정에의 적용 23
제1절 연구재료 23
제2절 연구방법 23
제3절 연구결과 및 고찰 30
제2세부과제 : 안토시아닌 등 플라보노이드 함유식품의 일중항산소 소거 및 산화억제 기능 80
제1절 연구재료 80
제2절 연구방법 80
제3절 연구결과 및 고찰 84
제3세부과제 : 안토시아닌의 일중항산소에 대한 안정성 114
제1절 연구재료 114
제2절 연구방법 114
제3절 연구결과 및 고찰 119
제4장 목표달성도 및 관련분야에의 기여도 139
제5장 연구 성과 및 활용계획 141
제1절 연구 성과 141
제2절 활용계획 142
제6장 참고문헌 145
표 1. 일중항산소에 의한 산화에 관한 연구 현황 22
Table 1-1. Instrument and analysis conditions for anthocyanins in mulberry fruits and wild grapes. 26
Table 1-2. Total yield of anthocyanin 31
Table 1-3. Antioxidant effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene by ORAC methods 36
Table 1-4. Effect of soymilk volume on the headspace oxygen of soymilk under light storage at 4℃ for 8 hrs 37
Table 1-5. Effect of soymilk volume on the headspace oxygen of soymilk under light storage at 30℃ for 8 hrs 38
Table 1-6. Effect of methlene blue on the headspace oxygen of soymilk under light storage at 4℃ for 8 hrs 40
Table 1-7. Effect of methlene blue on the pH of soymilk under light storage at 4℃ for 8 hrs 41
Table 1-8. Effect of methlene blue on the headspace oxygen of soymilk under light storage at 30℃ for 8 hrs 42
Table 1-9. Effect of methlene blue on the pH of soymilk under light storage at 30℃ for 8 hrs 43
Table 1-10. Effect of anthocyanin on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 44
Table 1-11. Effect of anthocyanin on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 45
Table 1-12. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 46
Table 1-13. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 47
Table 1-14. Effect of anthocyanin on the lightness value of soymilk under light stroage at 4℃ for 8 hrs 49
Table 1-15. Effect of anthocyanin on the redness value of soymilk under light stroage at 4℃ for 8 hrs 50
Table 1-16. Effect of anthocyanin on the yellowness value of soymilk under light stroage at 4℃ for 8 hrs 51
Table 1-17. Effect of cowmilk volume on the headspace oxygen of cowmilk under light stroage at 4℃ for 8 hrs 53
Table 1-18. Effect of cowmilk volume on the headspace oxygen of cowmilk under light stroage at 30℃ for 8 hrs 54
Table 1-19. Effect of methylene blue on the headspace oxygen of cowmilk under light stroage at 4℃ for 8 hrs 55
Table 1-20. Effect of methylene blue on the pH of cowmilk under light stroage at 4℃ for 8 hrs 56
Table 1-21. Effect of methylene blue on the headspace oxygen of cowmilk under light stroage at 30℃ for 8 hrs 57
Table 1-22. Effect of methylene blue on the pH of cowmilk under light stroage at 30℃ for 8 hrs 58
Table 1-23. Effect of Anthocyanin on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 60
Table 1-24. Effect of anthocyanin on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 61
Table 1-25. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 62
Table 1-26. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 63
Table 1-27. Effect of anthocyanin on the lightness value of cowmilk under light storage at 4℃ for 8 hrs 64
Table 1-28. Effect of anthocyanin on the redness value of cowmilk under light storage at 4℃ for 8 hrs 65
Table 1-29. Effect of anthocyanin on the yellowness value of cowmilk under light storage at 4℃ for 8 hrs 66
Table 1-30. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 68
Table 1-31. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 2000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 69
Table 1-32. Effect of anthocyanin on the lightness value of manufactured soymilk under light storage at 4℃ for 8 hrs 71
Table 1-33. Effects of anthocyanin on the redness value of manufactured soymilk under light storage at 4℃ for 8 hrs 72
Table 1-34. Effects of anthocyanin on the yellowness value of manufactured soymilk under light storage at 4℃ for 8 hrs 73
Table 1-35. Effect of ascorbic acid on the headspace oxygen of soymilk, cowmilk, skim milk, manufactured soymilk containing 5 ppm riboflavin under light storage at 4℃ for 8 hrs 75
Table 1-36. Area value of soymilk containing 1000 ppm antioxidant by Gas chromatography 78
Table 2-1. Effects of different meoru juice fractions on on the rubrene oxidation induced by signlet oxygen in a micro-emulsion system of H₂O₂/MoO₄²-(이미지참조) 95
Table 2-2/2. Identification of anthocyanins in Oll-Meoru and Neut-Meoru grape juices 105
Table 2-3/3. Identification of anthocyanins in Muscat Bailey A grape juice 107
Table 2-4/4. Identification of anthocyanins in Campbell Early grape juice 109
Table 2-5/5. Contents of anthocyanins in different grape juices 111
Table 2-6/5. Effects of cyanidin 3-glucoside and ascorbic acid on the rubrene oxidation induced by signlet oxygen in a micro-emulsion sysem of H₂O₂/MoO₄²-(이미지참조) 113
Table 3-1. Gradient program for anthocyanin determination 119
Table 3-2. Regression analysis between anthocyanin content and heating time of strawberry jam with different sugars under light 127
Table 3-3. Regression analysis between anthocyanin retention and illumination time of low sucrose wild vine jam during manufacturing 135
Table 3-4. Regression analysis between anthocyanin retention and illumination time of low glucose wild vine jam during manufacturing 137
Fig. 1-1. Extraction and purification of anthocyanins from mulberry and wild grape 24
Fig. 1-2. Purification of anthocyanin from wild grape and mulberry 25
Fig. 1-3. ORAC kinetic assay methods 27
Fig. 1-4. Outlined process for the preparation of soymilk 28
Fig. 1-5. Absorption spectra of fraction in the purified anthocyanin of wild grape 31
Fig. 1-6. Color change of wild grape at pHs 32
Fig. 1-7. Color change of mulberry at pHs 32
Fig. 1-8. HPLC chromatogram of anthocyanin standards... 34
Fig. 1-9. HPLC chromatogram of wild obtain of column chromatography... 35
Fig. 1-10. HPLC chromagogram of mulberry... 35
Fig. 1-11. Trolox standards curve 36
Fig. 1-12. Effect of soymilk volume on the headspace oxygen of soymilk under light storage at 4℃ for 8 hrs 38
Fig. 1-13. Effect of soymilk volume on the headspace oxygen of soymilk under light storage at 30℃ for 8 hrs 39
Fig. 1-14. Effect of methylene blue on the headspace oxygen of soymilk under light storage at 4℃ for 8 hrs 40
Fig. 1-15. Effect of methlene blue on the pH of soymilk under light storage at 4℃ for 8 hrs 41
Fig. 1-16. Effect of methlene blue on the headspace oxygen of soymilk under light storage at 30℃ for 8 hrs 42
Fig. 1-17. Effect of methlene blue on the pH of soymilk under light storage at 30℃ for 8 hrs 43
Fig. 1-18. Effect of anthocyanin on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 45
Fig. 1-19. Effect of anthocyanin on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 46
Fig. 1-20. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 47
Fig. 1-21. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 48
Fig. 1-22. Effect of anthocyanin on the lightness value of soymilk under light stroage at 4℃ for 8 hrs 49
Fig. 1-23. Effect of anthocyanin on the redness value of soymilk under light stroage at 4℃ for 8 hrs 50
Fig. 1-24. Effect of anthocyanin on the yellowness value of soymilk under light stroage at 4℃ for 8 hrs 51
Fig. 1-25. Effect of existence and nonexistence anthocyanin in soymilk... 52
Fig. 1-26. Effect of cowmilk volume on the headspace oxygen of cowmilk under light stroage at 4℃ for 8 hrs 53
Fig. 1-27. Effect of cowmilk volume on the headspace oxygen of cowmilk under light stroage at 30℃ for 8 hrs 54
Fig. 1-28. Effect of methylene blue on the headspace oxygen of cowmilk under light stroage at 4℃ for 8 hrs 56
Fig. 1-29. Effect of methylene blue on the headspace oxygen of cowmilk under light stroage at 4℃ for 8 hrs 57
Fig. 1-30. Effect of methylene blue on the headspace oxygen of cowmilk under light stroage at 30℃ for 8 hrs 58
Fig. 1-31. Effect of methylene blue on the pH of cowmilk under light stroage at 30℃ for 8 hrs 59
Fig. 1-32. Effect of anthocyanin on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 60
Fig. 1-33. Effect of anthocyanin on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 61
Fig. 1-34. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 62
Fig. 1-35. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of cowmilk containing 100 ppm methylene blue under light storage at 30℃ for 8 hrs 63
Fig. 1-36. Effect of anthocyanin on the lightness value of cowmilk under light storage at 4℃ for 8 hrs 65
Fig. 1-37. Effect of anthocyanin on the redness value of cowmilk under light storage at 4℃ for 8 hrs 66
Fig. 1-38. Effect of anthocyanin on the yellowness value of cowmilk under light storage at 4℃ for 8 hrs 67
Fig. 1-39. Difference of existence and nonexistence anthocyanin in cowmilk... 67
Fig. 1-40. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 1000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 69
Fig. 1-41. Effect of α-tocopherol, δ-tocopherol, anthocyanin and β-carotene 2000 ppm on the headspace oxygen of soymilk containing 100 ppm methylene blue under light storage at 4℃ for 8 hrs 70
Fig. 1-42. Effect of anthocyanin on the lightness value of manufactured soymilk under light storage at 4℃ for 8 hrs 71
Fig. 1-43. Effect of anthocyanin on the redness value of manufactured soymilk under light storage at 4℃ for 8 hrs 72
Fig. 1-44. Effects of anthocyanin on the yellowness value of manufactured soymilk under lights storage at 4℃ for 8 hrs 73
Fig. 1-45. Difference of existence and nonexistence anthocyanin in manufactured soymilk.... 74
Fig. 1-46. Effect of ascorbic acid on the headspace oxygen of (A) soymilk, (B) cowmilk, (C) skim milk, (D) manufactured soymilk containing 5 ppm riboflavin under light storage at 4℃ for 8 hrs 76
Fig. 1-47. Effect of ascorbic acid 1000 ppm on the headspace oxygen of soymilk, cowmilk, skim milk, manufactured soymilk containing 5 ppm riboflavin under light sotrage at 4℃ for 8 hrs 77
Fig. 1-48. Gas chromatography chromatogram of soymilk flavor 79
Fig. 1-49. Gas chromatorgraphy chromatogram of flavor standards... 79
Fig. 2-1. Effects of various vegetable and fruit juices on the singlet oxygen rubrene peroxidation induced by hydrogen peroxide-sodium molybdate in anw/0 microemulsion.... 84
Fig. 2-2. ASTS radical scavenging activity (ug vitamin C/ml) of various vegetable and fruit juices.... 85
Fig. 2-3. Total anthocyanin contents in various vegetable and fruit juices (refer to Fig 2-1 for the identities of juice samples) 86
Fig. 2-4. Total pheonlic contents in various vegetable and fruit juices (refer to Fig 2-1 for the identities of juice samples) 86
Fig. 2-5. Correlation between total anthocyanin versus inhibition of rubrene oxidation of juices 87
Fig. 2-6. Effects of grape juice (1%) on the lipid hydroperoxide formation in milk after 36 hr light illumination at 5℃. 88
Fig. 2-7. The GC chromatogram of volatile compounds formed in milk after 60 hr light illumination... 88
Fig. 2-8. Effects of grape juice (1%) on the hexanal formation in milk after 36 hr light illumination at 5℃. 89
Fig. 2-9. Effects of meoru juice on the self-sensitized photodecomposition during light illumination 90
Fig. 2-10. Effects of different amount of meoru juice on the lipid hydrogen peroxide formation in milks during light illumination 91
Fig. 2-11. Effects of different amount of meoru juice on the hexanal formation in milks during light illumination 91
Fig. 2-12. Effects of different amount of meoru juice on the tocopherol decomposition in milks during light illumination 92
Fig. 2-13. Comparison of meoru juice and ascorbic acid activities on the lipid hydroperoxide formation in milks after 36 hr light illumination 93
Fig. 2-14. Comparison of meoru juice and ascorbic acid activities on the hexanal formation in mklks after 36 hr light illumination 93
Fig. 2-15. Comparison of meoru juice and ascorbic acid activities on the tocopherol loss in milks after 36 hr light illumination 94
Fig. 2-16. Effects of different amount of meoru juice and ascorbic acid on the ESR spectra in methylene blue-TMPD system after light illumination. 95
Fig. 2-17. Effects of active Fraction (ARF) of Meoru juice on the lipid hydroperoxide formation in milk during light illumination 96
Fig. 2-18. The GC chromatorgrams for volatile compounds in the non-treated milk (top) and milks treated with 0.01% meoru juice active fraction (middle) and with 0.01% ascorbic acid (bottom) after 60hr light illumination at 5℃.... 97
Fig. 2-19. Effects of active Fraction (ARF) of Meoru juice on the hexanal formation in milk during light illumination 98
Fig. 2-20. Effects of active Fraction (ARF) of Meoru juice on the tocopherol loss in milk during light illumination 99
Fig. 2-21. HPLC chromatogram of anthocyanins in Oll-Meoru grape juice performed at 20℃ column oven temperature 99
Fig. 2-22. HPLC chromatograms of anthocyanins in Oll-Meoru grape juice performed at different column oven temperature. 100
Fig. 2-23. HPLC chromatograms of anthocyanins in Oll-Meoru and Neut-Meoru grape juices perfomed at 35℃ column oven temperature. 101
Fig. 2-24. Spectra of MS (A), MS/MS (B), and UV-Visible scanning (C) of peak 1 in HPLC chromatogram of Meoru grape juices. 103
Fig. 2-25. Chemical structure of peak 1 in HPLC chromatogram of Meoru grape juices 103
Fig. 2-26. Spectra of MS (A), MS/MS (B), and UV-Visible scanning (C) of peak 3 in HPLC chromatograms of Meoru grape juice. 104
Fig. 2-27. Chemical structure of peak 3 in HPLC chromagogram of Meoru grape juices 104
Figure 2-28. HPLC chromatogram of anthocyanins in Muscat Bailey A grape juice performed at 35℃ column oven temperature. 106
Figure 2-29. Spectra of MS (A), MS/MS (B), and UV-Visible scanning (C) of peak 10 in HPLC chromagograms of Muscat Bailey A grape juice. 106
Figure 2-30. HPLC chromatogram of anthocyanins in Campbell Early grape juice performed at 35℃ column oven temperature. 108
Figure 2-31. Spectra of MS (A), MS/MS (B), and UV-Visible scanning (C) of peak 13 in HPLC chromatograms of Campbell Early grape juice. 108
Figure 2-32. The chemical structure of cyanidin 3-(p-coumaroyl) glucoside 5-glucoside with its MS and MS/MS spectra pattern 109
Figure 2-33. ESR spectra of TAN radical after light illumination of a TMPO-methylene blue solution as affected by cyanidin 3-glucoside and ascorbic acid 112
Figure 3-1. Light box for singlet oxygen generation 116
Figure 3-2. Apparatus for strawberry jam manufacturing with singlet oxygen generation 117
Figure 3-3. Riboflavin changes during storage under light at 4℃ 120
Figure 3-4. Sodium azide degradation 121
Figure 3-5. Anthocyanin degradation upon storage under light at 4℃ 122
Figure 3-6. HPLC chromatogram of strawberry anthocyanins... 123
Figure 3-7. Effects of processing temperature on the stability of anthocyanin in strawberry jam made with sucrose under light 124
Figure 3-8. Effects of processing temperature on the stability of anthocyanin in strawberry jam made with glucose under light 124
Figure 3-9. Effects of processing temperature on the stability of anthocyanin in strawberry jam made with fructose under light 125
Figure 3-10. Effects of sugars on the anthocyanin contents during manufacturing strawberry jam at 60℃ 126
Figure 3-11. HPLC chromatogram of wild vine anthocyanins... 128
Figure 3-12. Anthocyanin degradation upon storage under light at 4℃ 129
Figure 3-13. Effects of 1.89 M of sugars on the viscosity (dPa·s) of wild vine jam manufactured at 90℃ 130
Figure 3-14. Effects of sucrose concentration on the viscosity (dPa·s) of wild vine jam manufactured at 90℃ 131
Figure 3-15. Effects of heating temperature on the viscosity (dPa·s) of wild vine jam manufactured with 2.92 M sucrose 132
Figure 3-16. Effects of pectin on the viscosity of low sugars wild vine jam by 50% of the control when manufactured at 90℃ for 3 hr, A: sucrose-added jam, B: glucose-added jam, C: fructose-added jam... 134
Figure 3-17. Content changes (A) and retention changes (B) of anthocyanins in low sucrose-added wild vine jam during manufacturing under light 135
Figure 3-18. Content changes (A) and retention changes (B) of anthocyanins in low glucose-added wild vine jam during manufacturing under light 136
Figure 3-19. Content changes (A) and retention changes (B) of anthocyanins in low fructose-added wild vine jam during manufacturing under light 137
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